Interfacing Lanthanide Metal-Organic Frameworks with ZnO Nanowires for Alternating Current Electroluminescence.

Alternating current electroluminescence (ACEL) devices are attractive candidates in cost-effective lighting, sensing, and flexible displays due to their uniform luminescence, stable performance, and outstanding deformability. However, ACEL devices have suffered from limited options for the light-emitting layer, which presents a significant constraint in the progress of utilizing ACEL. Herein, a new class of ACEL phosphors based on lanthanide metal-organic frameworks (Ln-MOFs) is devised. A synthesis of lanthanide-benzenetricarboxylate (Ln-BTC) thin film on a brass grid substrate seeded with ZnO nanowires (NWs) as anchors is developed. The as-synthesized Ln-BTC thin film is employed as the emissive layer and shows visible electroluminescence driven by alternating current (2.9 V µm-1 , 1 kHz) for the first time. Mechanistic investigations reveal that the Ln-based ACEL stems from impact excitation by accelerated electrons from ZnO NWs. Fine-tuning of the ACEL color is also demonstrated by controlling the Ln-MOF compositions and introducing an extra ZnS emitting layer. The advances in these optical materials expand the application of ACEL devices in anti-counterfeiting.

A Coordination-Derived Cerium-Based Amorphous-Crystalline Heterostructure with High Electrocatalytic Oxygen Evolution Activity.

The rational design of heterogeneous catalysts is crucial for achieving optimal physicochemical properties and high electrochemical activity. However, the development of new amorphous-crystalline heterostructures is significantly more challenging than that of the existing crystalline-crystalline heterostructures. To overcome these issues, a coordination-assisted strategy that can help fabricate an amorphous NiO/crystalline NiCeOx (a-NiO/c-NiCeOx ) heterostructure is reported herein. The coordination geometry of the organic ligands plays a pivotal role in permitting the formation of coordination polymers with high Ni contents. This consequently provides an opportunity for enabling the supersaturation of Ni in the NiCeOx structure during annealing, leading to the endogenous spillover of Ni from the depths of NiCeOx to its surface. The resulting heterostructure, featuring strongly coupled amorphous NiO and crystalline NiCeOx , exhibits harmonious interactions in addition to low overpotentials and high catalytic stability in the oxygen evolution reaction (OER). Theoretical calculations prove that the amorphous-crystalline interfaces facilitate charge transfer, which plays a critical role in regulating the local electron density of the Ni sites, thereby promoting the adsorption of oxygen-based intermediates on the Ni sites and lowering the dissociation-related energy barriers. Overall, this study underscores the potential of coordinating different metal ions at the molecular level to advance amorphous-crystalline heterostructure design.

Polyoxovanadate-Based Metal-Organic Frameworks with Dual Active Sites for the Synthesis of p-Benzoquinones.

p-Benzoquinones are important organic intermediates in the synthesis of biopharmaceuticals and fine chemicals. In this study, two crystalline 3D polyoxovanadate-based metal-organic frameworks, H[Cu(tpi)2]{Cu2V7O21}·H2O (1, tpi = C18N5H13) and [Co(Htpi)2]{V4O12} (2, Htpi = C18N5H14), were synthesized, which as heterogeneous catalysts showed excellent catalytic activities for the synthesis of p-benzoquinones. Both compounds were characterized by IR, UV-vis diffuse reflectance spectroscopy, TG, XPS, X-ray diffraction, etc. In 1, {Cu2V7} clusters are connected together by copper cations and 1D Cu-organic coordination chains to yield a 3D polyoxometalate-based metal-organic framework (POMOF); in 2, adjacent 2D bimetallic oxide layers, constructed from 1D polyoxovanadate chains and cobalt ions, are further connected by 1D Co-organic coordination chains to form a 3D POMOF. Noteworthily, in the synthesis of trimethyl-p-benzoquinone, the key intermediate of vitamin E, using 2,3,6-trimethylphenol as the model substrate, the turnover frequency values for compounds 1 and 2 can, respectively, reach 607 and 380 h-1 in 8 min. Furthermore, both compounds demonstrated excellent recyclability and structural stability, characterized by PXRD and IR. The catalytic mechanism reveals that both the homolytic radical mechanism and heterolytic oxygen atom transfer mechanism are involved.

