Precise arrangement of metal atoms at the interface by a thermal printing strategy.

The kinetics and pathway of most catalyzed reactions depend on the existence of interface, which makes the precise construction of highly active single-atom sites at the reaction interface a desirable goal. Herein, we propose a thermal printing strategy that not only arranges metal atoms at the silica and carbon layer interface but also stabilizes them by strong coordination. Just like the typesetting of Chinese characters on paper, this method relies on the controlled migration of movable nanoparticles between two contact substrates and the simultaneous emission of atoms from the nanoparticle surface at high temperatures. Observed by in situ transmission electron microscopy, a single Fe3O4 nanoparticle migrates from the core of a SiO2 sphere to the surface like a droplet at high temperatures, moves along the interface of SiO2 and the coated carbon layer, and releases metal atoms until it disappears completely. These detached atoms are then in situ trapped by nitrogen and sulfur defects in the carbon layer to generate Fe single-atom sites, exhibiting excellent activity for oxygen reduction reaction. Also, sites' densities can be regulated by controlling the size of Fe3O4 nanoparticle between the two surfaces. More importantly, this strategy is applicable to synthesize Mn, Co, Pt, Pd, Au single-atom sites, which provide a general route to arrange single-atom sites at the interface of different supports for various applications.

Effects of carnitine on glucose and lipid metabolic profiles and fertility outcomes in women with polycystic ovary syndrome: A systematic review and meta-analysis.

OBJECTIVES: To quantify the effect of carnitine on glucose and lipid metabolic profiles and fertility outcomes in women with Polycystic ovary syndrome (PCOS). DESIGN: A systematic review and meta-analysis were conducted. PATIENTS: Women with PCOS diagnosed by Rotterdam or Androgen Excess Society (AES) criteria and taking carnitine supplement were assessment. MEASUREMENTS: Fertility outcomes (ovulation, clinical pregnancy, live birth, and miscarriage), lipid parameters (BMI, triglyceride, total cholesterol, high-density lipoprotein, low-density lipoprotein), fasting glucose and insulin, and Homeostatic Model Assessment for Insulin Resistance (HOMA-IR). RESULTS: In total, 839 participants were included in this analysis. The dosage of carnitine and treatment duration reported by studies varied from 250 mg to 3000 mg daily and 84 to 90 days, respectively. The publication bias was absent. Compared with placebo, carnitine significantly improved ovulation rates (RR 3.42, 95% CI 2.39 to 4.89, I2 = 0%) and pregnancy rates (RR 11.05, 95% CI 1.21 to 100.58, I2 = 79%). None of included studies reported live birth. After treatment, carnitine resulted in significant reductions relative to baseline in body mass index (BMI, MD -0.93 kg/m2, 95% CI -1.15 to -0.70, I2 = 55.0%), insulin levels (MD -2.47 mIU/L, 95% CI -4.49 to -0.45, I2 = 0%) and the Homeostasis Model Assessment index (MD -0.67, 95% CI -1.20 to -0.14, I2 = 0%) than placebo, but not for lipid profiles including triglyceride, total cholesterol, and low-density lipoprotein. CONCLUSION: With the available literature, carnitine seems to improve ovulation and clinical pregnancy and insulin resistance, BMI in women with PCOS. These effects are warranted to be further validated, due to insufficient statistical power.

Tailoring Unsymmetrical-Coordinated Atomic Site in Oxide-Supported Pt Catalysts for Enhanced Surface Activity and Stability.

The catalytic properties of supported metal heterostructures critically depend on the design of metal sites. Although it is well-known that the supports can influence the catalytic activities of metals, precisely regulating the metal-support interactions to achieve highly active and durable catalysts still remain challenging. Here, the authors develop a support effect in the oxide-supported metal monomers (involving Pt, Cu, and Ni) catalysts by means of engineering nitrogen-assisted nanopocket sites. It is found that the nitrogen-permeating process can induce the reconstitution of vacancy interface, resulting in an unsymmetrical atomic arrangement around the vacancy center. The resultant vacancy framework is more beneficial to stabilize Pt monomers and prevent diffusion, which can be further verified by the density functional theory calculations. The final Pt-N/SnO2 catalysts exhibit superior activity and stability for HCHO response (26.5 to 15 ppm). This higher activity allows the reaction to proceed at a lower operating temperature (100 °C). Incorporated with wireless intelligent-sensing system, the Pt-N/SnO2 catalysts can further achieve continuous monitoring of HCHO levels and cloud-based terminal data storage.

