Na+/K+ ATPase α1 and ß3 subunits are localized to the basolateral membrane of trophectoderm cells in human blastocysts.

STUDY QUESTION: Is there a relation between specific Na+/K+ ATPase isoform expression and localization in human blastocysts and the developmental behavior of the embryo? SUMMARY ANSWER: Na+/K+ ATPase α1, ß1 and ß3 are the main isoforms expressed in human blastocysts and no association was found between the expression level of their respective mRNAs and the rate of blastocyst expansion. WHAT IS KNOWN ALREADY: In mouse embryos, Na+/K+ ATPase α1 and ß1 are expressed in the basolateral membrane of trophectoderm (TE) cells and are believed to be involved in blastocoel formation (cavitation). STUDY DESIGN, SIZE, DURATION: A total of 20 surplus embryos from 11 patients who underwent IVF and embryo transfer at a university hospital between 2009 and 2018 were analyzed. PARTICIPANTS/MATERIALS, SETTING, METHODS: After freezing and thawing Day 5 human blastocysts, their developmental behavior was observed for 24 h using time-lapse imaging, and the expression of Na+/K+ ATPase isoforms was examined using quantitative RT-PCR (RT-qPCR). The expressed isoforms were then localized in blastocysts using fluorescent immunostaining. MAIN RESULTS AND THE ROLE OF CHANCE: RT-qPCR results demonstrated the expression of Na+/K+ ATPase α1, ß1 and ß3 isoforms in human blastocysts. Isoforms α1 and ß3 were localized to the basolateral membrane of TE cells, and ß1 was localized between TE cells. A high level of ß3 mRNA expression correlated with easier hatching (P = 0.0261). LARGE SCALE DATA: N/A. LIMITATIONS, REASONS FOR CAUTION: The expression of mRNA and the localization of proteins of interest were verified, but we have not been able to perform functional analysis. WIDER IMPLICATIONS OF THE FINDINGS: Of the various Na+/K+ ATPase isoforms, expression levels of the α1, ß1 and ß3 mRNAs were clearly higher than other isoforms in human blastocysts. Since α1 and ß3 were localized to the basolateral membrane via fluorescent immunostaining, we believe that these subunits contribute to the dilation of the blastocoel. The ß1 isoform is localized between TE cells and may be involved in tight junction formation, as previously reported in mouse embryos. STUDY FUNDING/COMPETING INTEREST(S): This work was supported by the JSPS KAKENHI (https://www.jsps.go.jp/english/index.html), grant number 17K11215. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript. The authors have no conflicts of interest.

Enhanced photocatalytic performance of ultrasound treated GO/TiO2 composite for photocatalytic degradation of salicylic acid under sunlight illumination.

The current research work deals with the preparation of TiO2 and GO/TiO2 composite by simple, chemical, cost effective hydrothermal method. Graphene oxide (GO) is prepared by modified Hummer's method. Dispersion of GO is achieved by an ultrasonic cleaning bath for 1 h. using a power of 200 W and at a frequency of 40 kHz. The prepared catalyst material is characterized by different characterization techniques. XRD study confirms the prepared material is polycrystalline in nature. The synthesized TiO2 and GO/TiO2 photocatalyst materials are used to study the photocatalytic degradation of salicylic acid under sunlight illumination. GO/TiO2 composite shows superior photocatalytic activity than TiO2. GO/TiO2 composite shows 57% degradation of salicylic acid. Mineralization of salicylic acid is studied using chemical oxygen demand.

Pt-free solar driven photoelectrochemical hydrogen fuel generation using 1T MoS2 co-catalyst assembled CdS QDs/TiO2 photoelectrode.

The solar-to-hydrogen generation from the TiO2-CdS-ZnS-MoS2 (TCZM) heterointerface was demonstrated. We found that a Pt-free CdS quantum dot-sensitized TiO2 mesoporous electrode with a metallic-type 1T MoS2 co-catalyst resulted in 0.11 ml cm(-2) h(-1) H2 fuel generation in unassisted potential mode, which was strikingly improved to 1.47 ml cm(-2) h(-1) under 1 V applied potential.

Enhanced photocatalytic performance at a Au/N-TiO2 hollow nanowire array by a combination of light scattering and reduced recombination.