A toolkit for the identification of NEAT1_2/paraspeckle modulators.

Paraspeckles are ribonucleoprotein granules assembled by NEAT1_2 lncRNA, an isoform of Nuclear Paraspeckle Assembly Transcript 1 (NEAT1). Dysregulation of NEAT1_2/paraspeckles has been linked to multiple human diseases making them an attractive drug target. However currently NEAT1_2/paraspeckle-focused translational research and drug discovery are hindered by a limited toolkit. To fill this gap, we developed and validated a set of tools for the identification of NEAT1_2 binders and modulators comprised of biochemical and cell-based assays. The NEAT1_2 triple helix stability element was utilized as the target in the biochemical assays, and the cellular assay ('ParaQuant') was based on high-content imaging of NEAT1_2 in fixed cells. As a proof of principle, these assays were used to screen a 1,200-compound FDA-approved drug library and a 170-compound kinase inhibitor library and to confirm the screening hits. The assays are simple to establish, use only commercially-available reagents and are scalable for higher throughput. In particular, ParaQuant is a cost-efficient assay suitable for any cells growing in adherent culture and amenable to multiplexing. Using ParaQuant, we identified dual PI3K/mTOR inhibitors as potent negative modulators of paraspeckles. The tools we describe herein should boost paraspeckle studies and help guide the search, validation and optimization of NEAT1_2/paraspeckle-targeted small molecules.

Visible-Light-Responsive 2D Photocatalysts Assembled by Evans-Showell-Type POMs and Metalloviologen Frameworks for Sulfide-Sulfoxide Transformation.

Sulfide-sulfoxide aerobic photo-oxidation is of great interest in organic and medicinal chemistry; however, developing efficient and facile heterogeneous photocatalytic systems without additional additives remains challenging. Herein, we intentionally designed and synthesized two polyoxometalate (POM)-based metalloviologen frameworks, formulated as [MII(4-PBPY)2(H2O)][MII(H2O)4][CoIII2MoVI10H4O38]·nH2O (M = Cu, n = 10 for 1; M = Co, n = 11 for 2), prepared by the mild one-step synthesis strategy and characterized in detail. X-ray single-crystal diffraction analysis shows that they present a two-dimensional layered structure formed by two parallel metalloviologen layers pillared by dimeric Evans-Showell-type POMs. The connection of POM to the metalloviologen framework enables easier flow of electrons to the POM port, which can theoretically further induce O2 to generate reactive oxygen species (O2•-) to oxidize substrates to form target products. As expected, both 1 and 2 exhibit outstanding photocatalytic activity in the oxidation of sulfides. Within 6 h, methyl phenyl sulfide can be quantitatively converted into methyl phenyl sulfoxide. The in-depth mechanism reveals that there is also a synergistic energy-transfer pathway in the catalytic system in addition to the electron-transfer pathway. In addition, the corresponding catalytic activity and structure can be well maintained after at least 10 cycle experiments.

Analysis of Results of Continuous Invasive Arterial Blood Pressure Monitoring in Postoperative Patients.

