Intermolecular O-O Bond Formation between High-Valent Ru-oxo Species.

Despite extensive research on water oxidation catalysts over the past few decades, the relationship between high-valent metal-oxo intermediates and the O-O bond formation pathway has not been well clarified. Our previous study showed that the high spin density on O in RuV=O is pivotal for the interaction of two metal-oxyl radical (I2M) pathways. In this study, we found that introducing an axially coordinating ligand, which is favorable for bimolecular coupling, into the Ru-pda catalyst can rearrange its geometry. The shifts in geometric orientation altered its O-O bond formation pathway from water nucleophilic attack (WNA) to I2M, resulting in a 70-fold increase in water oxidation activity. This implies that the I2M pathway is concurrently influenced by the spin density on oxo and the geometry organization of the catalysts. The observed mechanistic switch and theoretical studies provide insights into controlling reaction pathways for homogeneous water oxidation catalysis.

Levosimendan: A New Therapeutical Strategy in Patients with Renal Insufficiency.

Levosimendan, a Ca2 + sensitizer with positive inotropic effects, is primarily employed for the short-term treatment of acute decompensated heart failure (ADHF). Levosimendan exerts renal function protection through various mechanisms, including anti-apoptosis, anti-inflammatory, and antioxidant effects in vivo. Additionally, levosimendan may have a protective effect on individuals with heart failure and renal insufficiency, as well as on renal function impairment after cardiac surgery. However, the application of levosimendan in patients with severe renal dysfunction remains controversial. This article delves into the use of levosimendan in severe renal insufficiency, explores its impact on renal function, and provides a comprehensive overview of its impact on renal function after cardiac surgery.

Safety and efficacy of apixaban versus vitamin K antagonists in patients undergoing dialysis: a systematic review and meta-analysis.

BACKGROUND: This review aims to evaluate the safety and efficacy of apixaban vs. vitamin K antagonists (VKAs) in patients on dialysis. METHODS: All types of studies published on PubMed, Embase, CENTRAL, and Web of Science up to 10 September 2023 and comparing outcomes of apixaban vs. VKA in dialysis patients were eligible. RESULTS: Two randomized controlled trials (RCTs) and six retrospective studies were included. Apixaban treatment was associated with significantly lower risk of major bleeding (RR: 0.61; 95% CI: 0.48, 0.77; I2 = 50%) and clinically relevant non-major bleeding (RR: 0.82, 95% CI: 0.68, 0.98, I2 = 9%) compared to VKA. Meta-analysis also showed that the risk of gastrointestinal bleeding (RR: 0.74, 95% CI: 0.64, 0.85, I2 = 16%) and intracranial bleeding (RR: 0.64, 95% CI: 0.49, 0.84, I2 = 0%) was significantly reduced with apixaban. Meta-analysis showed no difference in the risk of ischemic stroke (RR: 0.40, 95% CI: 0.06, 2.69, I2 = 0%), mortality (RR: 1.26, 95% CI: 0.74, 2.16, I2 = 94%) and recurrent venous thromboembolism (RR: 1.02, 95% CI: 0.87, 1.21, I2 = 0%) between the two groups. Subgroup analysis of RCTs showed no difference in bleeding outcomes. CONCLUSIONS: Low-quality evidence from a mix of RCTs and retrospective studies shows that apixaban may have better safety and equivalent efficacy as compared to VKA in dialysis patients. Apixaban treatment correlated with significantly reduced risk of major bleeding and clinically relevant nonmajor bleeding in observational studies but not in RCTs. The predominance of retrospective data warrants caution in the interpretation of results.

Bioinspired Active Site with a Coordination-Adaptive Organosulfonate Ligand for Catalytic Water Oxidation at Neutral pH.