We demonstrate one-step gold nanoparticle (AuNP) coating and the surface nitridation of TiO2 nanowires (TiO2-NWs) to amplify visible-light photon reflection. The surface nitridation of TiO2-NW arrays maximizes the anchoring of AuNPs, and the subsequent reduction of the band gap energy from 3.26 eV to 2.69 eV affords visible-light activity. The finite-difference time-domain (FDTD) simulation method clearly exhibits the enhancement in the strengths of localized electric fields between AuNPs and the nanowires, which significantly improves the photocatalytic (PC) performance. Both nitridation and AuNP decoration of TiO2-NWs result in beneficial effects of high (e(-)/h(+)) pair separation through healing of the oxygen vacancies. The combined effect of harvesting visible-light photons and reducing recombination in Au/N-doped TiO2-NWs promotes the photocatalytic activity towards degradation of methyl orange to an unprecedented level, ∼4 fold (1.1 × 10(-2) min) more than does TiO2-NWs (2.9 × 10(-3) min(-1)). The proposed AuNP decoration of nitridated TiO2-NW surfaces can be applied to a wide range of n-type metal oxides for photoanodes in photocatalytic applications.

Synergistic metal-metal oxide nanoparticles supported electrocatalytic graphene for improved photoelectrochemical glucose oxidation.

We report the fabrication of graphene-WO3-Au hybrid membranes and evaluate their photocatalytic activity towards glucose oxidase mediated enzymatic glucose oxidation. The dual-functionality of gold nanoparticles in the reinforcement of visible light activity of graphene-WO3 membranes and improving the catalytic activity of immobilized enzymes for unique photoelectrochemical sensing application is demonstrated. This work provides new insights into the fabrication of light-sensitive hybrid materials and facilitates their application in future.

Activity and selectivity of photocatalysts in photodegradation of phenols.

Photodegradation of phenol and 4-chlorophenol over six different TiO(2) samples was tested in order to establish whether an interconnection between the activity and selectivity of photocatalysts exists. The obtained experimental data were analyzed using correlation analysis. Some correlations between the activity in phenol(s) photodegradation and selectivity toward formation of primary intermediate products were established. The type of correlations depends on the type of studied photoreactions. The discussion of the observed correlations between the activity and selectivity of photocatalysts is given in terms of the difference of surface concentrations of electrons and holes and corresponding surface active sites which might be dependent on the types of dominating surface faces. On the basis of the obtained results of correlation analysis it was assumed that a higher activity of photocatalysts could be achieved provided that both reduction and oxidation reaction pathways occur with equally high efficiency.

Recurrent atrial fibrillation after high-dose methylprednisolone therapy in a girl with lupus-associated hemophagocytic syndrome.

Hemophagocytic syndrome (HPS) is a serious complication of systemic lupus erythematosus (SLE). A 15-year-old female with lupus-nephritis developed HPS. Bone marrow study showed florid thrombophagocytosis. There was no associated infection. High-dose methylprednisolone therapy ameliorated HPS. However, atrial fibrillation (Af) repeated after the infusion and required direct-current cardioversion. No underlying diseases were found in the heart and endocrine system. Chest roentgenogram and echocardiography were normal. Electrocardiogram showed slightly prolonged PR interval in sinus rhythm. Af occurred at high circulating levels of interferon-γ and interleukin (IL)-10, but not IL-6, IL-2, tumor necrosis factor-α, C-reactive protein or catecholamines. This is the first observation that high-dose corticosteroid induced Af in a case of lupus-HPS. Af is unusual in SLE children without cardiac disease, while conduction defect occurs associated with lupus-myocarditis. Lupus-HPS may be an aggressive SLE subset with cardiac involvement. High-dose corticosteroid infusion controls lupus activity, but could disclose the cardiac stress in lupus-HPS patients.

Safety studies of LP20 powder produced from heat-killed Lactobacillus plantarum L-137.