Single Iron Site Nanozyme for Ultrasensitive Glucose Detection.

Nanomaterials with enzyme-mimicking characteristics have engaged great awareness in various fields owing to their comparative low cost, high stability, and large-scale preparation. However, the wide application of nanozymes is seriously restricted by the relatively low catalytic activity and poor specificity, primarily because of the inhomogeneous catalytic sites and unclear catalytic mechanisms. Herein, a support-sacrificed strategy is demonstrated to prepare a single iron site nanozyme (Fe SSN) dispersed on the porous N-doped carbon. With well-defined coordination structure and high density of active sites, the Fe SSN performs prominent peroxidase-like activity by efficiently activating H2 O2 into hydroxyl radical (•OH) species. Furthermore, the Fe SSN is applied in colorimetric detection of glucose through a multienzyme biocatalytic cascade platform. Moreover, a low-cost integrated agarose-based hydrogel colorimetric biosensor is designed and successfully achieves the visualization evaluation and quantitative detection of glucose. This work expands the application of single-site catalysts in the fields of nanozyme-based biosensors and personal biomedical diagnosis.

Broadband, polarization insensitive low-scattering metasurface based on lossy Pancharatnam-Berry phase particles.

In this paper, a novel composite metasurface (MS) with diffuse scattering and absorbing characteristics is proposed to reduce the radar cross section (RCS) of a metal target in a broad band. The combination of absorption and diffusion is realized based on lossy Pancharatnam-Berry (PB) phase particles. The units are arranged according to a coding sequence which is obtained by an optimization algorithm based on simulated annealing algorithm. Simulation results show that the MS obtained based on the optimized coding sequence is insensitive to polarization. Due to the combination of absorption and diffusion, the MS has good performance in both monostatic and bistatic scenarios. Finally, the proposed MS is fabricated and measured, and the experimental results are in good agreement with simulation results. A 10 dB backward reflection reduction can be achieved from 21GHz to 38GHz and a 15 dB backward reflection reduction can be achieved from 22GHz to 35GHz under normal incidence. Furthermore, the MS has good performance under large angle (<45°) incidence.

Risk factors for intraoperative pressure injuries in patients undergoing digestive surgery: A retrospective study.

AIM AND OBJECTIVE: To investigate the incidence of intraoperative blanchable erythema and pressure injuries in patients undergoing digestive surgery and to explore potential risk factors. BACKGROUND: Pressure injuries pose significant economic and healthcare burden to patients and are used as one of the key indicators of nursing in the operation room with high incidence. DESIGN: A retrospective observational study. METHODS: Basic information and the results of 3S intraoperative risk assessment scale of pressure injury were obtained from the information system. And the patients with intraoperative blanchable erythema or pressure injuries were followed up for 72 hr by the information system. The clinical data were collected to analyse risk factors for intraoperative blanchable erythema and pressure injuries by univariate analysis and logistic regression analysis. STROBE checklist for cohort studies was applied in the preparation of the paper. RESULTS: Of 5,136 surgical cases, 134 (2.61%) had blanchable erythema, 37 (0.72%) had intraoperative pressure injuries, and 8 (0.16%) had pressure injuries at 72-hr follow-up. Preoperative skin under compression, preoperative physical activity, surgical position and extra intraoperative pressure were considered independent risk factors for intraoperative pressure injuries. CONCLUSION: The incidence of pressure injuries in our study was lower than those reported in the previous studies. Accessing preoperative skin under compression, preoperative physical activity, surgical position and extra intraoperative pressure was considered to be significant for preventing pressure injuries. RELEVANCE TO CLINICAL PRACTICE: The findings suggest that preoperative skin under compression, preoperative physical activity, surgical position and extra intraoperative pressure are associated with intraoperative pressure injuries in patients undergoing digestive surgery.

