Copper-Based Two-Dimensional Metal-Organic Frameworks for Fenton-like Photocatalytic Degradation of Methylene Blue under UV and Sunlight Irradiation.

To efficiently degrade organic pollutants, photocatalysts must be effective under both ultraviolet (UV) radiation and sunlight. We synthesized a series of new metal-organic frameworks by using mild hydrothermal conditions. These frameworks incorporate three distinct bipyridyl ligands: pyrazine (pyr), 4,4'-bipyridine (bpy), and 1,2-bis(4-pyridyl)ethane (bpe). The resulting compounds are denoted as [Cu(pyz)(H2O)2MF6], [Cu(bpy)2(H2O)2]·MF6, and [Cu(bpe)2(H2O)2]·MF6·H2O [M = Zr (1, 3, and 5) and Hf (2, 4, and 6)]. All six compounds exhibited a two-dimensional crystal structure comprising infinitely nonintersecting linear chains. Compound 3 achieved 100% degradation of methylene blue (MB) after 8 min under UV irradiation and 100 min under natural sunlight in the presence of H2O2 as the electron acceptor. For compound 5, 100% MB degradation was achieved after 120 min under sunlight and 10 min under UV light. Moreover, reactive radical tests revealed that the dominant species involved in photocatalytic degradation are hydroxyl (•OH), superoxide radicals (•O2-), and photogenerated holes (h+). The photodegradation process followed pseudo-first-order kinetics, with photodegradation rate constants of 0.362 min-1 (0.039 min-1) for 3 and 0.316 min-1 (0.033 min-1) for 5 under UV (sunlight) irradiation. The developed photocatalysts with excellent activity and good recyclability are promising green catalysts for degrading organic pollutants during environmental decontamination.

Thermodynamic, Spectroscopic, and Structural Study on a Sodium Uranyl Tri-2-Methoxybenzoate Dodecahydrate Coordination Compound with Considerably Low Solubility in Acidic Conditions.

A spontaneous crystallization of an uranium(VI)-organic coordination compound with sodium and 2-methoxybenzoate (2-mba) was observed in acidic solutions, and the solubility product, molecular vibrations, crystal structure, thermal stability, and emission properties of the atypically low-soluble U(VI) complex (Na[UO2(2-mba)3]·12H2O(s)) were fully investigated for the first time. A long-term solubility experiment and speciation modeling gave a solubility product of log Ks,0 = -12.18 ± 0.02 (T = 25 °C and I = 0.1 M NaClO4), and vibrational analyses confirmed the overall molecular structure of complex and the frequencies of characteristic stretching motions of uranyl moiety as well. The crystal quality of Na[UO2(2-mba)3]·12H2O(s) was improved by a digestion method, and X-ray diffraction analysis of the single crystalline specimen verified that the newly studied uranyl-organic compound contains one-dimensional channels with a diameter of 20 Å along the [001] direction; the sodium and water molecules are arranged in the channel structures. In the coordination environment around uranyl, three aromatic carboxylates are symmetrically bound in the equatorial plane of uranyl coplanarily, and the unit [UO2(2-mba)3]- complexes are further extended along the plane to form the layered-morphologies. The three-dimensional packing of [UO2(2-mba)3]- anions is driven by the parallel-displaced π-stacking of aromatic rings with a centroid-centroid distance of 3.7 Å. Additional thermogravimetric analysis confirmed that the Na[UO2(2-mba)3]·12H2O(s) is stable up to 250 °C, and dehydration and release of the organic ligand were subsequently observed beyond that temperature. Photoluminescence spectrum of the Na[UO2(2-mba)3]·12H2O(s) clearly displayed the characteristic U(VI) emission, and a band spacing between the ground electronic states of U(VI) uranyl was evaluated to be 831 ± 14 cm-1. Such detailed characterization of the unique Na[UO2(2-mba)3]·12H2O(s) is advancing upon a systematic understanding of the structural effects of the aromatic model ligands on U(VI) complexation, with relevance to the environmental chemistry of U(VI) and crystal engineering for development of diverse uranyl-organic frameworks.

Selective removal of radioactive iodine from water using reusable Fe@Pt adsorbents.

