Exploring metastable states in UO2using hybrid functionals and dynamical mean field theory.

A detailed exploration of thef-atomic orbital occupancy space for UO2is performed using a first principles approach based on density functional theory (DFT), employing a full hybrid functional within a systematic basis set. Specifically, the PBE0 functional is combined with an occupancy biasing scheme implemented in a wavelet-based algorithm which is adapted to large supercells. The results are compared with previous DFT +Ucalculations reported in the literature, while dynamical mean field theory is also performed to provide a further base for comparison. This work shows that the computational complexity of the energy landscape of a correlatedf-electron oxide is much richer than has previously been demonstrated. The resulting calculations provide evidence of the existence of multiple previously unexplored metastable electronic states of UO2, including those with energies which are lower than previously reported ground states.

New Compounds and Phase Selection of Nickel Sulfides via Oxidation State Control in Molten Hydroxides.

Molten salts are promising reaction media candidates for the discovery of novel materials; however, they offer little control over oxidation state compared to aqueous solutions. Here, we demonstrated that when two hydroxides are mixed, their melts become fluxes with tunable solubility, which are surprisingly powerful solvents for ternary chalcogenides and offer effective paths for crystal growth to new compounds. We report that precise control of the oxidation state of Ni is achievable in mixed molten LiOH/KOH to grow single crystals of all known ternary K-Ni-S compounds. It is also possible to access several new phases, including a new polytope of ß-K2Ni3S4, as well as low-valence KNi4S2 and K4Ni9S11. KNi4S2 is a two-dimensional low-valence nickel-rich sulfide, and ß-K2Ni3S4 has a hexagonal lattice. Moreover, using KNi4S2 as a template, we obtained a new layered binary Ni2S by topotactic deintercalation of K. The new binary Ni2S has a van der Waals gap and can function as a new host layer for intercalation chemistry, as demonstrated by the intercalation of LiOH between its layers. The oxidation states of low-valence KNi4S2 and Ni2S were studied using X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. Density functional theory calculations showed large antibonding interactions at the Fermi level for both KNi4S2 and Ni2S, corresponding to the flat-bands with large Ni-dx2-y2 character.

Immature Persimmon Suppresses Amyloid Beta (Aß) Mediated Cognitive Dysfunction via Tau Pathology in ICR Mice.

This study confirmed the ameliorating effect of immature persimmon (Diospyros kaki) ethanolic extract (IPEE) on neuronal cytotoxicity in amyloid beta (Aß)1-42-induced ICR mice. The administration of IPEE ameliorated the cognitive dysfunction in Aß1-42-induced mice by improving the spatial working memory, the short-term and long-term memory functions. IPEE protected the cerebral cholinergic system, such as the acetylcholine (ACh) level and acetylcholinesterase (AChE) activity, and antioxidant system, such as the superoxide dismutase (SOD), reduced glutathione (GSH) and malondialdehyde (MDA) contents. In addition, mitochondrial dysfunction against Aß1-42-induced toxicity was reduced by regulating the reactive oxygen species (ROS), mitochondrial membrane potential and ATP contents. In addition, IPEE regulated the expression levels of tau signaling, such as TNF-α, p-JNK, p-Akt, p-GSK3ß, p-tau, p-NF-κB, BAX and caspase 3. Finally, gallic acid, ellagic acid and quercetin 3-O-(6″-acetyl-glucoside) were identified as the physiological compounds of IPEE using ultra-performance liquid chromatography ion mobility separation quadrupole time-of-flight/tandem mass spectrometry (UPLC IMS Q-TOF/MS2).

Upper extremity revascularization with autologous femoral vein graft in an immunocompromised patient: 5-year computed tomographic findings.

Femoral veins have been used as a substitute graft for limb bypass in selected patients. The long-term efficacy of deep-vein grafts in neoaortoiliac system reconstruction has been shown to be excellent but the efficacy in extremity bypass is still unclear. Here, we report a case of subclavian-to-brachial artery bypass surgery using a femoral vein graft in a chronically immunocompromised patient with previous kidney transplantation. The patient remains symptom-free at 5 years with a patent bypass without any complications, such as aneurysmal dilatation, recurrent infection, stenosis or harvested limb oedema. The femoral vein would be a good option for extremity bypass in patients with high-risk immune problems when other veins are not available.

Unconventional slowing down of electronic recovery in photoexcited charge-ordered La1/3Sr2/3FeO3.