Many enzymes use adaptive frameworks to preorganize substrates, accommodate various structural and electronic demands of intermediates, and accelerate related catalysis. Inspired by biological systems, a Ru-based molecular water oxidation catalyst containing a configurationally labile ligand [2,2':6',2″-terpyridine]-6,6″-disulfonate was designed to mimic enzymatic framework, in which the sulfonate coordination is highly flexible and functions as both an electron donor to stabilize high-valent Ru and a proton acceptor to accelerate water dissociation, thus boosting the catalytic water oxidation performance thermodynamically and kinetically. The combination of single-crystal X-ray analysis, various temperature NMR, electrochemical techniques, and DFT calculations was utilized to investigate the fundamental role of the self-adaptive ligand, demonstrating that the on-demand configurational changes give rise to fast catalytic kinetics with a turnover frequency (TOF) over 2000 s-1, which is compared to oxygen-evolving complex (OEC) in natural photosynthesis.

Promoting Proton Transfer and Stabilizing Intermediates in Catalytic Water Oxidation via Hydrophobic Outer Sphere Interactions.

The outer coordination sphere of metalloenzyme often plays an important role in its high catalytic activity, however, this principle is rarely considered in the design of man-made molecular catalysts. Herein, four Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) based molecular water oxidation catalysts with well-defined outer spheres are designed and synthesized. Experimental and theoretical studies showed that the hydrophobic environment around the Ru center could lead to thermodynamic stabilization of the high-valent intermediates and kinetic acceleration of the proton transfer process during catalytic water oxidation. By this outer sphere stabilization, a 6-fold rate increase for water oxidation catalysis has been achieved.

Unveiling the Uncommon Fluorescent Recognition Mechanism towards Pertechnetate Using a Cationic Metal-Organic Framework Bearing N-Heterocyclic AIE Molecules.

As one of most problematic radionuclides, technetium-99, mainly in the form of anionic pertechnetate (TcO4 - ), exhibits high environmental mobility, long half-life, and radioactive hazard. Due to low charge density and high hydrophobicity for this tetrahedral anion, it is extremely difficult to recognize it in water. Seeking efficient and selective recognition method for TcO4 - is still a big challenge. Herein, a new water-stable cationic metal-organic framework (ZJU-X8) was reported, bearing tetraphenylethylene pyrimidine-based aggregation-induced emission (AIE) ligands and attainable silver sites for TcO4 - detection. ZJU-X8 underwent an obvious spectroscopic change from brilliant blue to flavovirens and exhibited splendid selectivity towards TcO4 - . This uncommon fluorescent recognition mechanism was well elucidated by batch sorption experiments and DFT calculations. It was found that only TcO4 - could enter into the body of ZJU-X8 through anion exchange whereas other competing anions were excluded outside. Subsequently, after interaction between TcO4 - and silver ions, the electron polarizations from pyrimidine rings to Ag+ cations significantly lowered the energy level of the π* orbital and thus reduced the π-π* energy gap, resulting in a red-shift in the fluorescent spectra.

99TcO4- Separation through Selective Crystallization Assisted by Polydentate Benzene-Aminoguanidinium Ligands.

99Tc is one of the most abundant radiotoxic isotopes in used nuclear fuel with a high fission yield and a long half-life. Effective removal of pertechnetate (TcO4-) from an aqueous solution is important for nuclear waste separation and remediation. Herein, we report a series of facilely obtained benzene-linked guanidiniums that could precipitate TcO4- and its nonradioactive surrogate ReO4- from a high-concentration acidic solution through self-assembly crystallization. The resulting perrhenate and pertechnetate solids exhibit exceptionally low aqueous solubility. The benzene-linked guanidiniums hold one of the highest TcO4- removal capacities (1279 mg g-1) among previously reported materials and possess a removal percentage of 59% for ReO4- in the presence of Cl- over 50 times. The crystallization mechanism was clearly illustrated by the single-crystal structures and density functional theory calculations, indicating that TcO4- is captured through a charge-assisted hydrogen bonding interaction and stabilized by π-π stacking layers. In addition, the removal process is easily recycled and no toxic organic reagents are introduced. This work provides a green approach to preliminarily separate TcO4- from high-level nuclear wastes.

Crystalline-Phase-Recognition-Induced Domino Phase Transition and Luminescence Switching for Advanced Information Encryption.

