Directed Dual Charge Pumping Tunes the d-Orbital Configuration of Pt Cluster Boosting Hydrogen Evolution Kinetic.

Achieving high catalytic activity with a minimum amount of platinum (Pt) is crucial for accelerating the cathodic hydrogen evolution reaction (HER) in proton exchange membrane (PEM) water electrolysis, yet it remains a significant challenge. Herein, a directed dual-charge pumping strategy to tune the d-orbital electronic distribution of Pt nanoclusters for efficient HER catalysis is proposed. Theoretical analysis reveals that the ligand effect and electronic metal-support interactions (EMSI) create an effective directional electron transfer channel for the d-orbital electrons of Pt, which in turn optimizes the binding strength to H*, thereby significantly enhancing HER efficiency of the Pt site. Experimentally, this directed dual-charge pumping strategy is validated by elaborating Sb-doped SnO2 (ATO) supported Fe-doped PtSn heterostructure catalysts (Fe-PtSn/ATO). The synthesized 3%Fe-PtSn/ATO catalysts exhibit lower overpotential (requiring only 10.5 mV to reach a current density of 10 mA cm- 2 ), higher mass activity (28.6 times higher than commercial 20 wt.% Pt/C), and stability in the HER process in acidic media. This innovative strategy presents a promising pathway for the development of highly efficient HER catalysts with low Pt loading.

In Situ Fast Construction of Ni3 S4 /FeS Catalysts on 3D Foam Structure Achieving Stable Large-Current-Density Water Oxidation.

By increasing the content of Ni3+ , the catalytic activity of nickel-based catalysts for the oxygen evolution reaction (OER), which is still problematic with current synthesis routes, can be increased. Herein, a Ni3+ -rich of Ni3 S4 /FeS on FeNi Foam (Ni3 S4 /FeS@FNF) via anodic electrodeposition to direct obtain high valence metal ions for OER catalyst is presented. XPS showed that the introduction of Fe not only further increased the Ni3+ concentration in Ni3 S4 /FeS to 95.02%, but also inhibited the dissolution of NiOOH by up to seven times. Furthermore, the OER kinetics is enhanced by the combination of the inner Ni3 S4 /FeS heterostructures and the electrochemically induced surface layers of oxides/hydroxides. Ni3 S4 /FeS@FNF shows the most excellent OER activity with a low Tafel slope of 11.2 mV dec-1 and overpotentials of 196 and 445 mV at current densities of 10 and 1400 mA cm-2 , respectively. Furthermore, the Ni3 S4 /FeS@FNF catalyst can be operated stably at 1500 mA cm-2 for 200 h without significant performance degradation. In conclusion, this work has significantly increased the high activity Ni3+ content in nickel-based OER electrocatalysts through an anodic electrodeposition strategy. The preparation process is time-saving and mature, which is expected to be applied in large-scale industrialization.

Contrast Media Ioversol Interferes with Urinalysis.

BACKGROUND: Ioversol is a commonly used non-ionic radiological contrast media in medical imaging to enhance the visualization of blood vessels, tissues, or organs. However, if it is not completely excreted, ioversol can interfere with urinalysis and lead to abnormal test results. METHODS: This study reported a case where the contrast media ioversol interfered with Sysmex UN automated urine analyzer. RESULTS: UC-3500 displayed no test results except the error code "0401". UF-4000 indicated "abnormally high RBCs" and no parameter results. CONCLUSIONS: Urine specimens containing contrast media are considered unqualified samples. Urinalysis should be performed only after the patient has completely excreted the contrast media.

Dual roles of sub-nanometer NiO in alkaline hydrogen evolution reaction: breaking the Volmer limitation and optimizing d-orbital electronic configuration.

