What Elements Really Intercalate into Pd Lattice When Heated in Dimethylformamide?

Palladium hydrides (PdHx) are pivotal in both fundamental research and practical applications across a wide spectrum. PdHx nanocrystals, synthesized by heating in dimethylformamide (DMF), exhibit remarkable stability, granting them widespread applications in the field of electrocatalysis. However, this stability appears inconsistent with their metastable nature. The substantial challenges in characterizing nanoscale structures contribute to the limited understanding of this anomalous phenomenon. Here, through a series of well-conceived experimental designs and advanced characterization techniques, including aberration-corrected scanning transmission electron microscopy (AC-STEM), in situ X-ray diffraction (XRD), and time-of-flight secondary ion mass spectrometry (TOF-SIMS), we have uncovered evidence that indicates the presence of C and N within the lattice of Pd (PdCxNy), rather than H (PdHx). By combining theoretical calculations, we have thoroughly studied the potential configurations and thermodynamic stability of PdCxNy, demonstrating a 2.5:1 ratio of C to N infiltration into the Pd lattice. Furthermore, we successfully modulated the electronic structure of Pd nanocrystals through C and N doping, enhancing their catalytic activity in methanol oxidation reactions. This breakthrough provides a new perspective on the structure and composition of Pd-based nanocrystals infused with light elements, paving the way for the development of advanced catalytic materials in the future.

Sandwich-type electrochemical immunosensing of CA125 by using nanoribbon-like Ti3C2Tx MXenes and toluidine blue/UIO-66-NH2.

CA125 (carbohydrate antigen 125) is an important biomarker of ovarian cancer, so developing effective method for its detection is of great significance. In the present work, a novel sandwich-like electrochemical immunosensor (STEM) of CA125 was constructed by preparing nanoribbon-like Ti3C2Tx MXenes (Ti3C2TxNR) to immobilize primary antibody (PAb) of CA125 and UIO-66-NH2 MOFs structure to immobilize second antibody (SAb) and electroactive toluidine blue (Tb) probe. In this designed STEM assay, the as-prepared Ti3C2TxNR nanohybrid offers the advantages in large surface area and conductivity as carrier, and UIO-66-NH2 provided an ideal platform to accommodate SAb and a large number of Tb molecules as signal amplifier. In the presence of CA125, the peak currents of Tb from the formed STEM structure increase with the increase of CA125 level. After optimizing the related control conditions, a wide linear range (0.2-150.0 U mL-1) and a very low detection limit (0.05 U mL-1) of CA125 were achieved. It's thus expected the developed STEM strategy has important applications for the detection of CA125.

Design of a new detachable pedicle screw based on medical optical imaging inspection to improve osteoporosis and enhance vertebral body revision effect.

Osteoporosis is a common bone disease that often leads to difficulty in vertebrae revision. Traditional pedicle screws are often complicated to operate and have poor visibility during implantation. A new detachable pedicle screw is needed to improve the revision effect. The aim of this study was to design a new detachable pedicle screw based on medical optical imaging to improve the outcome of vertebral revision in osteoporosis, and to improve operational feasibility and visibility. In this study, the parameters related to the degree of osteoporosis were obtained by optical imaging detection of the osteoporotic vertebral body. Then a new detachable pedicle screw was designed according to the test results to improve the effect of vertebral body revision. By preparing and optimizing the material and structure of the screw, it is ensured that it has sufficient mechanical strength and stability. Finally, the visibility and operability of the improved screw during implantation were verified by medical optical imaging. Compared with traditional screws, the new detachable pedicle screw can improve the vertebral body revision in the case of osteoporosis. The optical imaging test results show that the new screw has good visibility and maneuverability, providing more accurate guidance and positioning for the vertebral body revision operation.

Regulation of N6 -methyladenosine modification in erythropoiesis and thalassemia.