The safety of LP20 and its prototype, a powder, with potential use in food, produced from a mixture of dextrin and heat-killed Lactobacillus plantarum L-137, was assessed in an acute study in mice, and in an in vitro bacterial reverse mutation assay, an in vitro chromosome aberration assay, and an in vivo mouse micronucleus assay. LP20 prototype was not acutely toxic when administered to male and female Slc:ICR mice by single gavage at 2000mg/kg bw. Dosing was not associated with mortality, clinical signs, changes in bodyweight, or macroscopic abnormalities. The LD(50) in mice was greater than 2000mg/kg bw. There was no evidence of genotoxicity of LP20 in the Ames assay (0-5000microg/plate) or in the in vitro chromosome aberration assay with Chinese hamster lung fibroblasts (0-5000microg/mL). Administration of two consecutive daily doses of 500, 1000, or 2000mg/kg bw by gavage to male Crlj:CD-1 mice was not associated with an increased incidence of micronuclei and did not alter the ratio of polychromatic to normochromatic erythrocytes. These studies show that LP20 powder is not acutely toxic and is without genotoxic activity both in vitro and in vivo.

Cooperation of phosphate monomer and silica modification on zirconia.

Ceramic restorations with resin-based adhesive systems have been the focus of recent attention in clinical dentistry. Yttrium-oxide-partially-stabilized zirconia (YPSZ) ceramics have optimized physical properties and exhibit favorable fracture toughness, though their bonding properties are problematic. Although functional phosphate monomers and silica-coating by tribochemical modification were expected to improve the bonding properties between YPSZ ceramics and resin-based adhesives, these two methods remain controversial. This study evaluated the efficiency of silica-coating by tribochemical modification of YPSZ ceramics. The application of phosphate monomer and a silane coupling agent on silica-coated YPSZ was also investigated. The silica-coating of YPSZ ceramics by tribochemical modification was not efficient, given the higher mechanical toughness of the densely sintered ceramics. Stable shear bond strength was achieved on silica-coated YPSZ ceramics with the cooperative interaction of phosphate monomer and silane coupling.

Application of a "black body" like reactor for measurements of quantum yields of photochemical reactions in heterogeneous systems.

We report for the first time an experimental application of the concept of a "black body" like reactor to measure quantum yields (Phi) of photochemical reactions in liquid-solid heterogeneous systems. A major advantage of this new method is its simplicity since the fractions of reflected and transmitted light are negligible due to reactor geometry and high optical density of the heterogeneous systems. The average quantum yield of a test reaction (phenol photodegradation) over TiO(2) (Degussa P25) as determined by this method was 0.14, identical to the quantum yield measured earlier for this same reaction under similar conditions by Salinaro and Serpone. We also report the quantum yield of phenol photodegradation over N-doped TiO(2) during photoexcitation at the fundamental absorption band (lambda = 365 nm; Phi = 0.12) and at the N-doping induced extrinsic absorption band (lambda = 436 nm; Phi = 0.08) of the photocatalyst.

An alternative ionic liquid based electrolyte for dye-sensitized solar cells.

An ionic liquid based, environmentally friendly electrolyte LiI(C(2)H(5)OH)(4)-I(2) was used as the electrolyte to fabricate dye-sensitized solar cells (DSSC) with energy conversion efficiency of 4.9% under AM 1.5 (100 mW cm(-2)) irradiation.

Electrochemical oxidation of underivatized-nucleic acids at highly boron-doped diamond electrodes.

Boron-doped diamond (BDD) electrodes have been examined for the electrochemical oxidation of underivatized-nucleic acids in terms of single stranded and double stranded DNA. Cyclic voltammetry and square wave voltammetry have been used to study the oxidation reactions and to detect DNA without derivatization or hydrolysis steps. At the diamond electrode, at least two well-defined voltammetric peaks were observed for both single stranded and double stranded DNA. Diamond electrode is the first material to show a well-defined voltammetric peaks for adenine group oxidation directly in the helix structure of nucleic acid due to its wide potential window. For single stranded DNA, a third peak, related to the pyrimidine group oxidation was also observed. As-deposited diamond film with predominantly hydrogen-terminated surface exhibited superior performance over oxygen-terminated diamond in terms of sensitivity. However, by optimizing the ionic strength, sensitivity of O-terminated films could be improved. Linear calibration results have shown linearity of current with concentration in the range 0.1-8 microg mL(-1) for both guanine and adenine residues at as-deposited BDD. Detection limits (S/N = 3) of 3.7 and 10 ng mL(-1) for adenine and guanine residue in single stranded DNA, respectively, and 5.2 and 10 ng mL(-1) for adenine and guanine residue in double stranded DNA, respectively, were observed. This work shows the promising use of diamond as an electrochemical detector for direct detection of nucleic acids. The results also show the possibility of using the oxidation peak current of adenine group that is more sensitive for the direct detection of nucleicacids.