Objective: In patients with postoperative circulatory instability, the exploration of invasive arterial blood pressure (IABP) monitoring is of great significance because it can provide real-time cardiovascular function information and help medical staff to better assess and manage the patient's circulatory status. To explore the value of IABP monitoring for patients with postoperative circulatory instability in the postanesthesia care unit (PACU). Methods: From January to December 2021, 160 postoperative patients with circulatory instability were randomly divided into a control group and a study group (80 patients in each group). A random number sequence is generated through a random number table, and random numbers are distributed to different patients to achieve random grouping. SPSS was used for data processing and statistical analysis, t test was used for continuous variables, chi-square test was used for count data, and the significance level was P < .05.We compared various parameters, such as systolic blood pressure (SBP), PACU observation time, arterial partial pressure of oxygen (PaO2), total hospitalization time, heart rate (HR), arterial partial pressure of carbon dioxide (PaCO2), re-intubation rate, mean arterial pressure (MAP), adverse events, and blood oxygen saturation (SaO2), between the two groups. Flow cytometry was used to analyze changes in immune lymphocyte subsets in the patient's peripheral blood. Results: During the postoperative observation period, there were no significant differences in SBP, PaCO2, HR, SaO2, MAP, and PaO2 between the two groups (P > .05)The study group showed higher SBP, SaO2, MAP, and PaO2, and lower HR and PaCO2 compared to the control group (P < .05). The study group also had shorter PACU observation time, total hospitalization time, and a lower re-intubation rate compared to the control group (P < .05). There was no significant difference in the overall incidence of adverse events between the two groups (7.50% vs 3.75%) (P > .05). The study group showed significantly higher proportions of lymphocytes, CD3+ T cells, CD3+ CD4+ T cells, and CD3+ CD4+/CD3+ CD8+ ratio compared to the control group (P < .05). This change may reflect the patients with a positive response of the immune system, help to resist disease progress and infection. Conclusion: IABP monitoring can continuously, dynamically and accurately collect arterial blood pressure data of patients with postoperative circulatory instability, contributing to the recovery of immune competence in patients to help formulate the best clinical treatment and intervention plan. The dynamic and accurate arterial blood pressure data collection provided by IABP monitoring contributes not only to immune competence recovery but also to overall patient management and treatment planning.

Baicalin inhibits hepatocellular carcinoma cell growth and metastasis by suppressing ROCK1 signaling.

Hepatocellular carcinoma (HCC) is a common malignancy affecting many people worldwide. Baicalin is a flavonoid extracted from the dried root of Scutellaria baicalensis Georgi. It can effectively inhibit the occurrence and development of HCC. Nonetheless, the mechanism through which Baicalin inhibits HCC growth and metastasis remain unknown. This work discovered that Baicalin inhibited HCC cell proliferation, invasion, metastasis while inducing cell cycle arrest at the G0/G1 phase and apoptosis. In vivo HCC xenograft results indicated that Baicalin inhibited HCC growth. Western blotting analysis indicated that Baicalin suppressed the expressions of ROCK1, p-GSK-3ß, and ß-catenin, whereas it up-regulated the expressions of GSK-3ß and p-ß-catenin. Baicalin also reduced the expressions of Bcl-2, C-myc, Cyclin D1, MMP-9, and VEGFA, while increasing the expression of Bax. Molecular docking revealed that Baicalin docked in the binding site of the ROCK1 agonist, with a binding energy of -9 kcal/mol between the two. In addition, lentivirus-mediated suppression of ROCK1 expression improved the inhibitory effect of Baicalin on the proliferation, invasion, and metastasis of HCC and the expression of proteins associated with ROCK1/GSK-3ß/ß-catenin signaling pathway. Moreover, restoring ROCK1 expression decreased the anti-HCC efficacy of Baicalin. These findings suggest that Baicalin may decrease HCC proliferation and metastasis by suppressing ROCK1/GSK-3ß/ß-catenin signaling.

Postoperative recovery after breast cancer surgery: A randomised controlled trial of opioid-based versus opioid-free anaesthesia with thoracic paravertebral block.