Environmental damage from serious nuclear accidents should be urgently restored, which needs the removal of radioactive species. Radioactive iodine isotopes are particularly problematic for human health because they are released in large amounts and retain radioactivity for a substantial time. Herein, we prepare platinum-coated iron nanoparticles (Fe@Pt) as a highly selective and reusable adsorbent for iodine species, i.e., iodide (I-), iodine (I2), and methyl iodide (CH3I). Fe@Pt selectively separates iodine species from seawater and groundwater with a removal efficiency ≥ 99.8%. The maximum adsorption capacity for the iodine atom of all three iodine species was determined to be 25 mg/g. The magnetic properties of Fe@Pt allow for the facile recovery and reuse of Fe@Pt, which remains stable with high efficiency (97.5%) over 100 uses without structural and functional degradation in liquid media. Practical application to the removal of radioactive 129I and feasibility for scale-up using a 20 L system demonstrate that Fe@Pt can function as a reusable adsorbent for the selective removal of iodine species. This systematic procedure is a standard protocol for designing highly active adsorbents for the clean separation and removal of various chemical species dissolved in wastewater.

Structural and spectroscopic studies of spontaneously formed crystalline Eu(iii)-aliphatic dicarboxylates at room temperature.

Complexation of actinides and lanthanides with carboxylic organic ligands is a critical issue affecting radionuclide migration from deep geological disposal systems of spent nuclear fuel. A series of Eu(iii)-aliphatic dicarboxylate compounds, as chemical analogs of radioactive Am(iii) species, Eu2(Ox)3(H2O)6, Eu2(Mal)3(H2O)6, and Eu2(Suc)3(H2O)2, were synthesized and characterized using X-ray crystallography and time-resolved laser fluorescence spectroscopy to examine the ligand-dependent binding modes and the corresponding changes in spectroscopic properties. Powder X-ray crystallography results confirmed that all of the compounds presented a crystalline polymer structure with a trigonal prism square-face tricapped polyhedron geometry centered on Eu(iii) in a nine-coordinate environment involving nine oxygen atoms. This study captures the transition of the coordination modes of aliphatic dicarboxylate ligands from side-on to end-on binding as the carbon chain length increases. This transition is illustrated in malonate bindings involving a combination of side-on and end-on modes. Strongly enhanced luminescence, especially for the hypersensitive peak, indicates a low site symmetry in the formation of solid compounds. The number of remaining bound water molecules was estimated from the resultant increased luminescence lifetimes, which were in good agreement with crystal structures. The excitation-emission matrix spectra of these crystalline polymers suggest that Ox ligands promote the sensitized luminescence of Eu(iii), especially in the UV region. In the case of Mal and Suc ligands, charge transfer occurs in the opposite direction from Eu(iii) to the ligands under UV excitation, resulting in weaker luminescence.

KIn0.33IIITe0.67VITe2IVO7: Zirconolite-like Mixed-Valent Metal Oxide with a 3D Framework.

We provide the material synthesis method, crystal structure information, and characterization of a novel mixed-valent metal oxide KIn0.33IIITe0.67VITe2IVO7, closely related to zirconolite (CaZrTi2O7), a radioactive waste immobilized material, having a 3D framework. The reported metal oxide containing an alkali-metal cation (K+), main-group cation (In3+), tellurate, and tellurite has been synthesized as both single crystals and a pure polycrystalline phase through a hydrothermal synthesis method. Single-crystal X-ray diffraction indicates that KIn0.33Te2.67O7 crystallizing in the orthorhombic space group Cmcm (No. 63) reveals a 3D framework structure with a 1D channel consisting of Te/InO6 octahedra and TeO4 polyhedra. An interesting transition reaction from KIn0.33Te2.67O7 to KIn(TeO3)2 under hydrothermal conditions at 230 °C is discussed.

Interfacial properties of [Pt/Co/Pt] trilayers probed through magnetometry.

