Enthralling Anodic Protection by Molybdate on High-Entropy Alloy-Based Electrocatalyst for Sustainable Seawater Oxidation.

Efficient and sustainable seawater electrolysis is still limited due to the interference of chloride corrosion at the anode. The designing of suitable electrocatalysts is one of the crucial ways to boost electrocatalytic activity. However, the approach may fall short as achieving high current density often occurs in chlorine evolution reaction (CER)-dominating potential regions. Thereby, apart from developing an OER-active high-entropy alloy-based electrocatalyst, the present study also offers a unique way to protect anode surface under high current density or potential by using MoO4 2- as an effective inhibitor during seawater oxidation. The wide variation of d-band center of high-entropy alloy-based electrocatalyst allows great oxygen evolution reaction (OER) proficiency exhibiting an overpotential of 230 mV at current density of 20 mA cm-2. Besides, the electrocatalyst demonstrates impressive stability over 500 h at high current density of 1 A cm-2 or at a high oxidation potential of 2.0 V versus RHE in the presence of a molybdate inhibitor. Theoretical and experimental studies reveal MoO4 2- electrostatically accumulated at anode surface due to higher adsorption ability, thereby creating a protective layer against chlorides without affecting OER.

Persistent homology-based descriptor for machine-learning potential of amorphous structures.

High-accuracy prediction of the physical properties of amorphous materials is challenging in condensed-matter physics. A promising method to achieve this is machine-learning potentials, which is an alternative to computationally demanding ab initio calculations. When applying machine-learning potentials, the construction of descriptors to represent atomic configurations is crucial. These descriptors should be invariant to symmetry operations. Handcrafted representations using a smooth overlap of atomic positions and graph neural networks (GNN) are examples of methods used for constructing symmetry-invariant descriptors. In this study, we propose a novel descriptor based on a persistence diagram (PD), a two-dimensional representation of persistent homology (PH). First, we demonstrated that the normalized two-dimensional histogram obtained from PD could predict the average energy per atom of amorphous carbon at various densities, even when using a simple model. Second, an analysis of the dimensional reduction results of the descriptor spaces revealed that PH can be used to construct descriptors with characteristics similar to those of a latent space in a GNN. These results indicate that PH is a promising method for constructing descriptors suitable for machine-learning potentials without hyperparameter tuning and deep-learning techniques.

Ionic Rectification across Ionic and Mixed Conductor Interfaces.

In electrochemical devices, it is important to control the ionic transport between the electrodes and solid electrolytes. However, it is difficult to tune the transport without applying an electric field. This paper presents a method to modulate the transport via tuning of the electrochemical potential difference by controlling the electronic states at the interfaces. We fabricated thin-film solid-state Li batteries using LiTi2O4 thin films as positive electrodes. The spontaneous Li-ion transport between the solid electrolyte and LiTi2O4 is controlled by tuning the electrochemical potential difference via use of an electrically conducting Nb-doped SrTiO3 substrate. This study establishes the foundation for rectifying the ionic transport via electronic energy band alignment.

High level of phosphatidylcholines/lysophosphatidylcholine ratio in urine is associated with prostate cancer.

The altered levels of phospholipids (PLs) and lysophospholipids (LPLs) in prostate cancer (CaP) and benign tissues in our previous findings prompted us to explore PLs and LPLs as potential biomarkers for CaP. Urinary lipidomics has attracted increasing attention in clinical diagnostics and prognostics for CaP. In this study, 31 prostate tissues obtained from radical prostatectomy were assessed using high-resolution matrix-assisted laser desorption/ionization imaging mass spectrometry (HR-MALDI-IMS). Urine samples were collected after digital rectal examination (DRE), and urinary lipids were extracted using the acidified Bligh-Dyer method. The discovery set comprised 75 patients with CaP and 44 with benign prostatic hyperplasia (BPH) at Kyoto University Hospital; the validation set comprised 74 patients with CaP and 59 with BPH at Osaka University Hospital. Urinary lipidomic screening was performed using MALDI time-of-flight MS (MALDI-TOF/MS). The levels of urinary lysophosphatidylcholine (LPC) and phosphatidylcholines (PCs) were compared between the CaP and BPH groups. The (PC [34:2] + PC [34:1])/LPC (16:0) ratio was significantly higher (P < .001) in CaP tissues than in benign epithelial tissues. The urinary PCs/LPC ratio was significantly higher (P < .001) in the CaP group than in the BPH group in the discovery and validation sets.