BACKGROUND: Perioperative use of opioids has revealed significant adverse effects associated with poor postoperative outcomes. OBJECTIVE: To determine whether opioid-free anaesthesia based on thoracic paravertebral block (TPVB) could improve postoperative recovery after breast cancer surgery. DESIGN: A randomised controlled trial. SETTING: A tertiary teaching hospital. PATIENTS: Eighty adult women undergoing breast cancer surgery were enrolled. Key exclusion criteria included remote metastasis (but not to axillary lymph nodes of the surgical side), contraindication to interventions or drugs and a history of chronic pain or chronic opioid use. INTERVENTIONS: Eligible patients were randomised at a 1 : 1 ratio to receive either TPVB-based opioid-free anaesthesia (OFA group) or opioid-based anaesthesia (control group). MAIN OUTCOME MEASURES: The primary outcome was the global score of the 15-item Quality of Recovery (QoR-15) questionnaire at 24 h after surgery. Secondary outcomes included postoperative pain and health-related quality of life. RESULTS: The QoR-15 global score was 140.3 ±â€Š5.2 in the OFA group and 132.0 ±â€Š12.0 in the control group ( P  < 0.001). The percentage of patients with good recovery (QoR-15 global score ≥118) was 100% (40/40) in the OFA group and 82.5% (33/40) in the control group ( P  = 0.012). Improved QoR in the OFA group was also evident in sensitivity analysis that rated QoR as excellent for a score of 136 to 150, as good at 122 to 135, as moderate at 90 to 121 and as poor at 0 to 89. The OFA group had higher scores in the domains of physical comfort (45.7 ±â€Š3.0 versus 41.8 ±â€Š5.7, P  < 0.001) and physical independence (18.3 ±â€Š2.2 versus 16.3 ±â€Š4.5, P  = 0.014). The two groups did not differ in pain outcomes or health-related quality of life. CONCLUSION: TPVB-based opioid-free anaesthesia improved early postoperative quality of recovery without compromising pain control in patients undergoing breast cancer surgery. TRIAL REGISTRATION: Clinicaltrials.gov; Identifier: NCT04390698.

Dual Recycling of Depolymerization Catalyst and Biodegradable Polyester that Markedly Outperforms Polyolefins.

Chemically recyclable, circular polymers continue to attract increasing attention, but rendering both catalysts for depolymerization and high-performance polymers recyclable is a more sustainable yet challenging goal. Here we introduce a dual catalyst/polymer recycling system in that recyclable inorganic phosphomolybdic acid catalyzes selective depolymerization of high-ceiling-temperature biodegradable poly(δ-valerolactone) in bulk phase, which, upon reaching suitable molecular weight, exhibits outstanding mechanical performance with a high tensile strength of ≈66.6 MPa, fracture strain of ≈904 %, and toughness of ≈308 MJ m-3 , and thus markedly outperforms commodity polyolefins, recovering its monomer in pure state and quantitative yield at only 100 °C. In sharp contrast, the uncatalyzed depolymerization not only requires a high temperature of >310 °C but is also low yielding and non-selective. Importantly, the recovered monomer can be repolymerized as is to reproduce the same polymer, thereby closing the circular loop, and the recycled catalyst can be reused repeatedly for depolymerization runs without loss of its catalytic activity and efficiency.

ALS-linked cytoplasmic FUS assemblies are compositionally different from physiological stress granules and sequester hnRNPA3, a novel modifier of FUS toxicity.

Formation of cytoplasmic RNA-protein structures called stress granules (SGs) is a highly conserved cellular response to stress. Abnormal metabolism of SGs may contribute to the pathogenesis of (neuro)degenerative diseases such as amyotrophic lateral sclerosis (ALS). Many SG proteins are affected by mutations causative of these conditions, including fused in sarcoma (FUS). Mutant FUS variants have high affinity to SGs and also spontaneously form de novo cytoplasmic RNA granules. Mutant FUS-containing assemblies (mFAs), often called "pathological SGs", are proposed to play a role in ALS-FUS pathogenesis. However, structural differences between mFAs and physiological SGs remain largely unknown therefore it is unclear whether mFAs can functionally substitute for SGs and how they affect cellular stress responses. Here we used affinity purification to isolate mFAs and physiological SGs and compare their protein composition. We found that proteins within mFAs form significantly more physical interactions than those in SGs however mFAs fail to recruit many factors involved in signal transduction. Furthermore, we found that proteasome subunits and certain nucleocytoplasmic transport factors are depleted from mFAs, whereas translation elongation, mRNA surveillance and splicing factors as well as mitochondrial proteins are enriched in mFAs, as compared to SGs. Validation experiments for a mFA-specific protein, hnRNPA3, confirmed its RNA-dependent interaction with FUS and its sequestration into FUS inclusions in cultured cells and in a FUS transgenic mouse model. Silencing of the Drosophila hnRNPA3 ortholog was deleterious and potentiated human FUS toxicity in the retina of transgenic flies. In conclusion, we show that SG-like structures formed by mutant FUS are structurally distinct from SGs, prone to persistence, likely cannot functionally replace SGs, and affect a spectrum of cellular pathways in stressed cells. Results of our study support a pathogenic role for cytoplasmic FUS assemblies in ALS-FUS.