Herein, a new mechanism, namely, crystalline phase recognition (CPR), is proposed for the single-crystal-to-single-crystal (SCSC) transition of metal halides. Chiral ß-[Bmmim]2 SbCl5 (Bmmim=1-butyl-2,3-methylimidazolium) can recognize achiral α-[Bmmim]2 SbCl5 on the basis of a key-lock feature through intercontact of their single crystals, resulting in a domino phase transition (DPT). The concomitant photoluminescence (PL) switching enables observation of the DPT in situ. The liquid eutectic interface, stress-strain transfer, and feasible thermodynamics are key issues for the CPR. DFT calculations and PL measurements revealed that the optical absorption and emission of the isomers mainly originate from [SbCl5 ]2- anions. The structural effects (e.g., supramolecular interactions and [SbCl5 ]2- distortion) on the optical emission are clarified. As a novel type of stimuli response, the CPR-induced DPT and luminescence switching exhibit potential for application in advanced time-resolved information encryption.

Electron Beam Irradiation-Induced Formation of Defect-Rich Zeolites under Ambient Condition within Minutes.

Zeolites are a well-known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy-consuming. Herein, we utilize high-energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na-A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na-A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites.

Modulation of the Structure and Photoluminescence of Bismuth(III) Chloride Hybrids by Altering the Ionic-Liquid Cations.

Two bismuth(III) halides hybrids with room-temperature phosphorescence (RTP), namely, [BPy]2[Bi2Cl8(bpym)] (1, BPy = N-butylpyridinium) and [EPy]2[Bi2Cl8(bpym)] (2, EPy = N-ethylpyridinium), were synthesized and characterized. Structural comparison reveals that 1 and 2 possess similar anionic zigzaglike chain of [Bi2Cl8(bpym)]n2n-; however, different packing modes of anion/cations and thus different weak interactions. Interestingly, the utilization of pyridinium cations with different length of alkyl chain could tune the RTP behaviors efficiently. The RTP quantum yield (QY) is increased more than 5-fold from 1 to 2 probably due to more rigid structure of 2 arising from the additional H-bond and anion-π interactions, as confirmed by Hirshfeld surfaces analyses and PLATON calculations. Moreover, additional π-π interactions in 1 could stabilize the triplet excitons, leading to an average lifetime of 1 (11.36 ms at 77 K and 1.407 ms at 298 K) being higher than 2 (0.3618 ms at 77 K and 0.07511 ms at 298 K). Density functional theory (DFT) calculations confirm that inorganic moiety to organic ligand charge-transfer (IOCT) is involved in the phosphorescence process. The present work provides a new sight into the design of RTP metal halides through studying the structure-RTP relationship.

Injuries due to foreign body ingestion and insertion in children: 10 years of experience at a single institution.

AIM: Foreign body (FB) injuries represent a severe public health problem during childhood. The aim of this study was to report our experience with patients with injuries due to FB ingestion and insertion who were treated surgically at our institution. METHODS: A total of 78 paediatric patients who were hospitalised for FB injuries were retrospectively reviewed. RESULTS: The series was composed of 27 males and 51 females, with a median age of 3.6 years. The cases included 35 cases of FB ingestion and 43 cases of FB insertion, including 40 cases with a vaginal insertion, 2 cases with a rectal insertion and 1 case with a urethra insertion. Intestinal perforation (n = 26) was a more common complication than intestinal obstruction (n = 9) in patients who had ingested a FB. The main clinical symptom was persistent vaginal discharge, followed by vaginal bleeding for patients with a vaginal FB insertion. Exploratory laparotomy was performed on 36 patients, while a laparoscopic approach was employed in 1 patient. Forty patients underwent hysteroscopy and one patient underwent cystotomy to remove the FB. All FBs were successfully removed. Of the 78 FBs recovered, 26 were food objects, while non-food objects were found in 52 patients. All patients recovered well, except one patient with an intestinal obstruction from adhesions that occurred approximately 1 month after discharge. CONCLUSIONS: Early recognition of FB injuries and appropriate management can significantly reduce complications. Surgical removal of a FB can be safe and effective, and relatively better outcomes can be achieved.

miR-150 regulates glucose utilization through targeting GLUT4 in insulin-resistant cardiomyocytes.