[Influence of an Operative Strategy on Outcomes of Acute Type A Aortic Dissection Cases].

OBJECTIVE: To compare the surgical outcomes of total arch replacement with the outcomes of ascending aorta replacement in patients with acute Stanford type A aortic dissection. METHODS: From April 2002 to May 2014, 90 patients with acute Stanford type A aortic dissection underwent emergency surgical treatment at our institution. Among them, 16 underwent total arch replacement and 74 underwent ascending aorta replacement. The decision to perform total arch versus ascending aorta replacement was dependent on an intimal tearing site. RESULTS: There were no statistically significant differences in characteristics between the groups with regard to the 2 surgical procedures. Twenty early deaths were reported, but there was no statistically significant difference in mortality rate between the groups. The aortic operation had to be redone in 12 patients. The reoperations were not associated with an increased risk of death or neurological complications. Overall 5-year survival rates were 68% in the ascending aorta replacement group and 59% in the total arch replacement group. There was no statistically significant difference between the groups. CONCLUSIONS: The surgical outcome and prognosis of ascending aorta replacement is satisfactory among patients undergoing treatment of acute type A aortic dissection.

Does the Rewarmed Heart Restore the Myocardial Proteome to That of the Pre-Cooled State?--A Proteomic Analysis of Surgical Samples.

BACKGROUND: Hypothermia is utilized in cardiac and aortic surgery to protect organs from ischemic reperfusion injury. Although the cooled body is invariably rewarmed after the procedure, it is still unknown whether the rewarmed body regains its former biological state. This study determined the modulatory effects of hypothermia on the human myocardial proteome and whether subsequent rewarming restores the proteome to the state prior to cooling. METHODS AND RESULTS: A quantitative proteomic analysis was performed using isobaric tags for relative and absolute quantification labeling tandem mass spectrometry. Right atrial samples were taken 3 times (pre, during and post cooling) during deep hypothermic cardiopulmonary bypass (CPB) from 8 patients with aortic arch aneurysms and 3 corresponding time points during normothermic CPB from 8 patients with ascending aortic or valsalva aneurysms. In total, 697 proteins were identified, with 222 proteins having high protein confidence. Bioinformatic analyses revealed significant downregulation of 19 proteins associated with energy production at hypothermic cardioplegic arrest. On rewarmed beating, 10 proteins remained downregulated, including those regulating cardiac contraction and adaptor proteins, although levels of the aforementioned 19 downregulated proteins returned to their initial values. Additional echocardiographic evaluation demonstrated that hypothermia preserved the variables of diastolic function to a greater extent than normothermic surgery. CONCLUSIONS: Rewarming restores the human myocardial proteome to the pre-cooled state, except for proteins regulating cardiac contraction and adaptor proteins.

Severity of aortic regurgitation assessed by area of vena contracta: a clinical two-dimensional and three-dimensional color Doppler imaging study.

