Single Iridium Atom Doped Ni2P Catalyst for Optimal Oxygen Evolution.

Single-atom catalysts (SACs) with 100% active sites have excellent prospects for application in the oxygen evolution reaction (OER). However, further enhancement of the catalytic activity for OER is quite challenging, particularly for the development of stable SACs with overpotentials <180 mV. Here, we report an iridium single atom on Ni2P catalyst (IrSA-Ni2P) with a record low overpotential of 149 mV at a current density of 10 mA·cm-2 in 1.0 M KOH. The IrSA-Ni2P catalyst delivers a current density up to ∼28-fold higher than that of the widely used IrO2 at 1.53 V vs RHE. Both the experimental results and computational simulations indicate that Ir single atoms preferentially occupy Ni sites on the top surface. The reconstructed Ir-O-P/Ni-O-P bonding environment plays a vital role for optimal adsorption and desorption of the OER intermediate species, which leads to marked enhancement of the OER activity. Additionally, the dynamic "top-down" evolution of the specific structure of the Ni@Ir particles is responsible for the robust single-atom structure and, thus, the stability property. This IrSA-Ni2P catalyst offers novel prospects for simplifying decoration strategies and further enhancing OER performance.

3D digital image microscope system-assisted vasovasostomy and vasoepididymostomy in rats.

Optimal vision and ergonomics are essential factors contributing to the achievement of good results during microsurgery. The three-dimensional (3D) digital image microscope system with a better 3D depth of field can release strain on the surgeon's neck and back, which can improve outcomes in microsurgery. We report a randomized prospective study of vasoepididymostomy and vasovasostomy using a 3D digital image microscope system (3D-DIM) in rats. A total of 16 adult male rats were randomly divided into two groups of 8 each: the standard operating microscope (SOM) group and the 3D-DIM group. The outcomes measured included the operative time, real-time postoperative mechanical patency, and anastomosis leakage. Furthermore, a user-friendly microscope score was designed to evaluate the ergonomic design and equipment characteristics of the microscope. There were no differences in operative time between the two groups. The real-time postoperative mechanical patency rates were 100.0% for both groups. The percentage of vasoepididymostomy anastomosis leakage was 16.7% in the SOM group and 25.0% in the 3D-DIM group; however, no vasovasostomy anastomosis leakage was found in either group. In terms of the ergonomic design, the 3D-DIM group obtained better scores based on the surgeon's feelings; in terms of the equipment characteristics, the 3D-DIM group had lower scores for clarity and higher scores for flexibility and adaptivity. Based on our randomized prospective study in a rat model, we believe that the 3D-DIM can improve surgeon comfort without compromising outcomes in male infertility reconstructive microsurgery, so the 3D-DIM might be widely used in the future.

Ultrahigh-Loading of Ir Single Atoms on NiO Matrix to Dramatically Enhance Oxygen Evolution Reaction.

Engineering single-atom electrocatalysts with high-loading amount holds great promise in energy conversion and storage application. Herein, we report a facile and economical approach to achieve an unprecedented high loading of single Ir atoms, up to ∼18wt%, on the nickel oxide (NiO) matrix as the electrocatalyst for oxygen evolution reaction (OER). It exhibits an overpotential of 215 mV at 10 mA cm-2 and a remarkable OER current density in alkaline electrolyte, surpassing NiO and IrO2 by 57 times and 46 times at 1.49 V vs RHE, respectively. Systematic characterizations, including X-ray absorption spectroscopy and aberration-corrected Z-contrast imaging, demonstrate that the Ir atoms are atomically dispersed at the outermost surface of NiO and are stabilized by covalent Ir-O bonding, which induces the isolated Ir atoms to form a favorable ∼4+ oxidation state. Density functional theory calculations reveal that the substituted single Ir atom not only serves as the active site for OER but also activates the surface reactivity of NiO, which thus leads to the dramatically improved OER performance. This synthesis method of developing high-loading single-atom catalysts can be extended to other single-atom catalysts and paves the way for industrial applications of single-atom catalysts.

Sub-3 nm Intermetallic Ordered Pt3In Clusters for Oxygen Reduction Reaction.