Pt-based nanoclusters toward the hydrogen evolution reaction (HER) remain the most promising electrocatalysts. However, the sluggish alkaline Volmer-step kinetics and the high-cost have hampered progress in developing high-performance HER catalysts. Herein, we propose to construct sub-nanometer NiO to tune the d-orbital electronic structure of nanocluster-level Pt for breaking the Volmer-step limitation and reducing the Pt-loading. Theoretical simulations firstly suggest that electron transfer from NiO to Pt nanoclusters could downshift the Ed-band of Pt and result in the well-optimized adsorption/desorption strength of the hydrogen intermediate (H*), therefore accelerating the hydrogen generation rate. NiO and Pt nanoclusters confined into the inherent pores of N-doped carbon derived from ZIF-8 (Pt/NiO/NPC) were designed to realize the structure of computational prediction and boost the alkaline hydrogen evolution. The optimal 1.5%Pt/NiO/NPC exhibited an excellent HER performance and stability with a low Tafel slope (only 22.5 mv dec-1) and an overpotential of 25.2 mV at 10 mA cm-2. Importantly, the 1.5%Pt/NiO/NPC possesses a mass activity of 17.37 A mg-1 at the overpotential of 20 mV, over 54 times higher than the benchmark 20 wt% Pt/C. Furthermore, DFT calculations illustrate that the Volmer-step could be accelerated owing to the high OH- attraction of NiO nanoclusters, leading to the Pt nanoclusters exhibiting a balance of H* adsorption and desorption (ΔGH* = -0.082 eV). Our findings provide new insights into breaking the water dissociation limit of Pt-based catalysts by coupling with a metal oxide.

A nonsense mutation in the CUL3 gene in a Chinese patient with autism spectrum disorder and epilepsy: A case report.

RATIONALE: CUL3 (OMIM: 603136) encodes cullin-3, a core component of ubiquitin E3 ligase. Existing medical research suggests that CUL3 mutations are closely related to neurodevelopmental disorder with or without autism or seizures (neurodevelopmental disorder with autism and seizures, OMIM: 619239). However, the number of published case reports of autism spectrum disorder due to CUL3 gene mutations is limited. PATIENT CONCERN: A four-year-old Chinese girl presented with generalized epilepsy, and then exhibited developmental regression, including loss of her speaking ability, eye contact aversion, and stereotyped behavior. DIAGNOSES: Whole-exome sequencing identified a nonsense mutation in the CUL3 gene, being c.2065A > T (p.Lys689*); no previous similar case was reported. The final diagnosis was autism, epilepsy, and motor growth retardation. INTERVENTION: In order to improve quality of life of the patient, she was provided with exercise rehabilitation training and autism behavioral guidance therapy for 3 months. OUTCOMES: The patient's exercise capacity had improved, and improvements in autism symptoms were not obvious. LESSONS: For clinicians, patients with developmental regression accompanied with concurrent epilepsy and autism spectrum disorder should be advised that relevant genetic tests are necessary to clarify the diagnosis.

Clinical efficacy and safety of robotic retroperitoneal lymph node dissection for testicular cancer: a systematic review and meta-analysis.