MicroRNAs (miRNAs) play an important role in cardiac function and metabolism. However, whether they regulate insulin resistance (IR) of cardiomyocytes remains unclear. The aim of the present study was to shed light on this issue with a focus on miR-150. We found here that miR-150 level was elevated in myocardium of type 2 diabetes mellitus (T2DM) rat model and in insulin-resistant cardiomyocytes induced by high glucose (25 mM) and high insulin (1 µM). Deregulation of miR-150 downregulated the protein and mRNA levels of glucose transporter 4 (GLUT4) as assessed by western blot, real-time polymerase chain reaction (qPCR), and immunofluorescence assays. Overexpression of miR-150 inhibited glucose utilization in cardiomyocytes as detected by 2-deoxyglucose transport and glucose consumption assays. In contrast, knockdown of miR-150 significantly increased glucose uptake in cardiomyocytes. Moreover, GLUT4 translocation was increased after transfection of miR-150 inhibitor (AMO-150). Collectively, miR-150 reduced glucose utilization by directly decreasing the expression and translocation of GLUT4 in the cardiomyocytes with IR and therefore might be a new therapeutic target for metabolic diseases such as T2DM.

Emergence of a Radical-Stabilizing Metal-Organic Framework as a Radio-photoluminescence Dosimeter.

Radio-photoluminescence (RPL) materials display a distinct radiation-induced permanent luminescence center, and therefore find application in the detection of ionizing radiation. The current inventory of RPL materials, which were discovered by serendipity, has been limited to a small number of metal-ion-doped inorganic materials. Here we document the RPL of a metal-organic framework (MOF) for the first time: X-ray induced free radicals are accumulated on the organic linker and are subsequently stabilized in the conjugated fragment in the structure, while the metal center acts as the X-ray attenuator. These radicals afford new emission features in both UV-excited and X-ray excited luminescence spectra, making it possible to establish linear relationships between the radiation dose and the normalized intensity of the new emission feature. The MOF-based RPL materials exhibit advantages in terms of the dose detection range, reusability, emission stability, and energy threshold. Based on a comprehensive electronic structure and energy diagram study, the rational design and a substantial expansion of candidate RPL materials can be anticipated.

Designing Polymorphic Bi3+-Containing Ionic Liquids for Stimuli-Responsive Luminescent Materials.

Solid-state luminescent materials that possess reversible fluorescence changes toward external multistimuli are of immense interest because of their potential applications in data storage and sensors. While the recent developments in this field are mainly focused on the π-conjugated organic molecules. Herein two polymorphic luminescent ionic liquid (IL)-based stimuli-responsive materials were designed by the supramolecular assemblies of an organic-decorated chlorobismuthate anion and a rotationally flexible imidazolium cation, namely, α (1)/ß (2)-[Bmmim][BiCl4(2,2'-bpy)] (Bmmim = 1-butyl-2,3-dimethylimidazolium; 2,2'-bpy = 2,2'-bipyridine). Because of the different conformations of the n-butyl chains on the imidazolium cations, tuning of the supramolecular packing structures as well as luminescent colors for 1 and 2 was realized. Single-crystal X-ray diffraction and Hirshfeld surface analyses disclose that the polymorphism-dependent emission may be attributed to the different weak interactions, especially to the π-π interactions between adjacent [BiCl4(2,2'-bpy)]- anions in two compounds. Additionally, compound 2 could be transformed into 1 spontaneously at ambient conditions, which could be triggered by the moisture in the air. Both of the title compounds could detect NH3 vapor selectively through the luminescence "turn-off" method rapidly and reversibly because of the destruction of intermolecular interactions, indicating their stimuli-responsive property toward NH3.

Highly Responsive and Ultrasensitive Non-Enzymatic Electrochemical Glucose Sensor Based on Au Foam.