Gradient liquid chromatography of leucine-enkephalin peptide and its metabolites with electrochemical detection using highly boron-doped diamond electrode.

Boron-doped diamond thin film (BDD) electrodes have been used to study the oxidation reactions and to detect leucine-enkephalinamide (LEA) and its metabolites, tyrosine (T), tyrosyl-alanine (TA), tyrosyl-alanine-glycine (TAG) and leucine-enkephalin (LE) using cyclic voltammetry (CV), flow-injection analysis (FIA), and gradient liquid chromatography (LC) with amperometric detection. At diamond electrodes, well-defined and highly reproducible cyclic voltammograms were obtained with signal-to-background (S/B) ratios 5-10 times higher than those observed for glassy carbon (GC) electrodes. The analytical peaks of LC for LEA and its metabolites were well resolved. No deactivation of BDD electrodes was found after several experiments with standard as well as plasma samples, indicating high stability of the electrode. Calibration curves were linear over a wide range from 0.06 to 30 microM with regression coefficients of 0.999 for all compounds. The limits of detection obtained based on a signal-to-noise ratio of 3:1 were 3, 2.2, 2.7, 20 and 11 nM for T, TA, TAG, LE and LEA, respectively. These values were at least one order lower than those obtained at GC electrodes, which has given limits of detection of 22.88, 20.64, 89.57, 116.04 and 75.67 for T, TA, TAG, LE and LEA, respectively. Application of this method to real samples was demonstrated and validated using rabbit serum samples. This work shows the promising use of conducting diamond as an amperometric detector in gradient LC, especially for the analysis of enkephalinamide and its metabolites.

Reversible valence tautomerism induced by a single-shot laser pulse in a cobalt-iron Prussian blue analog.

Reversible valence tautomeric conversion induced by a single-shot laser pulse (8 ns duration) with a photon excitation energy of 2.38 eV has been observed in Na0.36Co1.32Fe(CN)(6).5.6H(2)O. A photoswitching process with accompanying magnetization and color changes was successfully achieved within the pulse duration at high temperature (above 200 K) in a thermal hysteresis loop. This unusual photoeffect originates from an optical charge transfer between Fe and Co atoms and evolves due to a cooperative interaction among the local photoexcited sites.

Direct electrochemical oxidation of disulfides at anodically pretreated boron-doped diamond electrodes.

Anodically oxidized diamond electrodes have been used to oxidize disulfides, thiols, and methionine in aqueous acidic media and tested for amperometric detection of these compounds after chromatographic separation. Cyclic voltammetric signals for 1 mM glutathione disulfide (GSSG) were observed at 1.39 and 1.84 V vs SCE, the values being less positive than those of its as-deposited counterpart as well as glassy carbon electrode. The voltammetric and chronocoulometric results have indicated the high stability of the electrode with negligible adsorption. A positive shift in the peak potential with increasing pH indicated the attractive electrostatic interaction between the anodically oxidized diamond surface and the positively charged GSSG in acidic media that promoted its analytical performance. The results of the electrolysis experiments of disulfides and thiols showed that the oxidation reaction mechanism of glutathione (GSH) and GSSG involves oxygen transfer. Following separation by liquid chromatography (LC), the determination of both GSH and GSSG in rat whole blood was achieved at a constant potential (1.50 V vs Ag/AgCl), and the limits of detection for GSH and GSSG were found to be 1.4 nM (0.028 pmol) and 1.9 nM (0.037 pmol) with a linear calibration range up to 0.25 mM. These detection limits were much lower than those reported for the amperometry using Bi-PbO2 electrodes and LC-mass spectrometry, and the LC method using diamond electrodes were comparable with enzymatic assay in real sample analysis. The high response stability and reproducibility together with the possibility of regeneration of the electrode surface by on-line anodic treatment at 3 V for 30 min further support the applicability of anodically pretreated diamond for amperometric detection of disulfides.

