Reticular Chemistry and In Situ "One-Pot" Strategy: A Dream Combination to Construct Metal-Organic Frameworks.

The establishment of reticular chemistry has significantly facilitated the development of porous materials, especially for metal-organic frameworks (MOFs). On the other hand, as an alternative approach, in situ "one-pot" strategy has been explored as a promising approach to constructing MOFs, in which the synthesis of organic linkers and the sequential construction of MOFs are integrated into one solvothermal condition. This strategy can efficiently avoid the limitations faced in the traditional construction method, such as time-consuming organic synthesis and multiple separation and purification. Herein, inspired by the reaction of aldehydes and o-phenylenediamine and deep structural analysis of UiO-68, a series of tetra-, hexa-, and octa-topic carboxylic acids are synthesized using 2',3'-diamino-[1,1':4',1'"-terphenyl]-4,4'"-dicarboxylic acid and di-, tri-, and tetra-topic aldehydes as precursor. Then nine multicarboxylate-based zirconium MOFs (Zr-MOFs) are successfully constructed via the combination of reticular chemistry and in situ "one-pot" strategy. The resultant Zr-MOFs can be regarded as the partial face decoration of UiO-68. More importantly, the emission properties of resultant Zr-MOFs can be well controlled using aldehydes with tunable electronic structures. This work provides a new path to rational design and construction of porous materials with specific structures guided by reticular chemistry and conducted using in situ "one-pot" strategy.

Porous organic polymers assisted aptamer signal amplification for enhanced photoeletrochemical detection of MUC1.

Mucin1 (MUC1) is an extensively glycosylated transmembrane protein that is widely distributed and overexpressed on the surface of cancer cells, playing an important role in tumor occurrence and metastasis. Therefore, highly sensitive detection of MUC1 is of great significance for early diagnosis, treatment monitoring, and prognosis of cancer. Here, an ultra-sensitive photoelectrochemical (PEC) sensing platform was developed based on an aptamer amplification strategy for highly selective and sensitive detection of MUC1 overexpressed in serum and on cancer cell surfaces. The sensing platform utilized copper phthalocyanine to fabricate porous organic polymers (CuPc POPs), and was effectively integrated with g-C3N4/MXene to form a ternary heterojunction material (g-C3N4/MXene/CuPc POPs). This material effectively improved electron transfer capability, significantly enhanced light utilization, and greatly enhanced photoelectric conversion efficiency, resulting in a dramatic increase in photocurrent response. MUC1 aptamer 1 was immobilized on a chitosan-modified photoelectrode for the selective capture of MUC1 or MCF-7 cancer cells. When the target substance was present, MUC1 aptamer 2 labeled with methylene blue (MB) was specifically adsorbed on the electrode surface, leading to enhanced photocurrent. The concentration of MUC1 directly correlated with the number of MB molecules attracted to the electrode surface, establishing a linear relationship between photocurrent intensity and MUC1 concentration. The PEC biosensor exhibited excellent sensitivity for MUC1 detection with a wide detection range from 1 × 10-7 to 10 ng/mL and a detection limit of 8.1 ag/mL. The detection range for MCF-7 cells was from 2 × 101 to 2 × 106 cells/mL, with the capability for detecting single MCF-7 cells. The aptamer amplification strategy significantly enhanced PEC performance, and open up a promising platform to establish high selectivity, stability, and ultrasensitive analytical techniques.

Recyclable Au@R-Fe3O4/g-C3N4 substrates for rapid SERS detection and degradation of multiple pollutants.

Developing a Surface-enhanced Raman spectroscopy (SERS) method with excellent detecting ability, good recyclability and analyzing multiple pollutants rapidly are critical for evaluation of water quality in emergency pollution affairs. While constructing a multifunctional substrate with these characteristics to realize the application of SERS in water quality monitoring remains a challenge. In this work, a reusable Au@R-Fe3O4/g-C3N4 SERS substrate is prepared by loading Au nanoparticles (Au NPs) on Fe3O4 nanorings (R-Fe3O4) and the formed Au@R-Fe3O4 is further combined with g-C3N4 nanosheets through a simple electrostatic assembly method. The Au@R-Fe3O4/g-C3N4 nanocomposite presents multifunction of magnetic enrichment, SERS signal enhancement, multiple pollutants analyzing, and photocatalytic activity, which achieves quantitative detection of rhodamine B (RhB), tetracycline hydrochloride (TC), and 4-chlorophenol (4-CP), with detection limits of 5.30 × 10-9, 7.50 × 10-8, 7.69 × 10-8 mol/L, respectively. Furthermore, the recyclable detection capability of Au@R-Fe3O4/g-C3N4 for multi components is demonstrated by the strong SERS signal after 9 cycles of "detection-degradation" processes. Combined with good uniformity and stability, this SERS method based on Au@R-Fe3O4/g-C3N4 substrate provides a new strategy for the multi-pollutants detection and degradation in water environment.