In eukaryotic RNA, N6 -methyladenosine (m6 A) is a prevalent form of methylation modification. The m6 A modification process is reversible and dynamic, written by m6 A methyltransferase complex, erased by m6 A demethylase, and recognized by m6 A binding proteins. Through mediating RNA stability, decay, alternative splicing, and translation processes, m6 A modification regulates gene expression at the post-transcriptional level. Erythropoiesis is the process of hematopoietic stem cells undergoing proliferation, a series of differentiation and maturation to form red blood cells (RBCs). Thalassemia is a common monogenic disease characterized by excessive production of ineffective RBCs in the peripheral circulation, resulting in hemolytic anemia. Increasing evidence suggests that m6 A modification plays a crucial role in erythropoiesis. In this review, we comprehensively summarize the function of m6 A modification in erythropoiesis and further generalize the mechanism of m6 A modification regulating ineffective erythropoiesis and fetal hemoglobin expression. The purpose is to improve the understanding of the pathogenesis of erythroid dysplasia and offer new perspectives for the diagnosis and treatment of thalassemia.

The interactions between ineffective erythropoiesis and ferroptosis in ß-thalassemia.

In Guangxi, Hainan, and Fujian Province in southern China, ß-thalassemia is a frequent monogenic hereditary disorder that is primarily defined by hemolytic anemia brought on by inefficient erythropoiesis. It has been found that ineffective erythropoiesis in ß-thalassemia is closely associated with a high accumulation of Reactive oxygen species, a product of oxidative stress, in erythroid cells. During recent years, ferroptosis is an iron-dependent lipid peroxidation that involves abnormalities in lipid and iron metabolism as well as reactive oxygen species homeostasis. It is a recently identified kind of programmed cell death. ß-thalassemia patients experience increased iron release from reticuloendothelial cells and intestinal absorption of iron, ultimately resulting in iron overload. Additionally, the secretion of Hepcidin is inhibited in these patients. What counts is both ineffective erythropoiesis and ferroptosis in ß-thalassemia are intricately linked to the iron metabolism and Reactive oxygen species homeostasis. Consequently, to shed further light on the pathophysiology of ß-thalassemia and propose fresh ideas for its therapy, this paper reviews ferroptosis, ineffective erythropoiesis, and the way they interact.

Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes.

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume a pivotal role in the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. The incorporation of various substituents into the C═C double bonds of tetrasubstituted alkenes is currently a highly significant research area. However, the synthesis of tetrasubstituted alkenes with diverse substituents on double bonds poses a significant challenge in achieving stereoselectivity. Here, we reported an efficient and convergent route of Cu-catalyzed borylalkynylation of both symmetrical and unsymmetrical 1,3-diynes, B2pin2, and acetylene bromide to the construction of boronated phenyldiethynylethylene (BPDEE) derivatives with excellent chemo-, stereo-, and regioselectivities. BPDEE derivatives could transform into novel tetrasubstituted organic π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), and phenyltriethynylethylene (PTEE) derivatives by a stepwise process, which provides a flexible platform for the synthesis of complex π-bond enrichment frameworks that were difficult to synthesize by previous methods. The initial optical characterization revealed that the synthesized molecules exhibited aggregation-induced emission (AIE) properties, which further establishes the groundwork for future applications and enriches and advances the field of functional π-conjugated frameworks research.

Generating active metal/oxide reverse interfaces through coordinated migration of single atoms.

Identification of active sites in catalytic materials is important and helps establish approaches to the precise design of catalysts for achieving high reactivity. Generally, active sites of conventional heterogeneous catalysts can be single atom, nanoparticle or a metal/oxide interface. Herein, we report that metal/oxide reverse interfaces can also be active sites which are created from the coordinated migration of metal and oxide atoms. As an example, a Pd1/CeO2 single-atom catalyst prepared via atom trapping, which is otherwise inactive at 30 °C, is able to completely oxidize formaldehyde after steam treatment. The enhanced reactivity is due to the formation of a Ce2O3-Pd nanoparticle domain interface, which is generated by the migration of both Ce and Pd atoms on the atom-trapped Pd1/CeO2 catalyst during steam treatment. We show that the generation of metal oxide-metal interfaces can be achieved in other heterogeneous catalysts due to the coordinated mobility of metal and oxide atoms, demonstrating the formation of a new active interface when using metal single-atom material as catalyst precursor.