BACKGROUND: Quantitation of aortic regurgitation (AR) using two-dimensional (2D) echocardiography, including vena contracta width (VCW) measurement, is still challenging. Three-dimensional (3D) echocardiography can directly measure the vena contracta area (VCA), regardless of the rheological characteristics. We intended to assess the possibility of 3D vena contracta area (3DVCA) as well as 2D vena contracta area (2DVCA) in the assessment of AR severity. METHODS: Sixty-one patients with AR [17 female (32.7%); mean age: 74.0 ± 10.1 years] underwent 2D and 3D color Doppler echocardiography. Using conventional 2D color Doppler imaging, we measured VCW, 2DVCA, regurgitant volume (RV), and effective regurgitant orifice area (EROA). We also measured 3DVCA manually off-line from 3D full-volume color Doppler datasets for reference. Comprehensive 2D and 3D data on AR severity were successfully obtained from 52 of the 61 (85.2%) patients. RESULTS: Significant correlations existed between 2DVCA and EROA (r = 0.89; p < 0.001). The cut-off 2DVCA for grading severe AR was 34 mm2 (area under curve: 0.95; sensitivity: 78%; specificity: 95%). Significant correlations existed between 3DVCA and EROA (r = 0.89; p < 0.001). The cut-off 3DVCA for grading severe AR was 32 mm2 (area under curve: 0.96; sensitivity: 89%; specificity: 98%). Significant correlations existed between 2DVCA and 3DVCA (r = 0.97; p < 0.001). CONCLUSION: Two-dimensional, as well as three dimensional, vena contracta area measurement is a simple technique suitable for clinical use during comprehensive Doppler echocardiographic AR assessment.

[Resection of Recurrent Leiomyosarcoma of the Inferior Vena Cava with Extention into the Right Atrium and Z stent implantation；Report of a Case].

79-year-old woman, who had undergone resection of a leiomyosarcoma of the inferior vena cava(IVC)[at 68 years old], was admitted to our hospital due to local recurrence of the leiomyosarcoma with extention into the right atrium (RA). She had progressive dyspnea and bilateral edema of the lower extremities. A computed tomography (CT) scan revealed a tumor that obstructed the IVC. A transthoracic echocardiography showed a large mobile right atrial mass. To prevent sudden death, a reoperation was performed. The tumor in the IVC and the RA was resected under deep hypothermic circulatory arrest. A postoperative CT scan showed stenosis of the IVC by residual tumor, and a Z-stent was therefore implanted in the IVC. Postoperative recovery was uneventful and the patient no longer showed any symptoms.

qShot MALDI analysis: A rapid, simple, convenient, and reliable quantitative phospholipidomics approach using MALDI-TOF/MS.

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI/MS) has potential applications in the qualitative analysis of phospholipids (PLs). However, its capability for quantitative analysis is limited by the unavailability and/or high cost of isotope-labeled internal standards (interSTDs, e.g., 1-oleoyl (d7)-2-hydroxy-sn-glycero-3-phosphocholine, 1-pentadecanoyl-2-oleoyl (d7)-sn-glycero-3-phosphocholine). This study investigated and validated whether only two PL interSTDs could be used to normalize the entire PL species in a complex bio-lipid background (i.e., urinary lipid extracts). The normalized intensities of PL ionization standards (ionSTDs) were found to have better linear regressions (R2 > 0.984 for all PL subcategories) than those of traditional methods, such as total ion current and matrix-peak normalization methods. Furthermore, the intra-day precision of all the analyte concentrations after normalizing using our ionSTD method was superior to those of traditional methods. The inter-day precision of all the negatively charged analytes also differed statistically between our ionSTD and the two traditional methods. Meanwhile, a comparison of the three normalization methods revealed that the precision of all the positive analytes using the ionSTD method was comparable. Consequently, a cost-effective, fast, simple, convenient, and reliable quantitative method, defined as "qShot MALDI analysis," was developed to analyze PLs that could potentially be applied in clinical biomarker screening, especially in a negative mode.

Drastic Reduction of the Solid Electrolyte-Electrode Interface Resistance via Annealing in Battery Form.

The origin of electrical resistance at the interface between the positive electrode and solid electrolyte of an all-solid-state Li battery has not been fully determined. It is well known that the interface resistance increases when the electrode surface is exposed to air. However, an effective method of reducing this resistance has not been developed. This report demonstrates that drastic reduction of the resistance is achievable by annealing the entire battery cell. Exposing the LiCoO2 positive electrode surface to H2O vapor increases the resistance by more than 10 times (to greater than 136 Ω cm2). The magnitude can be reduced to the initial value (10.3 Ω cm2) by annealing the sample in a battery form. First-principles calculations reveal that the protons incorporated into the LiCoO2 structure are spontaneously deintercalated during annealing to restore the low-resistance interface. These results provide fundamental insights into the fabrication of high-performance all-solid-state Li batteries.