Background: Retroperitoneal lymph node dissection (RPLND) is an effective treatment for testicular tumors. In recent years, with the development of robotics, many urological procedures performed via standard laparoscopy have been replaced by robots. Our objective was to compare the safety and efficacy of robotic retroperitoneal lymph node dissection (R-RPLND) versus Non-robotic retroperitoneal lymph node dissection (NR-RPLND) in testicular cancer. Methods: Pubmed, Embase, Scopus, Cochrane Library, and Web of Science databases were searched for literature on robotic surgery for testicular germ cell tumors up to April 2023. The statistical and sensitivity analyses were performed using Review Manager 5.3. Meta-analysis was performed to calculate mean difference (MD), odds ratio(OR), and 95% confidence interval (CI) effect indicators. Results: Eight studies with 3875 patients were finally included in this study, 453 with R-RPLND and 3422 with open retroperitoneal lymph node dissection (O-RPLND)/laparoscopic retroperitoneal lymph node dissection (L-RPLND). The results showed that R-RPLND had lower rates of intraoperative blood loss (MD = -436.39; 95% CI -707.60 to -165.19; P = 0.002), transfusion (OR = 0.06; 95% CI 0.01 to 0.26; P = 0.0001), total postoperative complication rates (OR = 0.39; 95% CI 0.21 to 0.70; P = 0.002), and length of stay (MD=-3.74; 95% CI -4.69 to -2.78; P<0.00001). In addition, there were no statistical differences between the two groups regarding perioperative and oncological outcomes regarding total operative time, the incidence of postoperative complications grade≥III, abnormal ejaculation rate, lymph node yield, and postoperative recurrence rate. Conclusions: The R-RPLND and O-RPLND/L-RPLND provide safe and effective retroperitoneal lymph node dissection for testicular cancer. Patients with R-RPLND have less intraoperative bleeding, shorter hospitalization period, fewer postoperative complications, and faster recovery. It should be considered a viable alternative to O-RPLND/L-RPLND. Systematic Review Registration: https://www.crd.york.ac.uk/PROSPERO, identifier CRD42023411696.

Clinical efficacy and safety of robot assisted surgery for choledochal cysts excisions: a systematic review and meta-analysis.

BACKGROUND: This study aimed to evaluate the safety and therapeutic effect of Robot-assisted surgery (RAS) for choledochal cysts (CCs) excisions. RESEARCH DESIGN AND METHODS: PubMed, EMBASE, Cochrane Library, Web of Science, CNKI, WanFang, VIP, and CBM were searched from database inception to 1 May 2022. The Newcastle-Ottawa scale (NOS) was used to conduct quality assessments, and RevMan (Version 5.4) was used to perform the meta-analysis. RESULTS: In all, 9 studies, involving 623 patients, were analyzed. RAS compared with LAS was associated with less intraoperative blood loss, shorter time to start solid diets, shorter postoperative hospital stay, and lower complications. There was no significant difference in operative time between the two groups, but the total costs were higher in RAS. Our subgroup analysis showed that RAS had significant advantages over LAS in the child group: minor bleeding, shorter length of hospital stay, and fewer postoperative complications. CONCLUSIONS: The available evidence indicates that the RAS system has the advantages of less intraoperative blood loss, minor tissue damage, quick recovery, and sound healing in treating choledochal cyst, which proves that the RAS is safely feasible. Especially in children, RAS tends to be a better choice.

Sperm telomere length as a novel biomarker of male infertility and embryonic development: A systematic review and meta-analysis.

Background: Telomeres have an essential role in maintaining the integrity and stability of the human chromosomal genome and preserving essential DNA biological functions. Several articles have been published on the association of STL with male semen parameters and clinical pregnancy. The results, however, are either inconclusive or inconsistent. Therefore, this meta-analysis aimed to systematically assess the accuracy and clinical value of sperm telomere length (STL) as a new marker for diagnosing male infertility and predicting the quality of embryonic development. Methods: We performed a comprehensive systematic search for relevant publications in PubMed, the Cochrane Library, Web of Science, Embase, Scopus, and Ovid, from database build to August 2022. All experimental studies exploring the association of STL with male semen quality, male infertility, or embryonic development were included. Results: Overall, Twelve prospective observational cohort studies (1700 patients) were eligible for inclusion in the meta-analysis. The meta-analysis showed a positive linear correlation between STL and semen parameters. The optimal cut-off value for STL diagnosing male infertility was 1.0, with a sensitivity and specificity of 80%. Regarding STL and embryonic development, the clinical pregnancy rate was associated with longer STL, and there was no significant difference between the two groups regarding fertilization rate. Conclusion: Our study showed that STL has good diagnostic and predictive value for male fertility and clinical pregnancy and could be used as a new biomarker for diagnosing male infertility and predicting embryonic development. Systematic Review Registration: https://www.crd.york.ac.uk/PROSPERO/, identifier CRD42022303333.