Effects of cognitive behavioral therapy on anxiety and depressive symptoms in advanced cancer patients: A meta-analysis.

OBJECTIVE: To evaluate the effects of cognitive behavioral therapy on anxiety and depressive symptoms in patients with advanced cancer. METHODS: A systematical search was conducted on Embase, PubMed, Web of Science, Cochrane Library, PsycINFO, Chinese Biomedical Database, CNKI, VIP Database, and Wanfang database, and the search time was from the inception to May 26, 2023. Randomized controlled trials focusing on the effects of cognitive behavioral therapy on anxiety and depressive symptoms in patients with advanced cancer were collected using relevant terms such as advanced stage, cancer, anxiety, depression, and cognitive behavioral therapy. The quality of included studies was evaluated using the Cochrane risk of bias (ROB 2.0) tool, and meta-analysis was performed using RevMan5.4 software. RESULTS: 15 articles, including 1,597 patients, were included. Twelve of the studies reported the effect of CBT on anxiety symptoms in 1,485 advanced cancer patients; Fifteen studies reported the effect of CBT on depressive symptoms in 1,861 advanced cancer patients. The results of meta-analysis showed that CBT was effective in decreasing anxiety [SMD = -0.55, 95% CI (-0.82, -0.27), P < 0.001, I2 = 84%] and depressive symptoms [SMD = -0.38, 95% CI (-0.58, -0.17), P < 0.001, I2 = 78%] in patients with advanced cancer compared to controls, especially the interventions that were delivered lasted for 2-8 weeks. CONCLUSION: Cognitive behavioral therapy lasting for 2-8 weeks is effective for anxiety and depressive symptoms in advanced cancer patients to a moderate degree, but more rigorous research is needed to guide the choice between online and face-to-face delivery mode and the priority of self-guided versus therapist-guided interventions still needs to be studied.

Efficacy and safety of removing peritoneal dialysis catheters using the pull technique.

PURPOSE: To study the efficacy and safety of peritoneal dialysis (PD) catheter removal using the pull technique. METHODS: We conducted a retrospective analysis of 36 patients in whom the pull technique was used to remove a PD catheter. We evaluated the efficacy, safety, and health economic benefits of this technique by analyzing the pain score, duration of the procedure, complications during or after the procedure, and cost. RESULTS: The mean age (± standard deviation) of the 36 patients was 51 ± 14 years involving 27 males and 9 females with a mean body mass index was 23.4 ± 2.6. The mean duration of PD was 28 months (range 4-96 months). The site of the pull technique for peritoneal dialysis catheter removal was at the bedside or in the treatment room, with local anesthesia or no anesthesia. The mean duration of the procedure (from anesthesia to complete removal of the PD catheter) was 5-15 min. Only one patient experienced catheter rupture and no patients developed procedural or post-procedural bleeding or abdominal wall leakage. Infection did not occur at the inner or outer cuffs, tunnel, or outlet. Pain scores analyzed by a 10-point visual analogue scoring technique both immediately and 24 h after the procedure were 3.5 ± 1.7 and 1.2 ± 0.8, respectively. CONCLUSIONS: The pull technique is simple to perform, takes a short time, results in few complications and small wounds, causes only mild pain, enables fast recovery, and results in low medical costs.

Isolation and identification of active ingredients and biological activity of Dioscorea nipponica Makino.