A Supported Nickel Catalyst Stabilized by a Surface Digging Effect for Efficient Methane Oxidation.

A surface digging effect of supported Ni NPs on an amorphous N-doped carbon is described, during which the surface-loaded Ni NPs would etch and sink into the underneath carbon support to prevent sintering. This process is driven by the strong coordination interaction between the surface Ni atoms and N-rich defects. In the aim of activation of C-H bonds for methane oxidation, those sinking Ni NPs could be further transformed into thermodynamically stable and active metal-defect sites within the as-generated surface holes by simply elevating the temperature. In situ transmission electron microscopy images reveal the sunk Ni NPs dig themselves adaptive surface holes, which would largely prevent the migration of Ni NPs without weakening their accessibility. The reported two-step strategy opens up a new route to manufacture sintering-resistant supported metal catalysts without degrading their catalytic efficiency.

Liquid Metal Encased in Biomimic Polydopamine Armor to Reinforce Photothermal Conversion and Photothermal Stability.

Liquid metal (LM) faces numerous obstacles like spontaneous coalescence, prone oxidizability, and deterioration in photothermal conversion, impeding the potential application as photothermal agent. To tackle these issues, several studies have focused on surface engineering strategy. Developing a feasible and efficient surface engineering strategy is crucial to prevent the aggregation and coalescence of LM, while also ensuring exceptional photothermal conversion and biosecurity. In order to achieve these goals in this work, the biomimetic polydopamine (PDA) armor was chosen to encase a typical LM (eutectic gallium-indium-tin alloy) via self-polymerization. Characterization results showed that the PDA encased LM nanoparticle exhibited enhanced photothermal stability, photothermal conversion, and biosecurity, which could be derived from the following factors: (1) The PDA protective shell acted as an "armor", isolating LM from dissolved oxygen and water, inhibiting heating-accelerated oxidation and shape morphing. (2) The exceptional near-infrared absorption of PDA was conducive to the photothermal conversion. (3) The biomimetic characteristic of polydopamine (PDA) was advantageous for improving the biosecurity. Hence, this work presented a new surface engineering strategy to reinforce LM for photothermal conversion application.

Cell-inspired design of cascade catalysis system by 3D spatially separated active sites.

Cells possess isolated compartments that spatially confine different enzymes, enabling high-efficiency enzymatic cascade reactions. Herein, we report a cell-inspired design of biomimetic cascade catalysis system by immobilizing Fe single atoms and Au nanoparticles on the inner and outer layers of three-dimensional nanocapsules, respectively. The different metal sites catalyze independently and work synergistically to enable engineered and cascade glucose detection. The biomimetic catalysis system demonstrates ~ 9.8- and 2-fold cascade activity enhancement than conventional mixing and coplanar construction systems, respectively. Furthermore, the biomimetic catalysis system is successfully demonstrated for the colorimetric glucose detection with high catalytic activity and selectivity. Also, the proposed gel-based sensor is integrated with smartphone to enable real-time and visual determination of glucose. More importantly, the gel-based sensor exhibits a high correlation with a commercial glucometer in real samples detection. These findings provide a strategy to design an efficient biomimetic catalysis system for applications in bioassays and nanobiomedicines.

Solid Migration to Assemble a Flower-like Nanozyme with Highly Dense Single Copper Sites for Specific Phenol Oxidation.