Reticular chemistry guided precise construction of zirconium-pentacarboxylate frameworks with 5-connected Zr6 clusters.

Zirconium-based metal-organic frameworks (Zr-MOFs) have been extensively studied due to their very rich structural chemistry. The combination of nearly unlimited carboxylic acid-based linkers and Zr6 clusters with multiple connectivities has led to diverse structures and specific properties of resultant Zr-MOFs. Herein, we demonstrate the successful use of reticular chemistry to construct two novel Zr-MOFs, HIAM-4040 and HIAM-4040-OH, with zfu topology. Based on a thorough structural analysis of (4,4)-connected lvt-type Zr-tetracarboxylate frameworks and a judicious linker design, we have obtained the first example of a Zr-pentacarboxylate framework featuring unprecedented 5-connected organic linkers and 5-connected Zr6 clusters. Compared with HIAM-4040, a larger Stokes shift is achieved in HIAM-4040-OH via hydroxyl group induced excited-state intramolecular proton transfer (ESIPT). HIAM-4040-OH exhibits high chemical and thermal stability and is used for HClO detection in aqueous solution with excellent sensitivity and selectivity.

Ultrabright Green-Emissive Nanodots for Precise Biological Visualization.

Developing general methods to fabricate water-dispersible and biocompatible fluorescent probes will promote different biological visualization applications. Herein, we report a metal-facilitated method to fabricate ultrabright green-emissive nanodots via the one-step solvothermal treatment of rose bengal, ethanol, and various metal ions. These metal-doped nanodots show good water dispersity, ultrahigh photoluminescence quantum yields (PLQYs) (e.g., the PLQY of Fe-doped nanodots (FeNDs) was ∼97%), and low phototoxicity. Owing to the coordination effect of metal ions, the FeNDs realize glutathione detection with outstanding properties. Benefiting from the high endoplasmic reticulum (ER) affinity of the chloride group, the FeNDs can act as an ER tracker with long ER imaging capacity (FeNDs: >24 h; commercial ER tracker: ∼1 h) and superb photostability and can achieve tissue visualization in living Caenorhabditis elegans. The metal-doped nanodots represent a general nanodot preparation method and may shed new light on diverse biological visualization uses.

Highly sensitive SERS detection of pesticide residues based on multi-hotspot buckypaper modified with gold nanoparticles.

To effectively extract target analytes from complex sample surfaces is of great significance for the practical application of surface-enhanced Raman scattering (SERS) spectroscopy. A plasmonic substrate with multiple "hotspots" for highly sensitive detection of pesticide residues were prepared successfully by assembling gold nanoparticles on buckypaper (AuNPs-BP). The substrate exhibited high SERS enhancement and excellent detection sensitivity, with a detection limit (LOD) of 2.03 × 10-11 M and 6.88 × 10-12 M for the probe molecule R6G and MB, respectively. Combined with 3D finite-difference time-domain (3D-FDTD) simulation, the excellent SERS performance of the substrate was attributed to the enhancement of the electromagnetic field around the "hotspots". Additionally, the substrates exhibited excellent flexibility, allowing easy contact with irregular surfaces and facilitating the collection of target molecules on the sample surface. Using a portable Raman spectrometer, the substrate achieved in situ analysis of chlorpyrifos residues on peach, with a LOD as low as 6.8 × 10-11 M. The method showed high accuracy, with a recovery value ranging from 94.2 % to 115.5 %. The results indicate that the substrate has great potential for rapid and highly sensitive detection of pollutants, especially on non-planar surfaces.