The magnetic and interface properties of [Pt/Co/Pt] were investigated. First, the magnetic properties were determined from the magnetic dead layer plots, in which the Co layer was considered as two distinct parts representing different magnetic properties. The two parts with low and high tCo ranges are close to and away from the top interface (Co/Pt), respectively. The part close to the top interface shows a smaller magnetization (M) value and nonlinear behavior. However, the other part shows a higher M value closer to the bulk value and a linear behavior. The nonlinear behavior of the M values of the low tCo range was converted to an impurity level using simple assumptions. The results showed the effect of the top Pt layer on the magnetic properties of the Co layer. The results clearly demonstrate that magnetometry could be utilized as a means to understand the interface quality of magnetic multilayer systems.

Synchrotron-based high-resolution photoemission spectroscopy study of ZIRLO cladding with H2O adsorption: Coverage and temperature dependence.

The coverage and temperature dependence of ZIRLO cladding with H2O adsorption are studied using synchrotron-based high-resolution photoemission spectroscopy (HRPES). Based on the analytical results of the Zr 3d, O 1 s, C 1 s, and Sn 3d HRPES profiles prior to H2O adsorption, we determine the surface compositions of O2-, hydroxyl OH-, chemisorbed H2O, zirconium carbide, adventitious carbon, Sn metal, and SnO2 in ZIRLO. When ZIRLO is exposed to H2O molecules, the relative proportion of zirconium metal decreases, whereas that of the total zirconium oxides increases, suggesting the reaction between H2O and the zirconium metal in ZIRLO. On annealing a sample with 1000 L H2O on ZIRLO at 300 °C, Zr2O3 and ZrO2 decompose, and oxygen diffuses into the bulk, thereby reducing the oxidation states of zirconium on the surface. Moreover, at this temperature, the excess H2O molecules on ZIRLO are thoroughly desorbed and tin element is diffused into the bulk in ZIRLO.

Tailoring of magnetic properties of giant magnetoresistance spin valves via insertion of ultrathin non-magnetic spacers between pinned and pinning layers.

The low-field sensitivity of a giant magnetoresistance (GMR) spin valve can be enhanced by tailoring the bias field of the free layer because this sensitivity and bias field are known to show a strong correlation. In this study, the free-layer bias field is reduced considerably to almost zero via the insertion of an ultrathin nonmagnetic spacer between the pinned layer and the pinning layer. The spacer promotes an increase in the density of Néel walls in the pinned layer. This increase, in turn, induces domain-wall-induced magnetostatic interactions of the free poles formed on the Néel walls inside the free and pinned layers. The magnetostatic interactions result in the formation of flux closures that act as pinning sites during the magnetization reversal process and stabilize the antiparallel magnetization state between the free layer and the pinned layer by suppressing the switching of the free layer from the antiparallel state to the parallel state. Furthermore, the spacer offers an additional advantage of increasing the GMR ratio by inducing a specular scattering effect at its top and bottom interfaces. A highly improved low-field sensitivity of 12.01 mV/mA·Oe is achieved in the sample with a Cu/Pt dual spacer.

Vapoluminescent Behavior and the Single-Crystal-to-Single-Crystal Transformations of Chloroform Solvates of [Au2 (µ-1,2-bis(diphenylarsino)ethane)2 ](AsF6 )2.

The mono- and di-chloroform solvates of [Au2 (µ-1,2-bis(diphenylarsino)ethane)2 ](AsF6 )2 undergo single-crystal-to-single-crystal transformations that result in gain (over 12 hours) or slow loss (over five years) of only one chloroform molecule. The change in solvation results in changes in the structure and luminescence of the digold cation. The cation consists of a pair of slightly bent As-Au-As units that are connected through the two bridging dpae ligands and by aurophilic interactions with Au⋅⋅⋅Au contacts of 3.05152(15) Šin the disolvate or 2.9570(5) Šin the monosolvate.

A very large perpendicular magnetic anisotropy in Pt/Co/MgO trilayers fabricated by controlling the MgO sputtering power and its thickness.