Pt3Sn nanoparticles enriched with SnO2/Pt3Sn interfaces for highly efficient alcohol electrooxidation.

Pt3Sn nanoparticles (NPs) enriched with Pt3Sn/ultra-small SnO2 interfaces (Pt3Sn@u-SnO2/NG) were synthesized through a thermal treatment of Pt2Sn/NG in a H2 atmosphere, followed by annealing under H2 and air conditions. The unique structure of Pt3Sn NPs enriched with Pt3Sn/SnO2 interfaces was observed on the Pt3Sn@u-SnO2/NG catalyst based on HRTEM. The optimized Pt3Sn@u-SnO2/NG catalyst achieves high catalytic activity with an ethanol oxidation reaction (EOR) activity of 366 mA mgPt -1 and a methanol oxidation reaction (MOR) activity of 503 mA mgPt -1 at the potential of 0.7 V, which are eight-fold and five-fold higher than those for the commercial Pt/C catalyst (44 and 99 mA mgPt -1, respectively). The Pt3Sn@u-SnO2/NG catalyst is found to be 3 times more stable and have higher CO tolerance than Pt/C. The outstanding performance of the Pt3Sn@u-SnO2/NG catalyst should be ascribed to the synergetic effect induced by the unique structure of Pt3Sn NPs enriched with Pt3Sn/SnO2 interfaces. The synergetic effect between Pt3Sn NPs and ultra-small SnO2 increases the performance for alcohol oxidation because the Sn in both Pt3Sn and SnO2 favors the removal of COads on the nearby Pt by providing OHads species at low potentials. The present work suggests that the Pt3Sn@u-SnO2 is indeed a unique kind of efficient electrocatalyst for alcohol electrooxidation.

Enhancement of the performance of Pd nanoclusters confined within ultrathin silica layers for formic acid oxidation.

The optimized design of highly active and stable anode electrocatalysts is essential for high performance direct formic acid fuel cells (DFAFCs). Herein, a facile and cost-effective strategy was proposed to fabricate a robust ultrasmall Pd nanocluster confined within ultrathin protective silica layers anchored on nitrogen doped reduced GO (NrGO) through generating amine functionalized graphene oxide with 3-aminopropyl triethoxysilane (APTES), followed by tuning the thickness of protective silica layers by precisely controlling the amount of tetraethylorthosilicate (TEOS). Amine functionalized graphene oxide generated by using APTES favors the formation of ultrasmall Pd nanoclusters due to the coordination of amine to PdCl24- while the confinement effect of ultrathin protective silica layers stabilizes ultrasmall Pd nanoclusters and impedes the agglomeration and sintering of ultrasmall Pd nanoclusters during electrocatalysis. As a result, the ultrasmall Pd nanoclusters (∼1.4 nm) confined in silica layers on NrGO (Pd/NrGO@SiO2) demonstrate a very high forward peak current density for formic acid oxidation (FAO) of 2.37 A mg-1, outperforming the Pd/C catalyst (0.30 A mg-1) and the Pd/rGO catalyst obtained by a conventional method (0.42 A mg-1). More importantly, our confined Pd catalysts show the highest stability of only 5% inconspicuous degradation of the initial mass activity after 1000 cycles, compared with Pd/C (almost 100% loss), Pd/rGO (61.5% loss) and Pd/NrGO (73.2% loss). These strategies in this work provide a new prospect for the design of excellent noble catalysts to overcome the challenges in the practical application of DFAFCs.

Encapsulating Pt Nanoparticles inside a Derived Two-Dimensional Metal-Organic Frameworks for the Enhancement of Catalytic Activity.