Fabrication of multifunctional g-C3N4-modified Au/Ag NRs arrays for ultrasensitive and recyclable SERS detection of bisphenol A residues.

Monolayer g-C3N4-modified Au/Ag nanorods (g-C3N4/Au/Ag NRs) array is fabricated as a dual-function platform with high surface-enhanced Raman scattering (SERS) response and excellent photocatalytic degradation ability for bisphenol A (BPA) residues. FDTD simulation results of Au/Ag NRs proves that the electromagnetic field intensity is significantly enhanced at the gap of Ag NRs and Au NPs and the protrusion of Au NPs, which endows the arrays with excellent SERS activity. The arrays exhibit high sensitivity for rhodamine 6G (R6G) (LOD = 1.1 × 10-11 mol/L) and high SERS enhancement (EF = 9.2 × 107). In addition, the g-C3N4/Au/Ag NRs could degrade ˃90% of BPA adsorbed on the substrate surface within 140 min under visible light irradiation, and maintains its SERS activity after repeated use for 4 times. The dual-function platform with high SERS response and excellent recycling capability is proved to be reliable and is very promising for monitoring of BPA residues in food.

PEC-SERS Dual-Mode Detection of Foodborne Pathogens Based on Binding-Induced DNA Walker and C3N4/MXene-Au NPs Accelerator.

In this paper, a photoelectrochemical (PEC)-surface-enhanced Raman scattering (SERS) dual-mode biosensor is constructed coupled with a dual-recognition binding-induced DNA walker with a carbon nitride nanosheet (C3N4)/MXene-gold nanoparticles (C/M-Au NPs) accelerator, which is reliable and capable for sensitive and accurate detection of Staphylococcus aureus (S. aureus). Initially, a photoactive heterostructure is formed by combining C3N4 and MXene via a simple electrostatic self-assembly as they possess well-matched band-edge energy levels. Subsequently, in situ growth of gold nanoparticles on the formed surface results in better PEC performance and SERS activity, because of the synergistic effects of surface plasmon resonance and Schottky barrier. Furthermore, a three-dimensional, bipedal, and dual-recognition binding-induced DNA walker is introduced with the formation of Pb2+-dependent DNAzyme. In the presence of S. aureus, a significant quantity of intermediate DNA (I-DNA) is generated, which can open the hairpin structure of Methylene Blue-tagged hairpin DNA (H-MB) on the electrode surface, thereby enabling the switch of signals for the quantitative determination of S. aureus. The constructed PEC-SERS dual-mode biosensor that can be mutually verified under one reaction effectively addresses the problem of the low detection accuracy of traditional sensors. Experimental results revealed that the effective combination of PEC and SERS is achieved for amplification detection of S. aureus with a detection range of 5-108 CFU/mL (PEC) and 10-108 CFU/mL (SERS), and a detection of limit of 0.70 CFU/mL (PEC) and 1.35 CFU/mL (SERS), respectively. Therefore, this study offers a novel and effective dual-mode sensing strategy, which has important implications for bioanalysis and health monitoring.

Modification of whey protein isolate by ultrasound-assisted pH shift for complexation with carboxymethylcellulose: Structure and interfacial properties.

The application of whey protein isolate (WPI) is limited because of its compact spherical structure. In this study, ultrasound-assisted pH shift was employed to modify WPI for complexation with carboxymethylcellulose (CMC). The foaming and emulsifying properties of WPI/CMC complexes were investigated. The results demonstrate that the pretreatment of ultrasound-assisted pH 12 shift increased the content of free sulfhydryl groups from 16.5 µmol/g to 34.7 µmol/g and enhanced protein hydrophobicity from 311.4 to 370.6 (p < 0.05). Compared to the complexes formed by untreated WPI and CMC, the complexes pretreated with ultrasound-assisted pH 12 shift had a smaller size of 293.4 nm and a more uniform distribution. Furthermore, WPI/CMC complexes pretreated by ultrasound-assisted pH 12 shift exhibited higher emulsifying activity and emulsion stability index, which were increased by 8.9 % and 42.6 % respectively, in comparison with the control group (p < 0.05). A positive correlation was found between the surface hydrophobicity of WPI and emulsifying activity of WPI/CMC complexes. Ultrasound-assisted pH 2 shift improved the foaming capacity of complexes by 28.3 % over the control (p < 0.05). All the results indicate that the interfacial properties of WPI/CMC complexes can be improved significantly by the combination of pH shift and ultrasound.