Nanozymes with high catalytic stability and sustainability have emerged as powerful competitors to natural enzymes for diverse biocatalytic applications. However, constructing a nanozyme with high specificity is one of their biggest challenges. Herein, we develop a facile solid migration strategy to access a flower-like single copper site nanozyme (Cu SSN) via direct transformation of copper foam activated by 2-methylimidazole. With highly clustered CuN3 sites whose local structure is similar to that of natural polyphenol oxidase, the Cu SSN exhibits excellent activity and specificity to oxidize phenols without peroxidase-like activity. Furthermore, the Cu SSN shows high sensitivity in the colorimetric detection of epinephrine with a low detection limit of 0.10 µg mL-1, exceeding that of most previously reported enzyme-mimicking catalysts. This work not only provides a simple method for the large-scale preparation of high-performance nanozymes but also offers an inspiration for the design of highly specific nanozymes by mimicking the synergy among sites in natural enzymes.

Facet Engineering of Nanoceria for Enzyme-Mimetic Catalysis.

Nanomaterials with natural enzyme-mimicking characteristics have aroused extensive attention in various fields owing to their economical price, ease of large-scale production, and environmental resistance. Previous investigations have demonstrated that composition, size, shape, and surface modification play important roles in the enzymelike activity of nanomaterials; however, a fundamental understanding of the crystal facet effect, which determines surface energy or surface reactivity, has rarely been reported. Herein, fluorite cubic CeO2 nanocrystals with controllably exposed {111}, {100}, or {110} facets are fabricated as proof-of-concept candidates to study the facet effect on the peroxidase-mimetic activity. Both experiments and theoretical results show that {110}-dominated CeO2 nanorods (CeO2 NR) possess the highest peroxidase-mimetic activity due to the richest defects on their surfaces, which are beneficial to capture metal atoms to further enrich their artificial enzymatic functionality for cascade catalysis. For instance, the introduction of atomically dispersed Au on CeO2 NR surfaces not only enhances the peroxidase activity but also endows the obtained catalyst with glucose oxidase (GOx)-mimicking activity, which realizes enzyme-free cascade reactions for glucose colorimetric detection. This work not only provides an understanding for crystal facet engineering of nanomaterials to enhance the catalytic activity but also opens up a new way for the design of biomimetic nanomaterials with multiple functions.

New macronarian from the Middle Jurassic of Chongqing, China: phylogenetic and biogeographic implications for neosauropod dinosaur evolution.

Macronaria is a clade of gigantic body-sized sauropod dinosaurs widely distributed from the Late Jurassic to the Late Cretaceous globally. However, its origin, early diversification, and dispersal are still controversial. Here, we report a new macronarian Yuzhoulong qurenensis gen. et sp. nov. excavated from the Middle Jurassic (Bathonian) Lower Shaximiao Formation. Yuzhoulong qurenensis bears a unique combination of features, such as two accessory fossae that exist on the posterior surface of dorsal diapophyses of anterior dorsal vertebrae. Results of phylogenetic analyses demonstrate it is one of the earliest-diverging macronarians. This new material represents a Middle Jurassic fossil record of macronarian sauropod worldwide and improves the understanding of the early diversity and dispersal of the Neosauropoda. This discovery further supports that sauropods achieved a more rapid and varied morphological diversity and palaeogeographical dispersal in the Middle Jurassic.

Dual confinement of high-loading enzymes within metal-organic frameworks for glucose sensor with enhanced cascade biocatalysis.

The intrinsically fragile nature and leakage of the enzymes is a major obstacle for the commercial sensor of a continuous glucose monitoring system. Herein, a dual confinement effect is developed in a three dimensional (3D) nanocage-based zeolite imidazole framework (NC-ZIF), during which the high-loading enzymes can be well encapsulated with unusual bioactivity and stability. The shell of NC-ZIF sets the first confinement to prevent enzymes leakage, and the interior nanocage of NC-ZIF provides second confinement to immobilize enzymes and offers a spacious environment to maintain their conformational freedom. Moreover, the mesoporosity of the formed NC-ZIF can be precisely controlled, which can effectively enhance the mass transport. The resulted GOx/Hemin@NC-ZIF multi-enzymes system could not only realize rapid detection of glucose by colorimetric and electrochemical sensors with high catalytic cascade activity (with an 8.3-fold and 16-fold enhancements in comparison with free enzymes in solution, respectively), but also exhibit long-term stability, excellent selectivity and reusability. More importantly, the based wearable sweatband sensor measurement results showed a high correlation (>0.84, P < 0.001) with the levels measured by commercial glucometer. The reported dual confinement strategy opens up a window to immobilize enzymes with enhanced catalytic efficiency and stability for clinical-grade noninvasive continuous glucose sensor.