Visible-Light-Driven Oxidation of Amines to Imines in Air Catalyzed by Polyoxometalate-Tris(bipyridine)ruthenium Hybrid Compounds.

The development of visible-light photocatalysts for the selective oxidative coupling of amines to imines is an area of great interest. Herein, four hybrid compounds based on polyoxometalate anions and tris(bipyridine)ruthenium cations, Ru(bpy)3[M6O19] (M = Mo, W) 1-2, [Ru(bpy)3]2[Mo8O26] 3, [Ru(bpy)3]2[W10O32] 4, are prepared and characterized by X-ray diffraction (single-crystal and powder), elemental analysis, energy-dispersive X-ray spectroscopy (EDS) analysis, infrared (IR) spectroscopy, and solid diffuse reflective spectroscopy. Single-crystal structural analysis indicates that polyoxometalate anions and tris(bipyridine)ruthenium cations interact with each other through extensive hydrogen bonds in these compounds. These hybrid species with strong visible-light-harvesting abilities and suitable photocatalytic energy potentials show excellent photocatalytic activity and selectivity for the oxidation of amines to imines at room temperature in air as an oxidant. Among them, compound 1 with the [Mo6O19]2- anion has the highest catalytic activity, which can swiftly convert >99.0% of benzylamine into N-benzylidenebenzylamine with a selectivity of 98.0% in 25 min illumination by a 10 W 445 nm light-emitting diode (LED). Its turnover frequency reaches 392 h-1, which is not only better than the homogeneous catalyst [Ru(bpy)3]Cl2 but also much superior to those achieved over most of reported heterogeneous catalysts. Moreover, it shows a wide generality for various aromatic amines, accompanied by the advantages of good recyclability and stability. The photocatalytic oxidation mechanism of amines to the corresponding imines over polyoxometalate-based hybrid compounds was fully investigated.

STED Imaging the Dynamics of Lysosomes by Dually Fluorogenic Si-Rhodamine.

Super-resolution microscopy (SRM) imaging of the finite subcellular structures and subtle bioactivities inside organelles delivers abundant cellular information with high fidelity to unravel the intricate biological processes. An ideal fluorescent probe with precise control of fluorescence is critical in SRM technique like stimulated emission depletion (STED). Si-rhodamine was decorated with both targeting group and H+ -receptor, affording the dually fluorogenic Si-rhodamine in which the NIR fluorescence was efficiently controlled by the coalescent of spirolactone-zwitterion equilibrium and PeT mechanism. The dually fluorogenic characters of the probe offer a perfect mutual enhancement in sensitivity, specificity and spatial resolution. Strong fluorescence only released in the existence of targeting protein at acidic lysosomal pH, ensured precisely tracking the dynamic of lysosomal structure and pH in living cells by STED.

Delirium in Older Patients after Combined Epidural-General Anesthesia or General Anesthesia for Major Surgery: A Randomized Trial.