Size- and Emission-Controlled Synthesis of Full-Color Luminescent Metal-Organic Frameworks for Tryptophan Detection.

The development of nanoscaled luminescent metal-organic frameworks (nano-LMOFs) with organic linker-based emission to explore their applications in sensing, bioimaging and photocatalysis is of great interest as material size and emission wavelength both have remarkable influence on their performances. However, there is lack of platforms that can systematically tune the emission and size of nano-LMOFs with customized linker design. Herein two series of fcu- and csq-type nano-LMOFs, with precise size control in a broad range and emission colors from blue to near-infrared, were prepared using 2,1,3-benzothiadiazole and its derivative based ditopic- and tetratopic carboxylic acids as the emission sources. The modification of tetratopic carboxylic acids using OH and NH2 as the substituent groups not only induces significant emission bathochromic shift of the resultant MOFs, but also endows interesting features for their potential applications. As one example, we show that the non-substituted and NH2 -substituted nano-LMOFs exhibit turn-off and turn-on responses for highly selective and sensitive detection of tryptophan over other nineteen natural amino acids. This work sheds light on the rational construction of nano-LMOFs with specific emission behaviours and sizes, which will undoubtedly facilitate their applications in related areas.

Thin layer chromatography coupled with surface enhanced Raman scattering for rapid separation and on-site detection of multi-components.

The separation and detection of multi-component mixtures has always been a challenging task. Traditional detection methods often suffer from complex operation, high cost, and low sensitivity. Surface enhanced Raman scattering (SERS) technique is a high sensitivity, powerful and rapid detection tool, which can realize the specific detection of single substance components, but it must solve the problem that multi-component mixtures cannot be accurately determined. Thin layer chromatography (TLC) technology, as a high-throughput separation technology, uses chromatographic plate as the stationary phase, and could select different developing phases for separation experiments. The advantages of TLC technology in short distance and rapid separation are widely used in protein, dye and biomedical fields. However, TLC technology has limitations in detection ability and difficulty in obtaining ideal signal intensity. The combination of TLC technology and SERS technology made the operation procedure simple and the sample size small, which can achieve rapid on-site separation and quantitative detection of mixtures. Due to the rapid development of TLC-SERS technology, it has been widely used in the investigation of various complex systems. This paper reviews the application of TLC-SERS technology in food science, environmental pollution and biomedicine.

Designing carbon nanotube sponge/Au@MgO2 for surface-enhanced Raman scattering detection and fenton-like degradation of organic pollutants.

With the acceleration of industry and agriculture process, the massive emission of organic pollutants is a major problem which seriously restricts the sustainable development of society. Rapid enrichment, efficient degradation and sensitive detection are three key steps to solve the problem of organic pollutants, while developing a simple method integrating the above three capabilities is still a challenge. Herein, a three-dimensional carbon nanotube sponge decorated with magnesium peroxide and gold nanoparticles (CNTs/Au@MgO2 sponge) was prepared for surface enhanced Raman scattering (SERS) detection and degradation of aromatic organics by advanced oxidation processes. The CNTs/Au@MgO2 sponge with porous structures adsorbed molecules rapidly through π-π and electrostatic interaction, thus more aromatic molecules were driven to the hot-spot areas for highly sensitive SERS detection. A detection of limit with 9.09 × 10-9 M was achieved for rhodamine B (RhB). The adsorbed molecules were degraded by an advanced oxidation process utilizing hydrogen peroxide produced by MgO2 nanoparticles under acidic condition with 99% efficiency. In addition, the CNTs/Au@MgO2 sponge exhibited high reproducibility with the relative standard deviation (RSD) at 1395 cm-1 of approximately 6.25%. The results showed the sponge can be used to effectively track the concentration of pollutants during the degradation process and maintain the SERS activity by re-modifying Au@MgO2 nanomaterials. Furthermore, the proposed CNTs/Au@MgO2 sponge demonstrated the simultaneous functions of enrichment, degradation, and detection for aromatic pollutants, thus significantly expanding the potential applications of nanomaterials in environmental analysis and treatment.