Glucose concentration is an important physiological index, therefore methods for sensitive detection of glucose are important. In this study, Au foam was prepared by electrodeposition with a dynamic gas template on an Au nanoparticle/Si substrate. The Au foam showed ultrasensitivity, high selectivity, and long-term stability in the quantitative detection of glucose. The foam was used as an electrode, and the amperometric response indicated excellent catalytic activity in glucose oxidation, with a linear response across the concentration range 0.5 µM to 12 mM, and a limit of detection of 0.14 µM. High selectivity for interfering molecules at six times the normal level and long-term stability for 30 days were obtained. The results for electrochemical detection with Au foam of glucose in human serum were consistent with those obtained with a sensor based on surface-enhanced Raman spectroscopy and a commercial sensor. This proves that this method can be used with real samples. These results show that Au foam has great potential for use as a non-enzymatic glucose sensor.

Hybrid Chloroantimonates(III): Thermally Induced Triple-Mode Reversible Luminescent Switching and Laser-Printable Rewritable Luminescent Paper.

Two hybrid chloroantimonates(III), [Bzmim]3 SbCl6 (1, Bzmim=1-benzyl-3-methylimidazolium, Tm1 =410 K) and [Bzmim]2 SbCl5 (2, Tm2 =348 K) are presented. 1 exhibits green emission (quantum efficiency of 87.5 %); 2 exhibits blue and red emissions under the irradiation of 310 and 396 nm light, respectively. Using different cooling methods, crystalline 1 and IL@2 (IL=ionic liquid of [Bzmim]Cl) could be generated from the molten 1. Reversible structural and PL transformation triggered by moisture or heat was observed between 1 and IL@2. Such PL switching, combined with the crystallization-induced PL properties of 1 and 2, resulted in the firstly reported triple-mode reversible PL switching, that is, on-off (T>Tm1 ), color switching (T

Supramolecular Organization of [TeCl6]2- with Ionic Liquid Cations: Studies on the Electrical Conductivity and Luminescent Properties.

A series of hybrid tellurium chlorides based on ionic liquids (ILs), namely, α-[Bmim]2TeCl6 (1, Bmim = 1-butyl-3-methyl imidazolium), ß-[Bmim]2TeCl6 (2), [HOOCMim]2TeCl6 (3, HOOCMim = 1-carboxymethyl-3-methyl imidazolium), [Bzmim]2TeCl6 (4, Bzmim = 1-benzyl-3-methyl imidazolium), [EPy]2TeCl6 (5, EPy = 1-ethylpyridinium), [Bmmim]2TeCl6 (6, Bmmim = 1-butyl-2,3-dimethyl imidazolium), have been synthesized and characterized. Different kinds of supramolecular networks have been obtained via self-assemblies of isolated [TeCl6]2- anions and various ionic liquid cations. Interestingly, all the title compounds exhibit semiconducting behaviors: their optical absorption edges calculated from reflectance spectra are in the range of 2.54-2.68 eV; their electrical conductivities measured by using two-probe direct current (DC) method indicate values from 2.06 × 10-9 to 4.65 × 10-6 S/cm, which are typical for semiconductors and comparable to the reported crystalline hybrid metal halides. The luminescent property studies reveal that only compounds 3 and 6 exhibit intense emissions both at 77 and 298 K, probably owing to the minimum distortion of the TeCl6 octahedra in 3 and 6.

Prepubertal testicular tumors in China: a 10-year experience with 67 cases.