BACKGROUND: Delirium is a common and serious postoperative complication, especially in the elderly. Epidural anesthesia may reduce delirium by improving analgesia, reducing opioid consumption, and blunting stress response to surgery. This trial therefore tested the hypothesis that combined epidural-general anesthesia reduces the incidence of postoperative delirium in elderly patients recovering from major noncardiac surgery. METHODS: Patients aged 60 to 90 yr scheduled for major noncardiac thoracic or abdominal surgeries expected to last 2 h or more were enrolled. Participants were randomized 1:1 to either combined epidural-general anesthesia with postoperative epidural analgesia or general anesthesia with postoperative intravenous analgesia. The primary outcome was the incidence of delirium, which was assessed with the Confusion Assessment Method for the Intensive Care Unit twice daily during the initial 7 postoperative days. RESULTS: Between November 2011 and May 2015, 1,802 patients were randomized to combined epidural-general anesthesia (n = 901) or general anesthesia alone (n = 901). Among these, 1,720 patients (mean age, 70 yr; 35% women) completed the study and were included in the intention-to-treat analysis. Delirium was significantly less common in the combined epidural-general anesthesia group (15 [1.8%] of 857 patients) than in the general anesthesia group (43 [5.0%] of 863 patients; relative risk, 0.351; 95% CI, 0.197 to 0.627; P < 0.001; number needed to treat 31). Intraoperative hypotension (systolic blood pressure less than 80 mmHg) was more common in patients assigned to epidural anesthesia (421 [49%] vs. 288 [33%]; relative risk, 1.47, 95% CI, 1.31 to 1.65; P < 0.001), and more epidural patients were given vasopressors (495 [58%] vs. 387 [45%]; relative risk, 1.29; 95% CI, 1.17 to 1.41; P < 0.001). CONCLUSIONS: Older patients randomized to combined epidural-general anesthesia for major thoracic and abdominal surgeries had one third as much delirium but 50% more hypotension. Clinicians should consider combining epidural and general anesthesia in patients at risk of postoperative delirium, and avoiding the combination in patients at risk of hypotension.

Long-term Survival after Combined Epidural-General Anesthesia or General Anesthesia Alone: Follow-up of a Randomized Trial.

BACKGROUND: Experimental and observational research suggests that combined epidural-general anesthesia may improve long-term survival after cancer surgery by reducing anesthetic and opioid consumption and by blunting surgery-related inflammation. This study therefore tested the primary hypothesis that combined epidural-general anesthesia improves long-term survival in elderly patients. METHODS: This article presents a long-term follow-up of patients enrolled in a previous trial conducted at five hospitals. Patients aged 60 to 90 yr and scheduled for major noncardiac thoracic and abdominal surgeries were randomly assigned to either combined epidural-general anesthesia with postoperative epidural analgesia or general anesthesia alone with postoperative intravenous analgesia. The primary outcome was overall postoperative survival. Secondary outcomes included cancer-specific, recurrence-free, and event-free survival. RESULTS: Among 1,802 patients who were enrolled and randomized in the underlying trial, 1,712 were included in the long-term analysis; 92% had surgery for cancer. The median follow-up duration was 66 months (interquartile range, 61 to 80). Among patients assigned to combined epidural-general anesthesia, 355 of 853 (42%) died compared with 326 of 859 (38%) deaths in patients assigned to general anesthesia alone: adjusted hazard ratio, 1.07; 95% CI, 0.92 to 1.24; P = 0.408. Cancer-specific survival was similar with combined epidural-general anesthesia (327 of 853 [38%]) and general anesthesia alone (292 of 859 [34%]): adjusted hazard ratio, 1.09; 95% CI, 0.93 to 1.28; P = 0.290. Recurrence-free survival was 401 of 853 [47%] for patients who had combined epidural-general anesthesia versus 389 of 859 [45%] with general anesthesia alone: adjusted hazard ratio, 0.97; 95% CI, 0.84 to 1.12; P = 0.692. Event-free survival was 466 of 853 [55%] in patients who had combined epidural-general anesthesia versus 450 of 859 [52%] for general anesthesia alone: adjusted hazard ratio, 0.99; 95% CI, 0.86 to 1.12; P = 0.815. CONCLUSIONS: In elderly patients having major thoracic and abdominal surgery, combined epidural-general anesthesia with epidural analgesia did not improve overall or cancer-specific long-term mortality. Nor did epidural analgesia improve recurrence-free survival. Either approach can therefore reasonably be selected based on patient and clinician preference.

2D Hybrid Architectures Constructed from Two Kinds of Polyoxovanadates as Efficient Heterogeneous Catalysts for Cyanosilylation and Knoevenagel Condensation.