The perpendicular magnetic anisotropy (PMA) properties of Pt/Co/MgO trilayers are investigated as a function of the MgO sputtering power (PMgO) and its thickness (tMgO), both of which are important parameters affecting the degree of oxygen interpenetration into Co during sputtering. A strong PMA is achieved at small values of PMgO and tMgO, where the oxygen interpenetration into Co is expected to be small. The range of oxygen interpenetration is relatively extended in such a way that it affects both the Pt/Co and Co/MgO interfaces. The PMA properties of as-deposited samples are improved by post-annealing for temperatures up to 400 °C examined in this study, probably due to the diffusion of the interpenetrated oxygen atoms toward the Co/MgO interface. In a structure of Pt/Co (0.6 nm)/MgO (2 nm), which is fabricated at PMgO = 50 W and then annealed at 400 °C, a huge saturation field is achieved (over 40 kOe) indicating a very strong PMA. Between the two interfaces of Pt/Co and Co/MgO, the PMA is mainly due to the former in the as-deposited state, but the contribution of the latter increases with the increase in the annealing temperature.

Critical switching current density induced by spin Hall effect in magnetic structures with first- and second-order perpendicular magnetic anisotropy.

In this study, we derive analytical expressions for the critical switching current density induced by spin Hall effect in magnetic structures with the first- and second-order perpendicular magnetic anisotropy. We confirm the validity of the expressions by comparing the analytical results with those obtained from a macrospin simulation. Moreover, we find that for a particular thermal stability parameter, the switching current density can be minimized for a slightly positive second-order perpendicular magnetic anisotropy and the minimum switching current density can further be tuned using an external magnetic field. The analytical expressions are of considerable value in designing high-density magnetic random access memory and cryogenic memory.

Large variation of magnetic properties of amorphous Fe-Zr thin films with Ar pressure during sputtering.

A large change is observed in the magnetic properties of amorphous Fe-Zr thin films sputtered at different Ar pressures. The change depends on the composition of the alloys and at compositions near 60 at.% Fe, for example, the magnetisation measured at 10 kOe increases 30-fold with an increase in the Ar pressure from 2 to 10 mTorr. The magnetic properties are well explained by a combination of two phenomena-superparamagnetism and spin glass behaviours-and the large change is partly related to the number density of a magnetically correlated region. Examinations of the microstructure by X-ray diffraction, transmission electron microscopy, and X-ray absorption fine structure spectroscopy reveal no appreciable difference in it as a function of the Ar pressure. This indicates that even a very slight change in the microstructure can greatly affect the magnetic properties of amorphous Fe-Zr thin films, thereby opening up the possibility of employing the magnetic properties of amorphous alloys for the characterisation of amorphous microstructures.

Anesthetic management during surgery for left ventricular aneurysm and false aneurysm occurring in stage: a case report.

Left ventricular aneurysm (LVA) and false aneurysm are complications of acute myocardial infarction, trauma, and cardiac surgery. Left ventricular false aneurysm (LVFA) is a particularly catastrophic complication owing to its high propensity for rupture. Surgical resection should be considered for LVFA occurring within three months after myocardial infarction or development of congestive heart failure. In this report, we describe a case of acute heart failure with LVA and LVFA occurring in stage as a complication of myocardial infarction in a 55-year-old man. The patient was also at risk of brain ischemia due to abnormal vessel status and a previous cerebrovascular accident with left-sided weakness. Successful perioperative anesthetic management was achieved by focusing on maintaining marginal upper normal blood pressure to ensure cerebral perfusion and to reduce the risk of false aneurysm rupture.

Single-port thoracoscopic surgery for pneumothorax under two-lung ventilation with carbon dioxide insufflation.

BACKGROUND: The development of single-port thoracoscopic surgery and two-lung ventilation reduced the invasiveness of minor thoracic surgery. This study aimed to evaluate the feasibility and safety of single-port thoracoscopic bleb resection for primary spontaneous pneumothorax using two-lung ventilation with carbon dioxide insufflation. METHODS: Between February 2009 and May 2014, 130 patients underwent single-port thoracoscopic bleb resection under two-lung ventilation with carbon dioxide insufflation. Access was gained using a commercial multiple-access single port through a 2.5-cm incision; carbon dioxide gas was insufflated through a port channel. A 5-mm thoracoscope, articulating endoscopic devices, and flexible endoscopic staplers were introduced through a multiple-access single port for bulla resection. RESULTS: The mean time from endotracheal intubation to incision was 29.2±7.8 minutes, the mean operative time was 30.9±8.2 minutes, and the mean total anesthetic time was 75.5±14.4 minutes. There were no anesthesia-related complications or wound problems. The chest drain was removed after a mean of 3.7±1.4 days and patients were discharged without complications 4.8±1.5 days from the operative day. During a mean 7.5±10.1 months of follow-up, there were five recurrences (3.8%) in operated thorax. CONCLUSIONS: The anesthetic strategy of single-lumen intubation with carbon dioxide gas insufflation can be a safe and feasible option for single-port thoracoscopic bulla resection as it represents the least invasive surgical option with the potential advantages of reducing operative time and one-lung ventilation-related complications without diminishing surgical outcomes.