Rapid screening for chromosomal aneuploidies using array-MLPA.

BACKGROUND: Chromosome abnormalities, especially trisomy of chromosome 21, 13, or 18 as well as sex chromosome aneuploidy, are a well-established cause of pregnancy loss. Cultured cell karyotype analysis and FISH have been considered reliable detectors of fetal abnormality. However, results are usually not available for 3-4 days or more. Multiplex ligation-dependent probe amplification (MLPA) has emerged as an alternative rapid technique for detection of chromosome aneuploidies. However, conventional MLPA does not allow for relative quantification of more than 50 different target sequences in one reaction and does not detect mosaic trisomy. A multiplexed MLPA with more sensitive detection would be useful for fetal genetic screening. METHODS: We developed a method of array-based MLPA to rapidly screen for common aneuploidies. We designed 116 universal tag-probes covering chromosomes 13, 18, 21, X, and Y, and 8 control autosomal genes. We performed MLPA and hybridized the products on a 4-well flow-through microarray system. We determined chromosome copy numbers by analyzing the relative signals of the chromosome-specific probes. RESULTS: In a blind study of 161 peripheral blood and 12 amniotic fluid samples previously karyotyped, 169 of 173 (97.7%) including all the amniotic fluid samples were correctly identified by array-MLPA. Furthermore, we detected two chromosome X monosomy mosaic cases in which the mosaism rates estimated by array-MLPA were basically consistent with the results from karyotyping. Additionally, we identified five Y chromosome abnormalities in which G-banding could not distinguish their origins for four of the five cases. CONCLUSIONS: Our study demonstrates the successful application and strong potential of array-MLPA in clinical diagnosis and prenatal testing for rapid and sensitive chromosomal aneuploidy screening. Furthermore, we have developed a simple and rapid procedure for screening copy numbers on chromosomes 13, 18, 21, X, and Y using array-MLPA.

Integrating single-cobalt-site and electric field of boron nitride in dechlorination electrocatalysts by bioinspired design.

The construction of enzyme-inspired artificial catalysts with enzyme-like active sites and microenvironment remains a great challenge. Herein, we report a single-atomic-site Co catalyst supported by carbon doped boron nitride (BCN) with locally polarized B-N bonds (Co SAs/BCN) to simulate the reductive dehalogenases. Density functional theory analysis suggests that the BCN supports, featured with ionic characteristics, provide additional electric field effect compared with graphitic carbon or N-doped carbon (CN), which could facilitate the adsorption of polarized organochlorides. Consistent with the theoretical results, the Co SAs/BCN catalyst delivers a high activity with nearly complete dechlorination (~98%) at a potential of -0.9 V versus Ag/AgCl for chloramphenicol (CAP), showing that the rate constant (k) contributed by unit mass of metal (k/ratio) is 4 and 19 times more active than those of the Co SAs/CN and state-of-the-art Pd/C catalyst, respectively. We show that Co single atoms coupled with BCN host exhibit high stability and selectivity in CAP dechlorination and suppress the competing hydrogen evolution reaction, endowing the Co SAs/BCN as a candidate for sustainable conversion of organic chloride.

Biocompatible Ruthenium Single-Atom Catalyst for Cascade Enzyme-Mimicking Therapy.