The design of heterogeneous catalysts for highly efficient catalysis for cyanosilylation reactions and Knoevenagel condensations is greatly significant, due to the important application of their products in industry. Herein, five hybrid compounds constructed from two types of polyoxovanadates, [MV12O38]12- (M = Ni, Mn) and [V10O28]6-, were successfully synthesized as heterogeneous catalysts for both reactions, which are {(dpdo)[Ln2(H2O)9(dpdo)][Ln(H2O)5]2[Ln(H2O)4]2[V10O28][NiV12O38]·nH2O} (1, Ln = La, n = 23; 2, Ln = Ce, n = 27; 3, Ln = Pr, n = 27; dpdo = 4,4'-bipyridine N,N'-dioxide) and {(dpdo)[Ln2(H2O)9(dpdo)][Ln(H2O)5]2[Ln(H2O)4]2[V10O28][MnV12O38]·27H2O} (4, Ln = La; 5, Ln = Pr). These compounds were characterized by IR spectroscopy, elemental analysis, TG analysis and X-ray diffraction (single crystal and powder) etc. Compounds 1-5 have similar 2D hybrid structures, in which isopolyvanadate [V10O28]6- and heteropolyvanadate [MV12O38]12- are linked together by hydrated Ln3+ cations and Ln-dpdo coordination complexes. Polyoxovanadates [V10O28]6- and [MV12O38]12- both originate from the transformation of the [MV13O38]7- raw material. This kind of extended structure containing isopolyvanadate and heteropolyvanadate has never been reported hitherto. Because of the Lewis acidity of the Ln3+ cation and the Lewis basicity of the polyoxovanadates, all five compounds exhibit excellent catalytic performance in cyanosilylation and Knoevengel condensation reactions. Especially, compound 3, with a Pr3+ cation, displayed the best catalytic results. Furthermore, these catalysts exhibit a truly heterogeneous nature and good recyclability.

Intravenous Tranexamic Acid Decreases Blood Transfusion in Off-Pump Coronary Artery Bypass Surgery: A Meta-analysis.

BACKGROUND: Tranexamic acid (TXA) has been widely used during on-pump coronary artery bypass graft (CABG) surgery owing to its antifibrinolytic effect. However, the efficacy and safety of TXA in off-pump CABG surgery remains unconfirmed, especially intravenous (IV) administration. OBJECTIVE: The aim of this study was to evaluate the effectiveness and safety of IV administration of TXA in off-pump CABG settings. METHODS AND RESULTS: A comprehensive literature search was performed to identify randomized controlled trials (RCTs) that compared IV use of TXA with placebo in the reduction of postoperative 24-hour blood transfusion, as well as postoperative death and thrombotic events. The combined estimations were compiled with a fixed-effects model or, if heterogeneity existed, a random-effects model. Funnel plots and Egger's test were used to assess potential publication bias. Subgroup analyses were used to explore possible sources of heterogeneity. In total, 12 RCTs met the inclusion criteria. IV administration of TXA significantly reduced the risk of packed red blood cell (PRBC) transfusion [risk ratio (RR) = 0.61, 95% confidence interval (CI) 0.503 to 0.756, P < .001, I2 = 0.0%) during the 24 hours after surgery. However, there was no statistical significance in platelet (RR = 0.613, 95% CI 0.112 to 3.348, P = .572, I2 = 0.0%) or total fresh frozen plasma (FFP) (RR = 0.511, 95% CI 0.246 to 1.063, P = .073, I2 = 0.0%) transfusion. Also, no significant difference was found in major adverse events (death or thrombotic complications) (RR = 0.917, 95% CI 0.532 to 1.581, P = .756, I2 = 0.0%) between the 2 groups. Interestingly, further subgroup analysis demonstrated that IV TXA decreased the risk of prothrombin time (PT)- and international normalized ratio (INR)-guided FFP transfusion (RR = 0.462, 95% CI 0.296 to 0.721, P = .001, I2 = 0.0%). CONCLUSION: IV TXA was effective in reducing allogeneic blood component transfusion (PRBCs and PT- or INR-guided FFP transfusion), without increasing the incidence of postoperative death or thrombotic complications in off-pump CAB surgery.

Bridge-Caging Strategy in Phosphorus-Substituted Rhodamine for Modular Development of Near-Infrared Fluorescent Probes.