Formation of Magnetic Anisotropy by Lithography.

Artificial interface anisotropy is demonstrated in alternating Co/Pt and Co/Pd stripe patterns, providing a means of forming magnetic anisotropy using lithography. In-plane hysteresis loops measured along two principal directions are explained in depth by two competing shape and interface anisotropies, thus confirming the formation of interface anisotropy at the Co/Pt and Co/Pd interfaces of the stripe patterns. The measured interface anisotropy energies, which are in the range of 0.2-0.3 erg/cm(2) for both stripes, are smaller than those observed in conventional multilayers, indicating a decrease in smoothness of the interfaces when formed by lithography. The demonstration of interface anisotropy in the Co/Pt and Co/Pd stripe patterns is of significant practical importance, because this setup makes it possible to form anisotropy using lithography and to modulate its strength by controlling the pattern width. Furthermore, this makes it possible to form more complex interface anisotropy by fabricating two-dimensional patterns. These artificial anisotropies are expected to open up new device applications such as multilevel bits using in-plane magnetoresistive thin-film structures.

Optimal Respiratory Rate for Low-Tidal Volume and Two-Lung Ventilation in Thoracoscopic Bleb Resection.

OBJECTIVES: One-lung ventilation is considered to be mandatory in video-assisted thoracoscopic surgery. However, the authors showed in a previous report that two-lung ventilation with low tidal volume is feasible in thoracoscopic bleb resection (TBR). In this study, they evaluated optimal respiratory rate during TBR under two-lung ventilation with low-tidal volume anesthesia. DESIGN: A prospective, randomized, single-blinded intervention study. SETTING: An operating room in a teaching hospital. PARTICIPANTS: Forty-eight patients who underwent scheduled TBR under general anesthesia. INTERVENTIONS: TBR was performed under low-tidal-volume (5 mL/kg), two-lung ventilation. Respiratory rate (RR) varied according to the protocol: 15 (group I), 18 (group II), and 22 cycles/min (group III). Using block randomization method, 16 patients were assigned to each of 3 groups. MEASUREMENTS AND MAIN RESULTS: Minute ventilation of group I was lowered significantly compared with the other groups (p<0.001). The results of arterial blood gas analysis were in the physiologic range in all patients. Surgery and anesthetic times and number of endostaples used were not significantly different among the 3 groups. CONCLUSIONS: The RR of 15 cycles/min with low-tidal volume (5 mL/kg) and two-lung ventilation did not produce abnormal physiologic changes including arterial pH, partial arterial oxygen pressure, and partial pressure of carbon dioxide and guaranteed an optimal surgical field. Therefore, these setting are considered acceptable for two-lung ventilation during TBR.

Management of traumatic pneumothorax with massive air leakage: role of a bronchial blocker: a case report.

Massive air leakage through a lacerated lung produces inadequate ventilation and hypoxemia. Tube exchange from a single to double lumen endotracheal tube (DLT), and lung separation to maintain oxygenation, are challenging for seriously injured patients. In this case report, we aim to describe how a bronchial blocker (BB) makes it easier to perform a lung separation in this situation; it also increases the overall safety of the procedure. A 35-year-old female (163 cm, 47 kg) suffered from blunt chest trauma due to a traffic accident; the accident caused right-sided lung laceration with massive air leakage. Paradoxically, positive ventilation worsened SaO2 and leakage increased through a chest tube. We introduced BB while the patient was still awake: Left-side one-lung ventilation (OLV) was established and anesthesia was induced. After PaO2 was maximized with OLV, we changed the endotracheal tube to DLT without a hypoxic event. By BB placement, we maintained PaO2 at a secure level, conducted mechanical ventilation and exchanged the tube without deterioration.