Industrial applications of Pt-based oxygen-reduction-reaction (ORR) catalysts are limited by high cost and low stability. Here, facile large-scale synthesis of sub-3-nm ordered Pt3In clusters on commercial carbon black as ORR catalyst that alleviates both these shortcomings is reported. As-prepared Pt3In/C exhibits a mass activity of 0.71 mA mg-1 and a specific area activity of 0.91 mA cm-2 at 0.9 V vs reversible hydrogen electrode, which are 4.1 and 2.7 times the corresponding values of commercial Pt/C catalysts. The as-prepared ordered Pt3In/C catalyst is also remarkably stable with negligible activity and structural decay after 20 000 accelerated electrochemical durability cycles, due to its ordered structure. Density-functional-theory calculations demonstrate that ordered-Pt3In is more energetically favorable for ORR than the commercial Pt/C catalysts because ∆G O is closer to the peak of the volcano plot after ordered incorporation of indium atoms.

CO Gas Induced Phase Separation in PtPb@Pt Catalyst and Formation of Ultrathin Pb Nanosheets Probed by In Situ Transmission Electron Microscopy.

PtPb@Pt catalysts are very useful and widely applied in various industrial reactions. Here, the phase stability of such catalysts is compared in both CO gas and vacuum conditions at elevated temperatures using aberration-corrected in situ transmission electron microscopy (TEM). A Pt aggregation process takes place affected by CO gas, which results in direct exposure of the PtPb core to CO. A phase separation process, in which Pb atoms are stripped off the original PtPb@Pt nanoparticles, is unambiguously identified in CO gas. At initial stages, the as nucleated Pb islands are amorphous. Once the ultrathin Pb islands reach ≈3.5 nm or higher, they suddenly became crystalline. The interaction between Pb and CO gas stabilizes the ultrathin Pb nanosheets, resulting in the formation of a large quantity of Pb nanosheets and Pb-depleted PtPb0.08 nanoparticles. In sharp contrast, when heated up in a vacuum, the PtPb@Pt catalyst remains intact. The results of this study shine light on the "toxic" effect of CO that results in failures of many Pt-based catalysts and discloses formation mechanism of ultrathin Pb nanosheets.

Population genetics of 15 autosomal STR loci in the Han population of Ili Kazakh Autonomous Prefecture, Northwestern China.

PURPOSE: China harbors 56 ethnic groups and Han accounts for >92% of the total Chinese population. We investigated the frequencies of 15 autosomal short tandem repeat (STR) loci in the Han population of the Ili Kazakh Autonomous Prefecture with the aim of expanding the available population information in human genetics databases and for forensic DNA analysis. SUBJECTS AND METHODS: We explored the genetic characteristics of 15 autosomal STR loci in 552 unrelated Chinese Han individuals from Ili Kazakh Autonomous Prefecture, Northwestern China using the AmpFISTR Identifiler PCR Amplification Kit. Moreover, phylogenetic analysis was performed between the Han population and other relevant populations based on the autosomal STR genotyping. The neighbor-joining tree and principle component analysis were generated based on the Nei's standard genetic distance and allelic frequencies, respectively. RESULTS: A total of 171 alleles were observed among 552 unrelated individuals and allelic frequencies ranged from 0.5145 to 0.0009. The combined power of discrimination and combined power of exclusion of the 15 autosomal STR loci were 0.9999999999999999964 and 0.999998243616671, respectively. CONCLUSIONS: Population comparison revealed that the Ili Han population were lining up together with other Han populations in China while showing significant differences from other Chinese and worldwide populations.

A multi-component Cu2O@FePO4 core-cage structure to jointly promote fast electron transfer toward the highly sensitive in situ detection of nitric oxide.

Electrochemical sensors actually involve an electrocatalytic process in efficient and selective energy conversion. In this work, we use different components to innovatively produce a core@cage material, in which the outer cage, iron phosphate, offers a high electrocatalytic ability to electrochemically oxidize NO, while the inner material, cuprous oxide, could absorb the intermediary HO- ions to kinetically promote NO oxidation for fast electron transfer, resulting in a strong synergistic effect. The unique core@cage structure also increases the active surface area and provides plenty of channels via the porous cage for significantly enhanced mass transport. The as-prepared core@cage NO sensor shows a high sensitivity of 326.09 µA cm-2 µM-1, which is the highest among the reported non-noble metal-based NO biosensors based on the electrooxidation scheme. A free-standing flexible NO sensor was further fabricated with the material for the in situ detection of NO released from cancer cells, demonstrating a low detection limit (0.45 nM) and a fast response time (0.8 s). This work holds great promise for its practical applications in the diagnosis or research of complicated biological processes, especially in real-time in situ detection approaches.

ATM rs189037 (G > A) polymorphism increased the risk of cancer: an updated meta-analysis.