Peroxidase-like Nanozymes for Point-of-Care SERS Sensing and Wound Healing.

The emergence of nanozymes provides a potential method for combating multidrug-resistant bacteria resulted from the abuse of antibiotics. However, in nanozyme-catalyzed systems, few studies have addressed the actual hydrogen peroxide (H2O2) level involved in sterilization. Herein, we designed a high-efficiency peroxidase-mimicking nanozyme with surface-enhanced Raman scattering (SERS) property by assembling gold nanoparticles on single-layer Cu2+-C3N4 (AuNP-Cu2+-C3N4). The nanozyme effectively converts the low-active Raman reporter 3,3',5,5'-tetramethylbenzidine (TMB) into its oxidized form with H2O2, resulting in SERS signal changes, thereby achieving highly sensitive quantification of H2O2 with limit of detection as low as 0.60 µM. More importantly, the nanozyme can specifically catalyze H2O2 into antibacterial hydroxyl radicals. In vitro and in vivo evaluations demonstrate the remarkable antibacterial efficacy of the nanozyme/H2O2 combination against Staphylococcus aureus (up to 99.9%), which could promote wound healing in mice and allow point-of-care monitoring the amount of H2O2 participated in effective sterilization. This study not only displays great potential in combining multiple functionalities of nanomaterials for versatile bioassays but also provides a promising approach to design nanozymes for biomedical and catalytic applications.

3-Year outcomes after left atrial appendage closure in patients with nonvalvular atrial fibrillation: cardiomyopathy related with increased death and stroke rate.

INTRODUCTION: Left atrial appendage closure (LAAC) is a novel treatment for stroke prevention in high-risk patients with non-valvular atrial fibrillation (NVAF). However, the long-term outcomes after LAAC in Chinese NVAF patients are still lacking. METHODS: This was a single-center, bidirectional, nonrandomized registered study. Patients who underwent LAAC implantation from May 2014 to April 2021 in a large Chinese center were enrolled. The primary endpoint was combined all-cause death and stroke. RESULTS: From May 2014 to April 2021, a total of 673 NVAF patients were enrolled. The overall successful implantation rate was 97.62% (657 of 673). The rate of perioperative adverse events was 1.19% (8 of 673), including 3 cardiac tamponades, 2 ischemic strokes, one device-related thrombus (DRT) and 2 device dislocations. 604 (92.24%) patients completed the follow-up, the median follow-up period was 36.9 months (IQR 24.8-56.5 months). 16 stroke events occurred in 15 patients (one patient suffered from both hemorrhagic and ischemic strokes). 13 patients (2.15%) had ischemic stroke, and the fatal rate was 0.33% (2 of 604). 3 patients (0.15%) suffered from hemorrhagic stroke, and the fatal rate was 0.17% (1 of 604). The overall stroke rate was 0.74% per-year. The combined death and stroke rate was 1.93% per-year. In the multivariate Cox regression analysis, age ≥ 75 (hazard ratio 2.264, 95% CI 1.074-4.772, P = 0.032) and ventricular cardiomyopathy (hazard ratio 2.738, 95% CI 1.060-7.071, P = 0.037) were independent predictors of combined mortality and stroke. CONCLUSION: The overall successful implantation rate of LAAC was 97.62% and the rate of perioperative adverse events was 1.19% in this study, and the stroke rate was 0.74% per year during the long-term follow-up. Age ≥ 75 years and ventricular cardiomyopathy were independent predictors of the primary endpoint. Trial registration This study was retrospectively registered.

Reticular Chemistry with Art: A Case Study of Olympic Rings-Inspired Metal-Organic Frameworks.

Herein, we demonstrate the successful utilization of reticular chemistry as an excellent designing strategy for the deliberate construction of a zirconium-tetracarboxylate metal-organic framework (MOF) inspired by the Olympic rings. HIAM-4017, with an unprecedented (4,8)-c underlying net topology termed jcs, was developed via insightful reconstruction of the rings and judicious design of a nonsymmetric organic linker. HIAM-4017 exhibits high porosity and excellent chemical and thermal stability. Furthermore, excited-state intramolecular proton transfer (ESIPT) was achieved in an isoreticular MOF, HIAM-4018, with a large Stokes shift of 155 nm as a result of introducing the hydroxyl group to the linker skeleton to induce OH···N interactions. Such interactions were analyzed thoroughly by employing the time-dependent density functional theory (TD-DFT). Because of their good thermal and chemical stability, and strong luminescence, nanosized HIAM-4017 and HIAM-4018 were fabricated and used for Cr2O72- detection. Both MOFs demonstrate excellent sensitivity and selectivity. This work represents a neat example of building structure- and property-specific MOFs guided by reticular chemistry.