Tuning the Schottky Barrier Height at the Interfaces of Metals and Mixed Conductors.

Understanding electronic and ionic transport across interfaces is crucial for designing high-performance electric devices. The adjustment of work functions is critical for band alignment at the interfaces of metals and semiconductors. However, the electronic structures at the interfaces of metals and mixed conductors, which conduct both electrons and ions, remain poorly understood. This study reveals that a Schottky barrier is present at the interface of the Nb-doped SrTiO3 metal and a LiCoO2 mixed conductor and that the interfacial resistance can be tuned by inserting an electric dipole layer. The interfacial resistance significantly decreased (by more than 5 orders of magnitude) upon the insertion of a 1 nm thick insulating LaAlO3 layer at the interface. We apply these techniques to solid-state lithium batteries and demonstrate that tuning the electronic energy band alignment by interfacial engineering is applicable to the interfaces of metals and mixed conductors. These results highlight the importance of designing positive electrode and current collector interfaces for solid-state lithium batteries with high power density.

Effect of Advanced Airway Management by Paramedics During Out-of-Hospital Cardiac Arrest on Chest Compression Fraction and Return of Spontaneous Circulation.

PURPOSE: To obtain effective systemic blood flow and coronary perfusion by chest compressions during cardiopulmonary resuscitation, it is recommended that the interruption time of chest compressions be kept to a minimum, and that the chest compression fraction (CCF) should be kept high. In this study, we examined the effects of advanced airway management by paramedics in out-of-hospital cardiac arrest (OHCA) cases on CCF and on return of spontaneous circulation (ROSC) before arrival at the hospital. PARTICIPANTS AND METHODS: A total of 283 adult, non-traumatic OHCA cases who were in cardiopulmonary arrest at the time of EMS contact between April 2015 and March 2017 were registered for this study. We retrospectively investigated the presence or absence of advanced airway clearance, CCF and ROSC during CPR. CCF was calculated by measuring the chest compression interruption time from the ECG waveform recorded on a semiautomatic defibrillator (Philips HeartStart MRX). The data obtained were recorded on a computer, and comparisons between groups were examined using an untested t-test and χ2- test. RESULTS: Of the 283 patients with OHCA, 159 were included in the analysis. The CCF of the AAM group was 89.4%, which was significantly higher than that in the BMV group (84.3%) (P<0.01). Forty-one patients had ROSC at the time of arrival at the hospital, and the CCF of ROSC patients was 89.7%, which was significantly higher than that of non-ROSC patients (87.2%) (P<0.01). ROSC was also obtained in 31.8% of the patients in the AAM group, which was significantly higher than that in the BMV group (12.2%). CONCLUSION: In this study, we found that advanced airway management during prehospital emergency transport by paramedics showed high CCF and ROSC rates and contributed to improving the prognosis of OHCA patients through high-quality resuscitation.

A narrative review of urinary phospholipids: from biochemical aspect towards clinical application.

As a newly emerged discipline, lipidomic studies have focused on the comprehensive characterization and quantification of lipids in a given biological system, which has remarkably advanced in recent years owing to the rapid development of analytical techniques, especially mass spectrometry. Among diverse lipid classes, phospholipids, which have fundamental roles in the formation of cellular membranes, signaling processes, and bioenergetics have gained momentum in several fields of research. The altered composition, concentration, spatial distribution, and metabolism of phospholipids in cells, tissues, and body fluids have been elucidated in various human diseases such as cancer, inflammation, as well as cardiovascular and metabolic disorders. Among the different kinds of phospholipid sources in the human body, urine has not been extensively investigated in recent years owing to the extremely low concentrations of phospholipids and high levels of salts and other contaminants, which can interfere with precise detection. However, with profound advances and rapid expansion in analytical methods, urinary phospholipids have attracted increasing attention in current biomedical research as urine is an easily available source for the discovery of noninvasive biomarkers. In this review, we provide an overview of urinary phospholipids, including their biochemical aspects and clinical applications, aimed at promoting this field of research.