BACKGROUND: Rs189037 (G > A) is a functional single nucleotide polymorphism (SNP) in the Ataxia-telangiectasia mutated (ATM) gene that may be associated with the risk of cancer. We performed a meta-analysis to determine whether rs189037 polymorphism influences the occurrence of cancer and examined the relationship between this SNP and the etiology of cancer. METHODS: Case-control studies were retrieved from literature databases in accordance with established inclusion criteria. Odds ratios (ORs) and 95% confidence intervals (CIs) were calculated to evaluate the strength of the association between rs189037 and cancer. Subgroup analysis and sensitivity analysis also were performed. RESULTS: After inclusion criteria were met, fifteen studies-comprising 8660 patients with cancer (cases) and 9259 controls-were included in this meta-analysis. Summary results indicated that an association was found between rs189037 and cancer risk. In the dominant model, the pooled OR using a random effects model was 1.207 (95% CI, 1.090-1.337; P < 0.001). The A allele of rs189037 increased the risk of lung cancer, breast cancer, and oral cancer. Results of subgroup analysis by ethnicity indicated that the SNP was associated with the risk of cancer among East Asian and Latino, but not Caucasian. CONCLUSIONS: Results of this meta-analysis suggest that rs189037 is associated with the occurrence of lung cancer, breast cancer, and oral cancer as the risk factor. These data provide possible avenues for future case-control studies related to cancer.

Ir-Alloyed Ultrathin Ternary PdIrCu Nanosheet-Constructed Flower with Greatly Enhanced Catalytic Performance toward Formic Acid Electrooxidation.

Ternary metal-element alloys have been reported as efficient electrocatalysts toward various electrochemical reactions, but a unique three-dimensional (3D) Ir-alloyed ternary nanosheet-composed flower (NCF) structure has not been explored yet. Herein, an innovated 1.8 nm Ir-alloyed ultrathin ternary PdIrCu NCF structure is synthesized via one-pot solvothermal reduction without using any surfactant. The as-prepared PdIrCu/C NCF catalyst remarkably improves the stability than commercial Pd/C toward formic acid electrooxidation while resulting in significantly increased mass activity. The improvement of electrocatalytic properties depends on the introduction of Ir and Cu atoms, which greatly prevented poisoning from CO while modifying the electronic structure of Pd for increased reaction active sites and accelerated charge-transfer rate as well as facilitated mass transport by ultrathin NCF 3D structure. Therefore, this catalyst possesses a promising application prospect in electrochemical energy storage/conversion systems.

Engineering Morphologies of Cobalt Pyrophosphates Nanostructures toward Greatly Enhanced Electrocatalytic Performance of Oxygen Evolution Reaction.

Herein, a surfactant- and additive-free strategy is developed for morphology-controllable synthesis of cobalt pyrophosphate (CoPPi) nanostructures by tuning the concentration and ratio of the precursor solutions of Na4 P2 O7 and Co(CH3 COO)2 . A series of CoPPi nanostructures including nanowires, nanobelts, nanoleaves, and nanorhombuses are prepared and exhibit very promising electrocatalytic properties toward the oxygen evolution reaction (OER). Acting as both reactant and pseudo-surfactant, the existence of excess Na4 P2 O7 is essential to synthesize CoPPi nanostructures for unique morphologies. Among all CoPPi nanostructures, the CoPPi nanowires catalyst renders the best catalytic performance for OER in alkaline media, achieving a low Tafel slope of 54.1 mV dec-1 , a small overpotential of 359 mV at 10 mA cm-2 , and superior stability. The electrocatalytic activities of CoPPi nanowires outperform the most reported non-noble metal based catalysts, even better than the benchmark Ir/C (20%) catalyst. The reported synthesis of CoPPi gives guidance for morphology control of transition metal pyrophosphate based nanostructures for a high-performance inexpensive material to replace the noble metal-based OER catalysts.

Growing Platinum-Ruthenium-Tin ternary alloy nanoparticles on reduced graphene oxide for strong ligand effect toward enhanced ethanol oxidation reaction.

Uniform Pt1Ru0.5Sn0.5 ternary alloy nanoparticles are in situ deposited on reduced graphene oxide (Pt1Ru0.5Sn0.5-RGO) through its functional groups and defects as nucleation sites to greatly electrocatalyze ethanol oxidation reaction for much higher mass current densities, larger apparent specific current densities and better stability than commercial Pt-C catalyst (Pt-C(commer)). Mechanistic studies indicate that the excellent electrocatalytic activity and anti-poisoning are resulted from a strong ligand effect of the ternary alloy components, in which the charge transfer is boosted while decreasing the density of states close to the Fermi level of Pt to reduce bond energy between Pt and CO-like adsorbates for greatly improved anti-poisoning ability. This work holds a great promise to fabricate a high performance anode catalyst with a low Pt loading for direct ethanol fuel cells.