The development of highly active and stable electrocatalysts toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is a key for commercial application of fuel cells and water splitting. Here, we report a highly active and stable Pt nanoparticles (NPs) encapsulated in ultrathin two-dimensional (2D) carbon layers derived from the ultrathin 2D metal-organic framework precursor (ZIF-67). Electrochemical tests reveal that our approach not only stabilized Pt NPs successfully but also boosted Pt activities toward ORR and HER. We found that our Pt catalysts encapsulated in ultrathin 2D carbon layers exhibited an ORR activity of 5.9 and 12 times greater than those of the commercial Pt/C and Pt/RGO without 2D carbon layer protection. Our encapsulated Pt catalysts also show more than nine times higher stability than those of Pt/C catalysts. In addition to ORR, our novel encapsulated Pt catalysts display an extraordinary stability and activity toward HER, with a lower overpotential (14.3 mV in acidic media and 37.2 mV in alkaline media) at a current density of 10 mA cm-2 than Pt/C catalysts (23.1 mV in acidic media and 92.1 mV in alkaline media). The enhanced electrochemical activities and stability of our encapsulated Pt catalysts are attributed to the synergistic effect of Pt-based NPs and ultrathin 2D carbon layers derived from ZIF-67 with enriched active sites Co-Nx. First-principles simulations reveal that the synergistic catalysis of Pt-based NPs and Co-Nx derived from ZIF-67 improves the activity for ORR and HER.

Highly Active and Durable Ultrasmall Pd Nanocatalyst Encapsulated in Ultrathin Silica Layers by Selective Deposition for Formic Acid Oxidation.

The low performance of palladium (Pd) is a considerable challenge for direct formic acid fuel cells in practical applications. Herein, we develop a simple strategy to synthesize a highly active and durable Pd nanocatalyst encapsulated in ultrathin silica layers with vertically aligned nanochannels covered graphene oxides (Pd/rGO@pSiO2) without blocking active sites by selective deposition. The Pd/rGO@pSiO2 catalyst exhibits very high performance for a formic acid oxidation (FAO) reaction compared with the Pd/rGO without protective silica layers and commercial Pd/C catalysts. Pd/rGO@pSiO2 shows an FAO activity 3.9 and 3.8 times better than those of Pd/rGO and Pd/C catalysts, respectively. The Pd/rGO@pSiO2 catalysts are also almost 6-fold more stable than Pd/C and more than 3-fold more stable than Pd/rGO. The outstanding performance of our encapsulated Pd catalysts can be ascribed to the novel design of nanostructures by selective deposition fabricating ultrasmall Pd nanoparticles encapsulated in ultrathin silica layers with vertically aligned nanochannels, which not only avoid blocking the active sites but also facilitate the mass transfer in encapsulated catalysts. Our work indicates an important method to the rational design of high-performance catalysts for fuel cells in practical applications.

Structurally ordered PtSn intermetallic nanoparticles supported on ATO for efficient methanol oxidation reaction.

The development of cost-effective methanol oxidation reaction (MOR) catalysts with a high activity and stability is highly desirable for direct methanol fuel cells. In this study, the structurally ordered PtSn intermetallic nanoparticles supported on Sb-doped SnO2 (ATO) have been successfully synthesized in ethylene glycol (EG) solution at 200 °C. Pt NPs were firstly formed on ATO, followed by the transformation from Pt into hexagonal PtSn on the surface of ATO. The obtained structurally ordered PtSn intermetallic NPs supported on ATO demonstrate significantly enhanced MOR activity and durability in comparison with commercial Pt/C. Our PtSn intermetallic NPs supported on ATO show a MOR activity 4.1 times higher than that of commercial Pt/C catalysts. Accelerated durability tests indicate that the commercial Pt/C catalysts lose about 50% of their initial current density after 500 cycles while the Pt/ATO-200-3 h catalyst loses only about 15% of its initial current density. Our PtSn intermetallic NPs supported on ATO are also found to have higher CO tolerance than commercial Pt/C. This work demonstrates an important strategy to rationally design high-performance structurally ordered Pt-based intermetallic NP catalysts for fuel cells and other applications.