A case of severe aortic stenosis caused by unicuspid unicommissural aortic valve.

Unicuspid aortic valve (UAV) is an extremely rare congenital malformation that frequently presents with valvular dysfunction or aortic aneurysm. Here we report the case of a 49-year-old man with severe aortic stenosis caused by UAV requiring the Bentall procedure. Two- and three-dimensional transesophageal echocardiography revealed an eccentric opening in an aortic valve and a lateral attachment to the aorta at the orifice level, suggestive of which is consistent with unicommissural UAV as confirmed by surgical findings. .

Dynamical Quantum Filtering via Enhanced Scattering of para-H2 on the Orientationally Anisotropic Potential of SrTiO3(001).

Quantum dynamics calculation, performed on top of density functional theory (DFT)-based total energy calculations, show dynamical quantum filtering via enhanced scattering of para-H2 on SrTiO3(001). We attribute this to the strongly orientation-dependent (electrostatic) interaction potential between the H2 (induced) quadrupole moment and the surface electric field gradient of ionic SrTiO3(001). These results suggest that ionic surfaces could function as a scattering/filtering media to realize rotationally state-resolved H2. This could find significant applications not only in H2 storage and transport, but also in realizing materials with pre-determined characteristic properties.

Plasma proteomic changes during therapeutic hypothermia in resuscitated patients after cardiac arrest.

Hypothermia is used for several h during cardiac and aortic surgery to protect ischemic organs. Therapeutic hypothermia (TH) is used for ≤24 h as a treatment for comatose patients after the return of spontaneous circulation (ROSC) following cardiac arrest. The proteomic approach may provide unbiased data on alterations in the abundance of proteins during TH. The objective of this study was to assess the effects of cooling/rewarming on the plasma proteome during TH after ROSC and to identify the mechanism underlying its therapeutic effects. A total of nine comatose adult patients, resuscitated shortly after cardiac arrest, were cooled to 34°C for 24 h and slowly rewarmed to 36°C. A quantitative gel-free proteomic analysis was performed using the isobaric tag for relative and absolute quantification labeling tandem mass spectrometry. Plasma samples were obtained prior to cooling and rewarming, and immediately after rewarming, from all patients during TH after ROSC. A total of 92 high-confidence proteins were identified. Statistically significant alterations were observed (>1.2-fold increase or <0.833-fold decrease) in the levels of 15 of those proteins (P=0.003-0.047), mainly proteins belonging to the acute-phase response or platelet degranulation. Unexpectedly, the levels of free hemoglobin (hemoglobin subunits α and ß) were significantly downregulated during TH (P<0.05). The level of the terminal complement complex (SC5b-9) showed significant reduction after cooling (P=0.023). Although the acute-phase response proteins were upregulated, the abundance of complement proteins did not change, and the levels of SC5b-9 and free hemoglobin decreased during TH in patients after ROSC.

Data processing on a comparative evaluation of the extraction and analysis procedures for urinary phospholipid and lysophospholipid using MALDI-TOF/MS.

In this dataset we provide MALDI-TOF/MS spectra for the testing and application of a quantitative method using external ionization standards (ionization STDs) for peak-intensity normalization. The presented data is related to our recent article entitled "a comparative evaluation of the extraction and analysis procedures for urinary phospholipid and lysophospholipid using MALDI-TOF/MS". Gradient dilutions of mixture containing thirteen phospho- and lysophospho-lipid species (internal STDs) were mixed with constant concentration of the ionization STDs and analyzed together. Peak intensities of the internal and ionization STDs were picked by a homemade workflow based on OpenMS (steps including noise filtration, baseline subtraction and peak-picking). The peak-intensity ratios between the internal and ionization STDs were linearly correlated with their concentration ratios. Using this method, the evaluation of efficiencies of six different lipid extraction methods was performed in urine samples. In summary, a free and easy-to-use method for phospholipid and lysophospholipid quantitative analysis based on MALDI-TOF/MS is provided in this article.