Formation and structure of two luminescent salts of [Au(SCSN3)2]- obtained through the [2 + 3] cyclization of carbon disulfide and azide ion.

The colorless, two-coordinate gold(i) complex, [(H2O)3Na][Au(SCSN3)2], has been synthesized through the [2 + 3] cyclic reaction of carbon disulfide and sodium azide in the presence of the labile complex (tht)AuCl. Metathesis of [(H2O)3Na][Au(SCSN3)2], with tetra(phenyl)arsonium chloride produced colorless needles of (Ph4As)[Au(SCSN3)2]. The structure of [(H2O)3Na][Au(SCSN3)2] involves linear gold coordination by two exocyclic sulfur atoms of the 1,2,3,4-thiatriazole-5-thiolate anions. These two-coordinate anions self-associate to form extended, zig-zag chains that are connected by aurophilic bonding with Au∙∙∙Au distances of 3.2653(3) Å and 3.3090(3) Å. Remarkably, the individual S-Au-S units that are connected though aurophilic interactions are eclipsed. The structure of (Ph4As)[Au(SCSN3)2] also contains linear, two-coordinate gold ions with bonding to the 1,2,3,4-thiatriazole-5-thiolate anionic ligands through the exocyclic sulfur atoms. However, in this salt, the anions self-associate through AuAu bonds (Au∙∙∙Au distance of 3.2007(3) Å) to form simple dimers, which also have an eclipsed arrangement of the ligands. Electronic structure calculations strongly suggest that the staggered geometry for the [(Au(SCSN3))2](+) dimer is energetically favored relative to the eclipsed geometry. However, attractive π-stacking interactions appear to promote the observed eclipsed arrangement of the ligands.

The use of a rigid tritopic phosphonic ligand for the synthesis of a robust honeycomb-like layered zirconium phosphonate framework.

1,3,5-Tris(4-phosphonophenyl)benzene was synthesized via a microwave heating assisted route and was subsequently used for the preparation of a new zirconium phosphonate with honeycomb-like structure displaying remarkable thermal stability and hydrolysis resistance.

Insights into the role of follicular helper T cells in autoimmunity.

Follicular helper T (TFH) cells are recently highlighted as their crucial role for humoral immunity to infection as well as their abnormal control to induce autoimmune disease. During an infection, naïve T cells are differentiating into TFH cells which mediate memory B cells and long-lived plasma cells in germinal center (GC). TFH cells are characterized by their expression of master regulator, Bcl-6, and chemokine receptor, CXCR5, which are essential for the migration of T cells into the B cell follicle. Within the follicle, crosstalk occurs between B cells and TFH cells, leading to class switch recombination and affinity maturation. Various signaling molecules, including cytokines, surface molecules, and transcription factors are involved in TFH cell differentiation. IL-6 and IL-21 cytokine-mediated STAT signaling pathways, including STAT1 and STAT3, are crucial for inducing Bcl-6 expression and TFH cell differentiation. TFH cells express important surface molecules such as ICOS, PD-1, IL-21, BTLA, SAP and CD40L for mediating the interaction between T and B cells. Recently, two types of microRNA (miRNA) were found to be involved in the regulation of TFH cells. The miR-17-92 cluster induces Bcl-6 and TFH cell differentiation, whereas miR-10a negatively regulates Bcl-6 expression in T cells. In addition, follicular regulatory T (TFR) cells are studied as thymus-derived CXCR5(+)PD-1(+)Foxp3(+) Treg cells that play a significant role in limiting the GC response. Regulation of TFH cell differentiation and the GC reaction via miRNA and TFR cells could be important regulatory mechanisms for maintaining immune tolerance and preventing autoimmune diseases such as systemic lupus erythematosus (SLE) and rheumatoid arthritis (RA). Here, we review recent studies on the various factors that affect TFH cell differentiation, and the role of TFH cells in autoimmune diseases.