Highly selective SERS detection of acetylcholinesterase in human blood based on catalytic reaction.

Acetylcholinesterase (AChE) is a key hydrolase in the cholinergic system, which directly determines the degradation of neurotransmitters. Therefore, it is a significant challenge to detect AChE in human blood with high sensitivity and selectivity in physiological and pathological processes. A novel nanoprobe by decorating the surface of gold nanoparticles with neostigmine (NE) AuNPs/NE was constructed for the AChE assay in serum. The principle is based on the specific recognition and cleavage of carbamate bonds in AuNPs/NE by AChE to form hydroxyl groups, resulting in changes of SERS spectra. The results show that 10 nm AuNPs/NE exhibit excellent catalytic activity for this reaction and the reaction rate is six times higher than that of 70 nm AuNPs/NE. Benefiting from the combined advantages of catalytic reaction specificity and molecular finger printing provided by SERS technology, AuNPs/NE exhibit high selectivity for AChE. The limit of detection (LOD) of this method for AChE activity was low to 0.02 U/mL. In addition, the spiked recovery of AChE in serum samples was 75.0%-119.2%. The proposed sensor also exhibits long-term stability and high biocompatibility with the increasing incubation time. More importantly, this work provides a new perspective for elucidating the role of AChE regulated by oxidative stress in the pathology of depression.

Nanozyme-mediated signal amplification for ultrasensitive photoelectrochemical sensing of Staphylococcus aureus based on Cu-C3N4-TiO2 heterostructure.

Food-borne pathogens are one of the leading causes of food poisoning, which vigorously affect food safety and human health. Therefore, the development of early and rapid detection methods for food pollution evaluation is the key to food safety and quality control. Herein, a simple and inexpensive photoelectrochemical (PEC) sensor is developed for highly selective and ultrasensitive detection of Staphylococcus aureus (S. aureus). The technique is based on "signal-off" that employs Cu-C3N4-TiO2 heterostructures as photoactive materials and monolayer Cu-C3N4 nanozyme as a signal amplifier. In the presence of S. aureus, the aptamer-modified Cu-C3N4 (Cu-C3N4@Apt, a signal amplifier) and S. aureus were specifically anchored on the surface of the ligand-modified photoelectrode. The Cu-C3N4@Apt nanozyme acted as a peroxidase to catalyze the oxidation of 4-chloro-1-naphthol (4-CN) to produce insoluble precipitate on the electrode surface and resulted in a significant decrease in photocurrent. Based on the signal-amplification by the Cu-C3N4@Apt nanozyme, the constructed PEC sensor demonstrated a wide linear range between 10-108 CFU/mL for the S. aureus detection with the detection limit (LOD) as low as 3.40 CFU/mL. Furthermore, the PEC sensor was capable of determining S. aureus in spiked orange juice and milk, with the recovery of 91%-113%, indicating the reliability of the sensor for S. aureus detection in real samples. This investigation provides a feasible strategy for the design of highly selective and ultrasensitive PEC sensors to determine analytes in complex systems.

Sex Differences in Efficacy and Safety After Left Atrial Appendage Closure: A 4.3-Year Follow-Up Analysis.