The electrochemical oxidation of homocysteine at boron-doped diamond electrodes with application to HPLC amperometric detection.

The electrochemical oxidation of homocysteine was studied at as-deposited and anodized (oxidized) boron-doped diamond (BDD) thin film electrodes with cyclic voltammetry, flow injection analysis and high-pressure liquid chromatography with amperometric detection. At anodized boron-doped diamond electrodes, highly reproducible, well-defined cyclic voltammograms for homocysteine oxidation were obtained in acidic media, while as-deposited diamond did not provide a detectable signal. In alkaline media, however, the oxidation response was obtained both at as-deposited and anodized diamond electrodes. The potential sweep rate dependence of homocysteine oxidation (peak currents for 1 mM homocysteine linearly proportional to v(1/2), within the range of 0.01 to 0.3 V s(-1)) indicates that the oxidation involves a diffusing species, with negligible adsorption on the BDD surface at this concentration. In the flow system, BDD exhibited a highly reproducible amperometric response, with a peak variation less than 2%. An extremely low detection limit (1 nM) was obtained at 1.6 V vs. Ag/AgCl. In addition, the determination of homocysteine in a standard mixture with aminothiols and disulfide compounds by means of isocratic reverse-phase HPLC with amperometric detection at diamond electrodes has been investigated. The results showed excellent separation, with a detection limit of 1 pmol and a linear range of three orders of magnitude.

Electrochemical detection of carbamate pesticides at conductive diamond electrodes.

Conductive boron-doped diamond thin-film electrodes were used for the electrochemical detection of selected N-methylcarbamate pesticides (carbaryl, carbofuran, methyl 2-benzimidazolecarbamate, bendiocarb) after liquid chromatographic separation. Two kinds of detection methods were adopted in this study. In the first method, a direct detection of underivatized pesticides was carried out at an operating potential of 1.45 V versus Ag/AgCl, which resulted in the detection limits of 5-20 ng/mL (or 5-20 ppb) with S/N = 2 due to the low background current and wide potential window of the diamond electrode. In the second method, the detection limits were improved by subjecting the pesticide samples to alkaline hydrolysis in a separate step prior to injection. The phenolic derivatives obtained by alkaline hydrolysis oxidize at a relatively lower potential (0.9 V vs Ag/AgCl), which increases the sensitivity drastically. The advantage of the diamond electrode for the detection of phenolic derivatives is that it offers excellent stability in comparison to other electrodes. This method gives the detection limits of 0.6-1 ng/mL (or 0.6-1 ppb), which are well below the maximum residue levels allowed for carbaryl, carbofuran, and bendiocarb. While the lowest detection limits (LOD) obtained by the direct detection of pesticides are comparable to the those reported by the well-established HPLC-fluorescence, the LODs of the alkaline hydrolysis method are found to be even lower than the reported limits. On-line reactivation of the diamond electrode surface was shown to be possible by an anodic treatment of the electrode at approximately 3 V for 30 min in case of electrode fouling, which may occur after a prolonged use. Such a treatment damages the glassy carbon (GC) and metal electrodes, while the diamond electrode remains stable. These results suggest that the diamond electrode is superior to the other previously used electrodes such as GC and Kelgraf type for highly sensitive and stable detection of carbamate pesticides.

Electrochemical oxidation of chlorophenols at a boron-doped diamond electrode and their determination by high-performance liquid chromatography with amperometric detection.