AIM: Prepubertal testicular tumors are rare in children. We aim to present clinical and histological features of prepubertal testicular tumors through the analysis of the long-term experiences of a single medical center of China. MATERIALS AND METHODS: A total of 67 children (≤ 14 years) treated for testicular tumor at our institution from 2005 to 2015 were retrospectively reviewed. Data relating the clinical characteristics, histopathology findings, serum tumor markers, treatment method, and outcome were collected. RESULTS: The patients' median age at diagnosis was 18 months (range 3-168 months), and 49 cases (73.1%) were diagnosed at age younger than 3 years. The most common clinical presentation was a painless scrotal mass or swelling. Regarding histology, 32 (47.8%) were teratomas and only one of these tumors presents immature teratomas, 20 (29.9%) were yolk sac tumors, 9 (13.4%) were epidermoid cyst, 1 (1.5%) was a Leydig cell tumor, 1 (1.5%) was a mixed malignant germ cell tumor, and 4 (8.3%) were paratesticular tumors. For germ cell tumors, the mean preoperative serum α-fetoprotein (AFP) level was significantly higher in patients with yolk sac tumor than in those with teratomas (2,078 ng/mL vs 5.7 ng/mL). Of all these patients, 37 (55.2%) were treated with radical inguinal orchiectomy and testis-sparing surgery was planned and achieved in 30 (44.8%). Surveillance was performed in 60 patients. None of the patients developed recurrence or testicular atrophy after appropriate treatment. CONCLUSIONS: The majority of our cases were benign, with the most common histopathological subtype being teratoma. A testis-sparing procedure should be performed in children with a palpable testicular mass and negative tumor markers. This study shows a better outlook for prepuberty patient with testicular tumors than their adult counterparts.

α- and ß-[Bmim][BiCl4 (2,2'-bpy)]: Two Polymorphic Bismuth-Containing Ionic Liquids with Crystallization-Induced Phosphorescence.

This work reports the syntheses, structures, and luminescence properties of two supramolecular polymorphic compounds composed of a hybrid bismuth(III) chloride anion and an imidazolium cation, namely α- (1) and ß- (2) [Bmim][BiCl4 (2,2'-bpy)] (Bmim=1-butyl-3-methyl imidazolium; 2,2'-bpy=2,2'-bipyridine). They are the first two examples of Bi3+ -containing ionic liquids (ILs). Their different packing modes may be ascribed to the rotational flexibility of the butyl group on the [Bmim]+ cation. A comparative study of the weak intermolecular interactions present in the two polymorphs has been performed by Hirshfeld surface and two-dimensional fingerprint analyses. Investigations of the luminescence properties revealed that crystallization induced greenish-yellow phosphorescence with quantum yields of 26.07 % for 1 and 36.59 % for 2, which are among the highest hitherto reported for hybrid halobismuthate compounds. The difference in phosphorescence may be attributed to the different weak interactions in 1 and 2, especially π-π contacts. This work opens the way to further research on new types of polymorphism-dependent luminescent materials based on a combination of rotationally isomeric IL cations with organic decorated bismuth(III) chloride anions.

Sulfophenyl-Functionalized Reduced Graphene Oxide Networks on Electrospun 3D Scaffold for Ultrasensitive NO2 Gas Sensor.

Ultrasensitive room temperature real-time NO2 sensors are highly desirable due to potential threats on environmental security and personal respiratory. Traditional NO2 gas sensors with highly operated temperatures (200-600 °C) and limited reversibility are mainly constructed from semiconducting oxide-deposited ceramic tubes or inter-finger probes. Herein, we report the functionalized graphene network film sensors assembled on an electrospun three-dimensional (3D) nanonetwork skeleton for ultrasensitive NO2 sensing. The functional 3D scaffold was prepared by electrospinning interconnected polyacrylonitrile (PAN) nanofibers onto a nylon window screen to provide a 3D nanonetwork skeleton. Then, the sulfophenyl-functionalized reduced graphene oxide (SFRGO) was assembled on the electrospun 3D nanonetwork skeleton to form SFRGO network films. The assembled functionalized graphene network film sensors exhibit excellent NO2 sensing performance (10 ppb to 20 ppm) at room temperature, reliable reversibility, good selectivity, and better sensing cycle stability. These improvements can be ascribed to the functionalization of graphene with electron-withdrawing sulfophenyl groups, the high surface-to-volume ratio, and the effective sensing channels from SFRGO wrapping onto the interconnected 3D scaffold. The SFRGO network-sensing film has the advantages of simple preparation, low cost, good processability, and ultrasensitive NO2 sensing, all advantages that can be utilized for potential integration into smart windows and wearable electronic devices for real-time household gas sensors.