Rationally constructing single-atom enzymes (SAEs) with superior activity, robust stability, and good biocompatibility is crucial for tumor therapy but still remains a substantial challenge. In this work, we adopt biocompatible carbon dots as the carrier material to load Ru single atoms, achieving Ru SAEs with superior multiple enzyme-like activity and stability. Ru SAEs behave as oxidase, peroxidase, and glutathione oxidase mimics to synchronously catalyze the generation of reactive oxygen species (ROS) and the depletion of glutathione, thus amplifying the ROS damage and finally causing the death of cancer cells. Notably, Ru SAEs exhibit excellent peroxidase-like activity with a specific activity of 7.5 U/mg, which surpasses most of the reported SAEs and is 20 times higher than that of Ru/C. Theoretical results reveal that the electrons of the Ru 4d orbital in Ru SAEs are transferred to O atoms in H2O2 and then efficiently activate H2O2 to produce •OH. Our work may provide some inspiration for the design of SAEs for cancer therapy.

Construction of highly accessible single Co site catalyst for glucose detection.

The development of high-performance glucose sensors is an urgent need, especially for diabetes mellitus diagnosis. However, the glucose monitoring is conventionally operated in an invasive finger-prick manner and their noninvasive alternatives largely suffered from the relatively poor sensitivity, selectivity, and stability, resulted from the lack of robust and efficient catalysts. In this paper, we design a concave shaped nitrogen-doped carbon framework embellished with single Co site catalyst (Co SSC) by selectively controlling the etching rate on different facet of carbon substrate, which is beneficial to the diffusion and contact of analyte. The Co SSC prompts a significant improvement in the sensitivity of the solution-gated graphene transistor (SGGT) devices, with three orders of magnitude better than those of SGGT devices without catalysts. Our findings expand the field of single site catalyst in the application of biosensors, diabetes diagnostics and personalized health-care monitoring.

Unraveling the enzyme-like activity of heterogeneous single atom catalyst.

Herein, we report a heterogeneous single iron atom catalyst exhibiting excellent peroxidase, oxidase and catalase enzyme-like activities (defined as single atom enzymes, SAEs), exceeding those of Fe3O4 nanozymes by a factor of 40. Our findings open up a new family of artificial materials that mimic natural enzymes.

Detection of Bisphenol A Using DNA-Functionalized Graphene Field Effect Transistors Integrated in Microfluidic Systems.

Bisphenol A (BPA) detection has attracted much attention recently for its importance to food safety and environment. The DNA-functionalized solution-gated graphene transistors are integrated in microfluidic systems and used for recycling detections of BPA for the first time. In the presence of BPA, both single- and double-stranded DNA molecules are detached and released from the graphene surface in aqueous solutions, leading to the change of device electrical performance. The channel currents of the devices change monotonically with the concentration of BPA. Moreover, the devices modified with double-stranded DNA are more sensitive to BPA and show the detection limit down to 10 ng/mL. The highly sensitive label-free BPA sensors are expected to be used for convenient BPA detections in many applications.

Highly selective and sensitive sensor based on an organic electrochemical transistor for the detection of ascorbic acid.

In this study, an organic electrochemical transistor sensor (OECT) with a molecularly imprinted polymer (MIP)-modified gate electrode was prepared for the detection of ascorbic acid (AA). The combination of the amplification function of an OECT and the selective specificity of MIPs afforded a highly sensitive, selective OECT sensor. Cyclic voltammetry and electrochemical impedance spectroscopy measurements were carried out to monitor the stepwise fabrication of the modified electrodes and the adsorption capacity of the MIP/Au electrodes. Atomic force microscopy was employed for examining the surface morphology of the electrodes. Important detection parameters, pH and detection temperature were optimized. With the change in the relative concentration of AA from 1µM to 100µM, the MIP-OECT sensor exhibited a low detection limit of 10nM (S/N > 3) and a sensitivity of 75.3µA channel current change per decade under optimal conditions. In addition, the MIP-OECT sensor exhibited excellent specific recognition ability to AA, which prevented the interference from other structurally similar compounds (e.g., aspartic acid, glucose, uric acid, glycine, glutathione, H2O2), and common metal ions (K+, Na+, Ca2+, Mg2+, and Fe2+). In addition, a series of vitamin C beverages were analyzed to demonstrate the feasibility of the MIP-OECT sensor. Using the proposed principle, several other sensors with improved performance can be constructed via the modification of organic electrochemical transistors with appropriate MIP films.