Anodically pretreated diamond electrodes have been used for the detection of chlorophenols (CPs) in environmental water samples after high-performance liquid chromatographic (HPLC) separation. The anodization of as-deposited boron-doped polycrystalline diamond thin-film electrodes has enabled the stable determination of phenols over a wide concentration range. Prior to the HPLC analysis, a comparative study with ordinary glassy carbon, as-deposited diamond, and anodized diamond was made to examine the oxidative behavior of phenols by cyclic voltammety and flow injection analysis with amperometric detection. At anodized diamond electrodes, reproducible, well-defined cyclic voltammograms were obtained even at high CP concentration (5 mM), due to a low proclivity for adsorption of the oxidation products on the surface. In addition, after prolonged use, the partially deactivated diamond could be reactivated on line by applying a highly anodic potential (2.64 Vvs SCE) for 4 min, which enabled the destruction of the electrodeposited polymer deposits. Hydroxyl radicals produced by the high applied potential, in which oxygen evolution occurs, are believed to be responsible for the oxidation of the passivating layer on the surface. When coupled with flow injection analysis (FIA), anodized diamond exhibited excellent stability, with a response variability of 2.3% (n = 100), for the oxidation of a high concentration (5 mM) of chlorophenol. In contrast, glassy carbon exhibited a response variability of 39.1%. After 100 injections, the relative peak intensity, for diamond decreased by 10%, while a drastic decrease of 70% was observed for glassy carbon. The detection limit obtained in the FIA mode for 2,4-dichlorophenol was found to be 20 nM (S/N = 3), with a linear dynamic range up to 100 microM. By coupling with the column-switching technique, which enabled on-line preconcentration (50 times), the detection limit was lowered to 0.4 nM (S/N = 3). By use of this technique, anodized diamond electrodes were demonstrated for the analysis of CPs in drainwater that was condensed from the flue gas of waste incinerators.

Selective amperometric detection of dopamine using OPPy-modified diamond microsensor system.

Highly boron-doped diamond microfiber electrodes (BDDMF) were fabricated and characterized by the use of Scanning Electron Microscopy (SEM), Raman spectroscopy, and cyclic voltammetry. Amperometric detection of dopamine (DA), a neurotransmitter was achieved at pH 7.0, using BDDMF electrodes. The interferences from ascorbic acid (AA) and DOPAC were efficiently eliminated by using overoxidized polypyrrole-modified BDDMF electrodes, which also increased the sensitivity for the detection of dopamine. The limit of detection (S/N = 3) for dopamine was 0.1 nM, which is one order lower than that observed for carbon microfiber electrodes (CMFE), and the linear dynamic range was obtained from 0.5 nM to 100 microM (r2 = 0.997). The amperometric response for 0.5 nM dopamine has shown high stability with an RSD of 5.4% (n = 5). Highly reproducible results were obtained with an RSD of 6.2% for 10 measurements of 1 nM DA taken during 10 h and also remained the same, during measurements for 7 days, with no variation in efficiency for rejection of AA and DOPAC.

Iron(III) spin-crossover compounds with a wide apparent thermal hysteresis around room temperature.

The magnetic properties of the spin-crossover compounds, [Fe(qsal)2]NCSe-MeOH (1) and [Fe(qsal)2]NCSe-CH2Cl2 (2), have been measured. We have discovered that both compounds 1 and 2 exhibit a wide thermal hysteresis loop of 140 K (T(1/2) upward arrow = 352 K and T(1/2) downward arrow = 212 K) and 180 K (T(1/2) upward arrow = 392 K and T(1/2) downward arrow = 212 K), respectively, in the first cycle. Thermogravimetric analysis shows that solvent molecules escape from compounds 1 and 2 around 340 and 395 K, respectively. This means that the hysteresis loops observed for the first cycle are only apparent ones. Following the first loop, they show a two-step spin-crossover in warming mode. The so-called "step 1" and "step 2" are centered around T(1/2(S1)) upward arrow = 215 K and T(1/2(S2)) upward arrow = 282 K, respectively. On the other hand, a one-step spin-crossover occurs at T(1/2) downward arrow = 212 K in cooling mode. The hysteresis widths can be estimated to be 3 K (step 1) and 70 K (step 2), assuming that the widths in steps 1 and 2 are defined as the differences between T(1/2(S1)) upward arrow and T(1/2) downward arrow, and T(1/2(S2)) upward arrow and T(1/2) downward arrow, respectively. The hysteresis width of 70 K in step 2 is one of the widest values reported so far for spin-crossover complexes. It is thought that the cooperativity operating in the complexes arises mainly from the intermolecular pi interactions between quinoline and phenyl rings. Using a previously reported model, we are able to simulate the hysteresis loop with a two-step spin-crossover in warming mode and a one-step transition in cooling mode.