The coupling of ordered electronic phases with lattice, spin, and orbital degrees of freedom are of central interest in strongly correlated systems. Their interplay has been intensively studied from femtosecond to picosecond time scales, while their dynamics beyond nanoseconds are usually assumed to follow lattice cooling. Here, we report an unusual slowing down of the recovery of an electronic phase across a first-order phase transition. Following optical excitation, the recovery time of both transient optical reflectivity and X-ray diffraction intensity from the charge-ordered superstructure in a La1/3Sr2/3FeO3 thin film increases by orders of magnitude as the sample temperature approaches the phase transition temperature. In this regime, the recovery time becomes much longer than the lattice cooling time. The combined experimental and theoretical investigation shows that the slowing down of electronic recovery corresponds to the pseudo-critical dynamics that originates from magnetic interactions close to a weakly first-order phase transition.

Coherent band excitations in CePd3: A comparison of neutron scattering and ab initio theory.

In common with many strongly correlated electron systems, intermediate valence compounds are believed to display a crossover from a high-temperature regime of incoherently fluctuating local moments to a low-temperature regime of coherent hybridized bands. We show that inelastic neutron scattering measurements of the dynamic magnetic susceptibility of CePd3 provides a benchmark for ab initio calculations based on dynamical mean field theory. The magnetic response is strongly momentum dependent thanks to the formation of coherent f-electron bands at low temperature, with an amplitude that is strongly enhanced by local particle-hole interactions. The agreement between experiment and theory shows that we have a robust first-principles understanding of the temperature dependence of f-electron coherence.

Association Between Intraoperative Platelet Transfusion and Early Graft Regeneration in Living Donor Liver Transplantation.

OBJECTIVE: To evaluate the association between anesthetic management before and after graft reperfusion and early graft regeneration in living donor liver transplantation (LDLT). BACKGROUND: Sufficient graft regeneration is essential for the success of LDLT. Diverse signals start to trigger liver regeneration immediately after graft reperfusion. METHODS: Graft volume at 14 ±â€Š2 days after LDLT was measured in 379 consecutive recipients using computed tomography images with 3-dimensional reconstruction. The association between anesthetic variables and the degree of graft regeneration for 2 weeks was analyzed using simple and multiple linear regressions. The anesthetic variables included hemodynamics, laboratory measurements, vasoactive drugs, and blood products transfusion. RESULTS: The degree of graft regeneration for 2 weeks was 52% in median and ranged from 5% to 123%. Platelet transfusion was identified as the sole independent anesthetic factor contributing to graft regeneration. Platelet concentrate transfusion of 1 to 6 units vs none was correlated with a 6.5% increase in graft regeneration (P = 0.012). Platelet concentrate transfusion of more than 6 units vs none was further correlated with an 18.4% increase in regeneration (P < 0.001). In the subgroup of recipients without intraoperative platelet transfusion, mean platelet count measured during the intraoperative reperfusion phase was positively associated with graft regeneration (P = 0.033). CONCLUSIONS: Graft regeneration after LDLT increased in relation to a graded increase in the amount of transfused platelets and higher postreperfusion platelet counts during surgery. These results offer additional evidence regarding the important role of platelets in initiating liver regeneration and, furthermore, the indications for and the benefits vs risks of platelet transfusion during LDLT.

Novel Electronic Behavior Driving NdNiO3 Metal-Insulator Transition.

We present evidence that the metal-insulator transition (MIT) in a tensile-strained NdNiO3 (NNO) film is facilitated by a redistribution of electronic density and that it neither requires Ni charge disproportionation nor a symmetry change [U. Staub et al., Phys. Rev. Lett. 88, 126402 (2002); R. Jaramillo et al., Nat. Phys. 10, 304 (2014)]. Given that epitaxial tensile strain in thin NNO films induces preferential occupancy of the e(g) d(x(2)-y(2)) orbital we propose that the larger transfer integral of this orbital state with the O 2p orbital state mediates a redistribution of electronic density from the Ni atom. A decrease in the Ni d(x(2)-y(2)) orbital occupation is directly observed by resonant inelastic x-ray scattering below the MIT temperature. Furthermore, an increase in the Nd charge occupancy is measured by x-ray absorption at the Nd L(3) edge. Both spin-orbit coupling and crystal field effects combine to break the degeneracy of the Nd 5d states, shifting the energy of the Nd e(g) d(x(2)-y(2)) orbit towards the Fermi level, allowing the A site to become an active acceptor during the MIT. This work identifies the relocation of electrons from the Ni 3d to the Nd 5d orbitals across the MIT. We propose that the insulating gap opens between the Ni 3d and O 2p states, resulting from Ni 3d electron localization. The transition seems to be neither a purely Mott-Hubbard transition nor a simple charge transfer.

Macrosteatotic and nonmacrosteatotic grafts respond differently to intermittent hepatic inflow occlusion: Comparison of recipient survival.