Replacement of the bridging oxygen atom in rhodamine with phosphorus is one of the most efficient ways for bright near-infrared (NIR) fluorophores with wavelengths over 700 nm. However, the organophosphorus bridge is more versatile than just being a spectrum tuner, it is also a profound solubility booster and photostability enhancer, as proved by a series of phosphorus-substituted rhodamines (PRBs). A unique bridge-caging strategy for efficiently manipulating fluorescence has further been innovated in example PRB2. Consistent with theoretical calculations, the formation of organophosphinate by a caging group as a fluorescence-controller locks the spirolactone into a colorless and nonfluorescent form, whereas decaging, a process induced by a specific stimulus, results in a ring-opened form, which yields strong fluorescence. The bridge-caging strategy is feasible for the modular development of NIR probes. Efficient in vivo imaging of photoillumination, hydrogen peroxide, and enzyme have been achieved on the PRB2 scaffold as a photoactivatable fluorophore, PRB2-hν; fluorescent indicator, PRB2-H2 O2 ; and fluorogenic enzyme substrate, PRB2-NTR, respectively.

Oligo-peptide I-C-F-6 inhibits hepatic stellate cell activation and ameliorates CCl4-induced liver fibrosis by suppressing NF-κB signaling and Wnt/ß-catenin signaling.

Oligo-peptide I-C-F-6 is a Carapax trionycis extract component that has an effect on hepatic fibrosis, however, its mechanism of action is still unclear. This study investigated whether oligo-peptide I-C-F-6 could inhibit liver fibrosis by suppressing NF-κB and Wnt/ß-catenin signaling, which are important in liver fibrosis. HSC-T6 cells were treated with oligo-peptide I-C-F-6, and rats were divided randomly into five groups: control (saline), CCl4, CCl4 plus oligo-peptide I-C-F-6 (0.12 and 0.24 mg/kg), and CCl4 plus colchicine (0.11 mg/kg). Here, we demonstrated that oligo-peptide I-C-F-6 ameliorated liver injury, inflammation, and hepatic fibrogenesis induced by CCl4. Oligo-peptide I-C-F-6 also inhibited the activation of hepatic stellate cells (HSCs) in vivo and in vitro, as evaluated by the expression of transforming growth factor-ß1 (TGF-ß1) and α-smooth muscle actin (α-SMA), which is a specific marker of HSC activation. Moreover, oligo-peptide I-C-F-6 significantly reduced the expression and distribution of ß-catenin, P-AKT, phospho (P)-GSK-3ß, nuclear factor κB (NF-κB) P65, phospho-P65, and IκB kinase α/ß (IKK-α/ß) levels; additionally, IκB-α level was elevated both in vivo and in vitro. Together, these results indicate that oligo-peptide I-C-F-6 has hepatoprotective and anti-fibrotic effects in animal models of liver fibrosis, the mechanism of which may be related to modulating NF-κB and Wnt/ß-catenin signaling.

Evans-Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic-Organic Hybrid Compounds with Copper-Organic Coordination Complexes: Synthesis and Oxidation Catalysis.

Four new hybrid architectures containing a [Co2Mo10H4O38]6- polyoxoanion, (en)[Cu3(ptz)4(H2O)4][Co2Mo10H4O38]·24H2O (1), (Hbim)2[{Cu(bim)2(H2O)2}2{Co2Mo10H4O38}]·5H2O (2), H2[Cu(dpdo)3(H2O)4][{Cu2(dpdo)3(H2O)4(CH3CN)}2{Co2Mo10H4O38}2]·9H2O (3), and (H2bpp)4[{Cu(H2O)2}{NaCo2Mo10H4O38}2]·10H2O (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host-guest framework composed of 3D Cu-ptz as the host and Evans-Showell-type polyoxoanion [Co2Mo10H4O38]6- as the guest. Compound 2 is constructed from [Co2Mo10H4O38]6- polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [Co2Mo10H4O38]6- polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [Co2Mo10H4O38]6- polyoxoanions joined together by Na+ and Cu2+ cations. As far as we know, compound 1 is the first host-guest compound with an Evans-Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic-organic hybrid architectures constructed from Evans-Showell-type polyoxometalates. Compounds 1-4 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.