Facile one-pot surfactant-free synthesis of uniform Pd6Co nanocrystals on 3D graphene as an efficient electrocatalyst toward formic acid oxidation.

Ultrasmall and uniform Pd6Co nanocrystals were deposited on 3D graphene by a facile one-pot surfactant-free route for a catalyst toward formic acid oxidation, showing a much higher electrocatalytic activity, larger peak current density and better stability than Pd/3DG, Pd/C as well as commercial Pd-C, and thus offering great potential for an efficient anode catalyst toward high performance direct formic acid fuel cells.

Preparation and in vitro and in vivo characterization of cyclosporin A-loaded, PEGylated chitosan-modified, lipid-based nanoparticles.

BACKGROUND AND METHODS: A new cyclosporin A-loaded, PEGylated chitosan-modified lipid-based nanoparticle was developed to improve upon the formulation of cyclosporin A. PEGylated chitosan, synthesized in three steps using mild reaction conditions, was used to modify the nanoparticles. Cyclosporin A-loaded, PEGylated chitosan-modified nanoparticles were prepared using an emulsification/solvent evaporation method. The drug content and encapsulation efficiency of the cyclosporin A-loaded, PEGylated chitosan-modified nanoparticles were measured by high-performance liquid chromatography. The average size of the nanoparticles was determined by transmission electron microscopy and dynamic light scattering. The pharmacokinetic behavior of the nanoparticles was investigated in rabbits after intravenous injection. Cyclosporin A concentrations in a whole blood sample were analyzed by high-performance liquid chromatography using tamoxifen as the internal standard. The pharmacokinetic parameters were calculated using the 3p87 software program. RESULTS: Fourier transform infrared spectroscopy and nuclear magnetic resonance confirmed the structure of PEGylated chitosan. The drug content and encapsulation efficiency of the cyclosporin A-loaded, PEGylated chitosan-modified nanoparticles were 37.04% and 69.22%, respectively. The average size of the nanoparticles was 89.4 nm. The nanoparticles released 30% cyclosporin A-loaded in 48 hours in vitro, with no initial burst release. The mode of release in vitro was prone to bulk erosion. The in vivo results showed the biological half-life of the elimination phase (t(1/2ß)) of the nanoparticles was 21 times longer than that of the cyclosporin A solution, and the area under the curve for the nanoparticles was 25.8 times greater than that of the cyclosporin A solution. CONCLUSION: Modification of PEGylated chitosan prolonged the retention time of the nanoparticles in the circulatory system and improved the bioavailability of cyclosporin A.

[Influence of receptor activity modifying protein 1 overexpression on enhancing effect of calcitonin gene-related peptide on MG-63 cells proliferation].

OBJECTIVE: To investigate the influnce of receptor activity modifying protein 1(RAMP-1) overexpression on enhancing effect of calcitonin gene-related peptide on MG-63 cells proliferation. METHODS: Cultured MG-63 osteoblasts in exponential phase of growth were randomly divided into three groups: RAMP-1 overexpression group, empty vector control group and negative control group. RAMP-1 eukaryotic expression vector was constructed and stably transfected into MG-63 cells. Realtime-polymerase chain reaction, Western blotting and immunofluroescence were used respectively to detect the expression of calcitonin receptor-like receptor (CRLR) in the cells and its distribution on cell membrane. The status of proliferation was detected respectively at 0, 24, 48, 72, 96 h by cell counting kit-8 (CCK-8) and cells were collected to analyze their cycle respectively at 0, 8, 16, 24 h by flow cytometry. RESULTS: CRLR protein and mRNA expression levels of MG-63 cells in RAMP-1 overexpression group were significantly higher than the other two groups (P < 0.05). The A value of RAMP-1 overexpression group at 24, 48, 72, 96 h were 0.628 ± 0.175, 0.896 ± 0.592, 1.055 ± 0.004, 1.179 ± 0.618, respectively, which were significantly higher than that of the other two groups (P < 0.05). The difference was most pronounced at 72 h. S-phase fraction of RAMP-1 overexpression group was (1.25 ± 0.13)%, (68.79 ± 0.56)%, (64.49 ± 1.59)%, (57.82 ± 0.75)%, respectively, which were significantly higher than the other two groups (P < 0.05). The difference was most pronounced at 8 h. CONCLUSIONS: RAMP-1 overexpression can promote CRLR distribution on MG-63 cell membrane and enhance CGRP's promotion effect on MG-63 cell proliferation.