This study reported the isolation and identification of bioactive compounds from Dioscorea nipponica Makino, a plant used in traditional medicine for various ailments. Nine compounds were isolated, including a new compound named as diosniposide E, which was elucidated by analyzing its 1H-NMR, 13C-NMR, DEPT, COSY, HMBC and MS data and comparing them with data available in literature. The other eight compounds were identified as known compounds. Theoretical calculations of energy and the generation of a molecular electrostatic potential surface map were employed to assess the antioxidant capacity of nine compounds, the calculation results exhibited that compounds 5 and 6 had strong antioxidant capacities. To further evaluate the antioxidant activities of the investigated compounds, the DPPH and ABTS assays were conducted. The results from the DPPH scavenging activity test revealed that compounds 4-6 exhibited enhanced scavenging activities compared to L-ascorbic acid, while displaying similar efficacy to trolox. Moreover, the ABTS scavenging activities of compounds 4-6 were found to surpass those of L-ascorbic acid and trolox. In terms of α-glucosidase inhibition, compounds 3 and 4 displayed remarkable inhibitory activities that surpassed the effects of acarbose. Additionally, compound 2 exhibited potent anticholinesterase activities, outperforming donepezil. This research provides insights into the potential bioactive compounds present in Dioscorea nipponica Makino and may contribute to its use in traditional medicine.

Improving the Hydrogen Oxidation Reaction Rate of Ru by Active Hydrogen in the Ultrathin Pd Interlayer.

Enhancing the catalytic activity of Ru metal in the hydrogen oxidation reaction (HOR) potential range, improving the insufficient activity of Ru caused by its oxophilicity, is of great significance for reducing the cost of anion exchange membrane fuel cells (AEMFCs). Here, we use Ru grown on Au@Pd as a model system to understand the underlying mechanism for activity improvement by combining direct in situ surface-enhanced Raman spectroscopy (SERS) evidence of the catalytic reaction intermediate (OHad) with in situ X-ray diffraction (XRD), electrochemical characterization, as well as DFT calculations. The results showed that the Au@Pd@Ru nanocatalyst utilizes the hydrogen storage capacity of the Pd interlayer to "temporarily" store the activated hydrogen enriched at the interface, which spontaneously overflows at the "hydrogen-deficient interface" to react with OHad adsorbed on Ru. It is the essential reason for the enhanced catalytic activity of Ru at anodic potential. This work deepens our understanding of the HOR mechanism and provides new ideas for the rational design of advanced electrocatalysts.

CeO2/Cu2O/Cu Tandem Interfaces for Efficient Water-Gas Shift Reaction Catalysis.

Metal-oxide interfaces on Cu-based catalysts play very important roles in the low-temperature water-gas shift reaction (LT-WGSR). However, developing catalysts with abundant, active, and robust Cu-metal oxide interfaces under LT-WGSR conditions remains challenging. Herein, we report the successful development of an inverse copper-ceria catalyst (Cu@CeO2), which exhibited very high efficiency for the LT-WGSR. At a reaction temperature of 250 °C, the LT-WGSR activity of the Cu@CeO2 catalyst was about three times higher than that of a pristine Cu catalyst without CeO2. Comprehensive quasi-in situ structural characterizations indicated that the Cu@CeO2 catalyst was rich in CeO2/Cu2O/Cu tandem interfaces. Reaction kinetics studies and density functional theory (DFT) calculations revealed that the Cu+/Cu0 interfaces were the active sites for the LT-WGSR, while adjacent CeO2 nanoparticles play a key role in activating H2O and stabilizing the Cu+/Cu0 interfaces. Our study highlights the role of the CeO2/Cu2O/Cu tandem interface in regulating catalyst activity and stability, thus contributing to the development of improved Cu-based catalysts for the LT-WGSR.

Comparative transcriptomics provides insights into the pathogenic immune response of brown leaf spots in weeping forsythia.

Weeping forsythia is an important ornamental, ecological and medicinal plant. Brown leaf spots limit the large-scale production of weeping forsythia as a medicinal crop. Alternaria alternata is a pathogen causing brown leaf spots in weeping forsythia; however, its pathogenesis and the immune response mechanisms of weeping forsythia remain unclear. In this study, we identified two mechanisms based on morphological anatomy, physiological indexes and gene expression analyses. Our results showed that A. alternata induced leaf stomata to open, invaded the mesophyll, dissolved the cell wall, destroyed the cell membrane and decreased the number of chloroplasts by up-regulating the expression of auxin-activated signaling pathway genes. Alternaria alternata also down-regulated iron-ion homeostasis and binding-related genes, which caused an increase in the levels of iron ions and reactive oxygen species in leaves. These processes eventually led to programmed cell death, destroying palisade and spongy tissues and causing the formation of iron rust spots. Alternaria alternata also caused defense and hypersensitive responses in weeping forsythia through signaling pathways mediated by flg22-like and elf18-like polypeptides, ethylene, H2O2 and bacterial secretion systems. Our study provides a theoretical basis for the control of brown leaf spots in weeping forsythia.