Intermittent hepatic inflow occlusion (IHIO) during liver graft procurement is known to confer protection against graft ischemia/reperfusion injury and thus may benefit the recipient's outcome. We evaluated whether the protective effect of IHIO differs with the presence of macrosteatosis (MaS) and with an increase or decrease in the cumulative occlusion time. The subgroup of 188 recipients who received grafts with MaS was divided into 3 groups according to the number of total IHIO rounds during graft procurement: no IHIO, n = 70; 1 to 2 rounds of IHIO, n = 50; and ≥3 rounds of IHIO, n = 68. Likewise, the subgroup of 200 recipients who received grafts without MaS was divided into 3 groups: no IHIO, n = 108; 1 to 2 rounds of IHIO, n = 40; and ≥3 rounds of IHIO, n = 52. The Cox model was applied to evaluate the association between the number of total IHIO rounds and recipient survival separately in the subgroup of MaS recipients and the subgroup of non-MaS recipients. Analyzed covariables included the etiology, Milan criteria, transfusion, immunosuppression, and others. In the subgroup of MaS recipients, 1 to 2 rounds of IHIO were favorably associated with recipient survival [hazard ratio (HR), 0.29; 95% confidence interval (CI), 0.10-0.80; P = 0.03 after Bonferroni correction], whereas ≥3 rounds of IHIO were not associated with recipient survival (HR, 0.56; 95% CI, 0.25-1.23). In the subgroup of non-MaS recipients, neither 1 to 2 rounds of IHIO (HR, 0.69; 95% CI, 0.30-1.61) nor ≥3 rounds of IHIO (HR, 0.91; 95% CI, 0.42-1.96) were associated with recipient survival. In conclusion, 1 to 2 rounds of IHIO may be used for the procurement of MaS grafts with potential benefit for recipient survival, whereas IHIO has a limited impact on recipient survival regardless of the cumulative occlusion time when it is used for non-MaS grafts.

Intraoperative hyperglycemia during liver resection: predictors and association with the extent of hepatocytes injury.

BACKGROUND: Patients undergoing liver resection are at risk for intraoperative hyperglycemia and acute hyperglycemia is known to induce hepatocytes injury. Thus, we aimed to evaluate whether intraoperative hyperglycemia during liver resection is associated with the extent of hepatic injury. METHODS: This 1 year retrospective observation consecutively enrolled 85 patients undergoing liver resection for hepatocellular carcinoma. Blood glucose concentrations were measured at predetermined time points including every start/end of intermittent hepatic inflow occlusion (IHIO) via arterial blood analysis. Postoperative transaminase concentrations were used as surrogate parameters indicating the extent of surgery-related acute hepatocytes injury. RESULTS: Thirty (35.5%) patients developed hyperglycemia (blood glucose > 180 mg/dl) during surgery. Prolonged (≥ 3 rounds) IHIO (odds ratio [OR] 7.34, P = 0.004) was determined as a risk factors for hyperglycemia as well as cirrhosis (OR 4.07, P = 0.022), lower prothrombin time (OR 0.01, P = 0.025), and greater total cholesterol level (OR 1.04, P = 0.003). Hyperglycemia was independently associated with perioperative increase in transaminase concentrations (aspartate transaminase, ß 105.1, standard error 41.7, P = 0.014; alanine transaminase, ß 81.6, standard error 38.1, P = 0.035). Of note, blood glucose > 160 or 140 mg/dl was not associated with postoperative transaminase concentrations. CONCLUSIONS: Hyperglycemia during liver resection might be associated with the extent of hepatocytes injury. It would be rational to maintain blood glucose concentration < 180 mg/dl throughout the surgery in consideration of parenchymal disease, coagulation status, lipid profile, and the cumulative hepatic ischemia in patients undergoing liver resection for hepatocellular carcinoma.

Site-selective Mott transition in rare-earth-element nickelates.

A combination of density functional and dynamical mean field theory calculations are used to show that the remarkable metal-insulator transition in the rare-earth-element nickelate perovskites arises from a site-selective Mott phase, in which the d electrons on half of the Ni ions are localized to form a fluctuating moment while the d electrons on other Ni ions form a singlet with holes on the surrounding oxygen ions. The calculation reproduces key features observed in the nickelate materials, including an insulating gap in the paramagnetic state, a strong variation of static magnetic moments among Ni sites and an absence of charge order. A connection between structure and insulating behavior is documented. The site-selective Mott transition may be a more broadly applicable concept in the description of correlated materials.

Magnetic excitation spectra in BaFe2As2: a two-particle approach within a combination of the density functional theory and the dynamical mean-field theory method.

We study the magnetic excitation spectra in the paramagnetic state of BaFe(2)As(2) from the ab initio perspective. Both the one-particle and the magnetic two-particle excitation spectra are determined within the combination of the density functional theory and the dynamical mean-field theory method. This method reproduces all the experimentally observed features in inelastic neutron scattering and relates them to both the one-particle excitations and the collective modes. The magnetic excitation dispersion is well accounted for by our theoretical calculation in the paramagnetic state without any broken symmetry; hence, nematic order is not needed to explain the inelastic neutron scattering experimental data.