Comparative evaluation of the extraction and analysis of urinary phospholipids and lysophospholipids using MALDI-TOF/MS.

Lipids, particularly phospholipids (PLs) and lysophospholipids (LPLs), are attracting increasing scientific interest for their biological functions in cells and their potential as disease biomarkers for Alzheimer's disease and several types of cancer. Urinary PLs and LPLs could be ideal clinical biomarkers, because urine can be collected easily and noninvasively. However, due to their very low concentrations in urine compared with the relatively large quantity of contaminants in this matrix, efficient extraction and sensitive detection are required for analyzing urinary PLs and LPLs. In this study, various methods for analyzing PLs and LPLs in urine were compared and optimized from a clinical perspective. An optimized lipid extraction method and a matrix for matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) were established using two external ionization standards and an internal standard mix containing 13 human urinary lipids. 9-Aminoacridine (9-AA) was a useful and effective matrix for the MALDI-TOF/MS analysis of all the internal standard lipids in both positive and negative ion modes. However, it was necessary to determine the proportional lipid concentrations from the balance between the extracted lipid and the matrix. The extraction efficiency and reproducibility of the acidified Bligh and Dyer method were excellent for both positively and negatively charged lipids. Analysis of small volumes of urine was the most efficient with the 9-AA MALDI matrix at concentrations of or below 5 mM. The combined analytical procedures allowed rapid and comprehensive screening of low concentrations of PLs and LPLs in clinical samples.

Developmental abnormalities of the thymus in hea/hea mutant mice.

This study found that the thymus of hea/hea mutant mice (hea mice) became atrophic in early phase of life and that the differentiation of CD4-CD8- (Double Negative; DN) into CD4+CD8+ (Double Positive; DP) cells during the development of T cells in the thymus was abnormal. The thymus development of hea mice was different from that of normal littermates. After 6 days of age, the numbers of thymocytes in hea mice decreased. The total numbers of DP cells in the thymus of hea mice reached the maximum at 6-9 days of age and then decreased after 10 days. The total numbers of DN cells in the thymus were almost constant in hea mice and normal littermates. These results indicate abnormalities in the process of differentiation from DN to DP cells in the thymus of hea mice. Flow cytometoric analysis indicated the presence of a large number of apoptotic and necrotic cells in the thymus of 13-15-day-old hea mice. However, there were no significant differences in the amount of mRNAs of Fas, Fas ligand and IL-7 between hea mice and normal littermates. Splenocytes from hea mice produced the same amount of cytokine mRNAs as normal littermate mice and the hea mutation (Ttc7(fsn-hea)) did not affect serum levels of IgM immunoglobulin. However, activated T cells from hea mice showed more secretion of cytokines derived from Th2 cells than from Th1 cells, so they might be affected by abnormalities of the immune system.

Recovery from very long aortic cross-clamping in redo complex aortic surgery.

A 68-year-old man had undergone ascending aortic replacement for acute type A aortic dissection. Three months later, he had a new aortic dissection with an ulcer-like projection located in the aortic arch with suspected graft infection. An emergent redo total aortic arch and root replacement was performed because of the coexistence of a fragile aortic root wall. The extensive redo procedure necessitated a very long aortic cross-clamping time (516 min). After 25 min of assisted circulation, he was easily weaned from the cardiopulmonary bypass. Finally, an omental flap was harvested to cover the graft. Postoperative ECG and CK-MB examinations showed no significant myocardial injury. He had no symptoms of heart failure and was discharged after a month of antibiotic therapy. One-year follow-up UCG study revealed no abnormal findings except for signs of pericardial adhesion.