Low-Velocity Impact Resistance of 3D Re-Entrant Honeycomb Sandwich Structures with CFRP Face Sheets.

Lightweight sandwich structures have been receiving significant attention. By studying and imitating the structure of biomaterials, its application in the design of sandwich structures has also been found to be feasible. With inspiration from the arrangement of fish scales, a 3D re-entrant honeycomb was designed. In addition, a honeycomb stacking method is proposed. The resultant novel re-entrant honeycomb was utilized as the core of the sandwich structure in order to increase the impact resistance of the sandwich structure under impact loads. The honeycomb core is created using 3D printing. By using low-velocity impact experiments, the mechanical properties of the sandwich structure with Carbon-Fiber-Reinforced Polymer (CFRP) face sheets under different impact energies were studied. To further investigate the effect of the structural parameters on the structural, mechanical properties, a simulation model was developed. Simulation methods examined the effect of structural variables on peak contact force, contact time, and energy absorption. Compared to traditional re-entrant honeycomb, the impact resistance of the improved structure is more significant. Under the same impact energy, the upper face sheet of the re-entrant honeycomb sandwich structure sustains less damage and deformation. The improved structure reduces the upper face sheet damage depth by an average of 12% compared to the traditional structure. In addition, increasing the thickness of the face sheet will enhance the impact resistance of the sandwich panel, but an excessively thick face sheet may decrease the structure's energy absorption properties. Increasing the concave angle can effectively increase the energy absorption properties of the sandwich structure while preserving its original impact resistance. The research results show the advantages of the re-entrant honeycomb sandwich structure, which has certain significance for the study of the sandwich structure.

Radiologic Features of Atlas Occipitalization and Its Clinical Implications.

STUDY DESIGN: Retrospective radiographic analysis. OBJECTIVES: Evaluation of the anatomic features of the craniovertebral junction in patients with occipitalization with and without atlantoaxial dislocation (AAD). SUMMARY OF BACKGROUND DATA: Atlas occipitalization is a common feature of congenital AAD and usually requires surgical intervention. However, not all instances of occipitalization necessarily lead to AAD. No study has specifically examined and compared the craniovertebral bony morphology in occipitalization with, and without, AAD. MATERIALS AND METHOD: We reviewed computed tomography (CT) scans of 2500 adult outpatients. Occipitalization cases without AAD (ON) were selected. Meanwhile, a series of 20 inpatient occipitalization cases with AAD (OD) were obtained in parallel. Another 20 control cases without occipitalization were also included. Multi-directional reconstructed CT images of all cases were analyzed. RESULTS: A total of 18 adults with ON were found in all 2500 outpatients (0.7%). Both anterior height and posterior height of C1 lateral mass in the control group were significantly larger than those in both the ON and OD groups, whereas posterior height in the OD group was significantly less than that in the ON group. Three morphologic types of the occipitalized atlas posterior arch were identified: Type I, bilateral sides were unfused with opisthion; Type II, unilateral side was unfused with opisthion, whereas the other side was fused; and Type III, bilateral sides were fused with opisthion. In the ON group, three cases were type I (17%), six cases were type II (33%), and nine cases were type III (50%). In the OD group, all 20 cases were type III (100%). CONCLUSIONS: Atlas occipitalization with, and without, AAD results from a distinctly different bony morphology at the craniovertebral junction. The novel classification system based on reconstructed CT images may be useful in prognosticating AAD in the setting of atlas occipitalization.

Identification of the active triple-phase boundary of a non-Pt catalyst layer in fuel cells.