Introduction: Women are related to higher stroke risk and poorer outcome after stroke attack in patients with non-valvular atrial fibrillation (NVAF). The sex differences in efficacy and safety after left atrial appendage closure (LAAC) have remained elusive. This retrospective study aimed to investigate the safety, feasibility, and clinical outcomes of LAAC between women and men. Methods: From 2014 to 2018, 395 patients who underwent LAAC in our center were enrolled in this retrospective study. Baseline clinical characteristics, procedural parameters, and postoperative follow-up data were collected and compared between women and men. Results: The study included 154 women and 241 men. Compared with men, women were older (68.1 ± 7.9 vs. 64.6 ± 8.8, p < 0.01**), with higher CHA2DS2-VASc score (4.0 ± 1.7 vs. 3.0 ± 1.6, p < 0.01**). During the mean follow-up duration of 1,566 days (4.3 years), there were 39 major adverse cardiovascular events (MACE, including 19 cardiovascular or unexplained deaths, 15 ischemic strokes, and 5 major bleedings) recorded in 34 patients. The overall rate of ischemic stroke was 0.9 per 100 patient-years, and the overall rate of MACE was 2.1 per 100 patient-years. The cardiovascular or unexplained death and major bleeding were comparable between women and men. Compared with men, women had lower rates of ischemic stroke, fatal or disabling ischemic stroke, MACE, and fatal or disabling MACE, but none of them reached statistical differences (HR: 0.361, p = 0.099, HR: 0.429, p = 0.276, HR: 0.600, p = 0.170, and HR: 0.621, p = 0.254, respectively). In the adjusted analyses with multivariate Cox regression models, women had a lower fatal or disabling ischemic stroke rate compared with men (HR: 0.100, p = 0.041). Conclusion: Left atrial appendage closure was feasible and safe for patients of both genders. The ischemic stroke, cardiovascular or unexplained death, and major bleeding were comparable between women and men. However, women were the independent protective factors against fatal or disabling ischemic stroke after LAAC implantation.

Rapid and non-invasive surface-enhanced Raman spectroscopy (SERS) detection of chlorpyrifos in fruits using disposable paper-based substrates charged with gold nanoparticle/halloysite nanotube composites.

Chlorpyrifos is one of the most widely used organophosphate insecticides in agricultural production. Nevertheless, the residues of chlorpyrifos in agricultural by-product seriously threaten human health. Thus, the ultrasensitive detection of chlorpyrifos residues in agri-food products is of great demand. Herein, an AuNP/HNT-assembled disposable paper SERS substrate was prepared by an electrostatic self-assembly method to detect chlorpyrifos residues. The AuNP/HNT paper substrate exhibited high SERS activity, good reproducibility, and long-term stability, which was successfully used for quantitative detection of chlorpyrifos; the detection limit reached 7.9 × 10-9 M. For spiked apple samples the calculated recovery was 87.9% with a RSD value of 6.1%. The excellent detection ability of AuNP/HNT paper-based SERS substrate indicated that it will play an important role in pesticide detection in the future. AuNP/HNT assembled disposable paper SERS substrate was prepared by an electrostatic self-assembly method to detect chlorpyrifos residues in fruits.

Reusable ring-like Fe3O4/Au nanozymes with enhanced peroxidase-like activities for colorimetric-SERS dual-mode sensing of biomolecules in human blood.

Peroxidase-like nanozymes have led to important progress in biosensing, but most of nanozyme sensing systems are currently established by a single-signal output mode, which is susceptible to environmental and operational factors. Thus construction of a dual-signal output nanozyme sensing system is essential for obtaining reliable and robust performance. In this study, a novel peroxidase mimicking nanozyme was developed by decorating magnetic ring-like Fe3O4 with gold nanoparticles (R-Fe3O4/Au) for the colorimetric and surface-enhanced Raman scattering (SERS) dual-mode detection of biomolecules in human serum. The R-Fe3O4/Au nanozymes served as mimetic peroxidase which can catalyze the oxidation of colorless 3,3',5,5'-tetramethylbenzidine by hydrogen peroxide, and concomitantly as SERS substrates for detecting the Raman signals of oxidized products, providing an effective approach to investigate the reaction kinetics of enzymes. Based on the redox reactions, the nanozymes achieved colorimetric-SERS dual-mode sensing of glutathione (GSH) and cholesterol with detection limits as low as 0.10 µM and 0.08 µM, respectively. Furthermore, the nanozymes enabled rapid detection of GSH and cholesterol in serum without any complicated sample pretreatment. The R-Fe3O4/Au catalyst still displayed excellent peroxidase activity even after repeated use for 5 times. The proposed colorimetric-SERS dual-mode sensors exhibited good accuracy and reproducibility, which provides a new avenue for exploiting multifunctional sensors and has a great application prospect in biosensing.