The rational design of non-Pt oxygen reduction reaction (ORR) catalysts and catalyst layers in fuel cells is largely impeded by insufficient knowledge of triple-phase boundaries (TPBs) in the micropore and mesopore ranges. Here, we developed a size-sensitive molecular probe method to resolve the TPB of Fe/N/C catalyst layers in these size ranges. More than 70% of the ORR activity was found to be contributed by the 0.8- to 2.0-nanometer micropores of Fe/N/C catalysts, even at a low micropore area fraction of 29%. Acid-alkaline interactions at the catalyst-polyelectrolyte interface deactivate the active sites in mesopores and macropores, resulting in inactive TPBs, leaving micropores without the interaction as the active TPBs. The concept of active and inactive TPBs provides a previously unidentified design principle for non-Pt catalyst and catalyst layers in fuel cells.

Layered Pd oxide on PdSn nanowires for boosting direct H2O2 synthesis.

Hydrogen peroxide (H2O2) has the wide range of applications in industry and living life. However, the development of the efficient heterogeneous catalyst in the direct H2O2 synthesis (DHS) from H2 and O2 remains a formidable challenge because of the low H2O2 producibility. Herein, we develop a two-step approach to prepare PdSn nanowire catalysts, which comprises Pd oxide layered on PdSn nanowires (PdL/PdSn-NW). The PdL/PdSn-NW displays superior reactivity in the DHS at zero Celcius, presenting the H2O2 producibility of 528 mol kgcat-1·h-1 and H2O2 selectivity of >95%. A layer of Pd oxide on the PdSn nanowire generates bi-coordinated Pd, leading to the different adsorption behaviors of O2, H2 and H2O2 on the PdL/PdSn-NW. Furthermore, the weak adsorption of H2O2 on the PdL/PdSn-NW contributes to the low activation energy and high H2O2 producibility. This surface engineering approach, depositing metal layer on metal nanowires, provides a new insight in the rational designing of efficient catalyst for DHS.

Maximizing noble metal utilization in solid catalysts by control of nanoparticle location.

Maximizing the utilization of noble metals is crucial for applications such as catalysis. We found that the minimum loading of platinum for optimal performance in the hydroconversion of n-alkanes for industrially relevant bifunctional catalysts could be reduced by a factor of 10 or more through the rational arranging of functional sites at the nanoscale. Intentionally depositing traces of platinum nanoparticles on the alumina binder or the outer surface of zeolite crystals, instead of inside the zeolite crystals, enhanced isomer selectivity without compromising activity. Separation between platinum and zeolite acid sites preserved the metal and acid functions by limiting micropore blockage by metal clusters and enhancing access to metal sites. Reduced platinum nanoparticles were more active than platinum single atoms strongly bonded to the alumina binder.

Ankle Arthrodesis Combined With Mosaic Bone Autograft Transplantation for End-Stage Ankle Osteoarthritis With Large Cysts of Talar Dome.

End-stage ankle osteoarthritis with large cysts of talar dome can be challenging to treat. Twenty patients diagnosed as end-stage ankle arthritis with large talar cysts between 04/2010 and 02/2016 were randomly divided into experimental group (10 cases) and conventional group (10 cases) by random number method. Patients in the experimental group were treated with ankle arthrodesis combined with a concomitant procedure of mosaic bone autograft transplantation, the conventional group under the ankle arthrodesis. The operation time, intraoperative blood loss, postoperative hospital stay, the time of bone union, and postoperative height of the talus between the 2 groups were compared. The preoperative and postoperative American Orthopaedic Foot and Ankle Society ankle-hindfoot scale score were also recorded and compared. There was no significant difference in the operation time, intraoperative blood loss, and postoperative hospital stay between the 2 groups. The postoperative height of the talus body and the time of bone union were better in the experimental group than that in the conventional group (p < .05). The results of follow-up showed that the American Orthopaedic Foot and Ankle Society scores of the conventional group were lower than those in the experimental group (p < .001). And the incidence of complication (10%) in the experimental group was significantly lower than that in the conventional group (40%). The use of tibiotalar arthrodesis combined with mosaic bone autograft transfer may be potentially an effective option for the treatment of end-stage ankle arthritis with large talar cysts.