Two Different Three-Dimensional Uranium-Containing Polymolybdates Based on Zn(II) for the Heterogeneous Catalytic Construction of C-N Bond.

The introduction of transition metal (TM) ions into polyoxometalates (POMs) cannot only bring about interesting structural diversities but also enable changes in properties. However, TM-containing Silverton-type polyoxomolybdates are still lacking in terms of structural diversity and application development. Herein, two Zn(II)-containing Silverton-type {UMo12O42}-based polyoxomolybdates, H1.89Na4.11(H2O)9Zn[UMo12O42]·4.5H2O (Zn-1) and H1.8Na4.2(H2O)12Zn[UMo12O42] (Zn-2) were hydrothermally synthesized, demonstrating a practical strategy to assembly of TM-containing Silverton-type POMs. Zn-1 is proven to be an excellent and recyclable heterogeneous catalyst in cross-dehydrogenation coupling of 1,4-naphthoquinones with amines reactions, and a series of 2-amino-1,4-naphthoquinones with potential medicinal value have been constructed.

Pure separation of acetylene based on a sulfonic acid and amino group functionalized Zn-MOF.

The dual-ligand strategy was employed to synthesize a new microporous material, [Zn3(SNDC)(AmTAZ)3(H2O)]·H2O·CH3CN (1), incorporating sulfonic acid and amino groups for enhancing gas adsorption and separation. The activated 1 (named 1a) exhibited selective adsorption of acetylene over carbon dioxide and methane. Hence, the dual-ligand strategy optimized the pore environment and provided an effective approach for pure separation of gases.

CPhaMAS: An online platform for pharmacokinetic data analysis based on optimized parameter fitting algorithm.

BACKGROUND AND OBJECTIVE: Clinical pharmacological modeling and statistical analysis software is an essential basic tool for drug development and personalized drug therapy. The learning curve of current basic tools is steep and unfriendly to beginners. The curve is even more challenging in cases of significant individual differences or measurement errors in data, resulting in difficulties in accurately estimating pharmacokinetic parameters by existing fitting algorithms. Hence, this study aims to explore a new optimized parameter fitting algorithm that reduces the sensitivity of the model to initial values and integrate it into the CPhaMAS platform, a user-friendly online application for pharmacokinetic data analysis. METHODS: In this study, we proposed an optimized Nelder-Mead method that reinitializes simplex vertices when trapped in local solutions and integrated it into the CPhaMAS platform. The CPhaMAS, an online platform for pharmacokinetic data analysis, includes three modules: compartment model analysis, non-compartment analysis (NCA) and bioequivalence/bioavailability (BE/BA) analysis. Our proposed CPhaMAS platform was evaluated and compared with existing WinNonlin. RESULTS: The platform was easy to learn and did not require code programming. The accuracy investigation found that the optimized Nelder-Mead method of the CPhaMAS platform showed better accuracy (smaller mean relative error and higher R2) in two-compartment and extravascular administration models when the initial value was set to true and abnormal values (10 times larger or smaller than the true value) compared with the WinNonlin. The mean relative error of the NCA calculation parameters of CPhaMAS and WinNonlin was <0.0001 %. When calculating BE for conventional, high-variability and narrow-therapeutic drugs. The main statistical parameters of the parameters Cmax, AUCt, and AUCinf in CPhaMAS have a mean relative error of <0.01% compared to WinNonLin. CONCLUSIONS: In summary, CPhaMAS is a user-friendly platform with relatively accurate algorithms. It is a powerful tool for analysing pharmacokinetic data for new drug development and precision medicine.

Three Polyoxometalate-Based Ag-Organic Compounds as Heterogeneous Catalysts for the Synthesis of Benzimidazoles.

Three new POM-based compounds, with formulae [Na0.63Ag3(Htba)2.37(tba)0.63(H2O)2(PMo12O40)]·4H2O (Ag3PMo), [Ag4(Htba)4(H2O)2(PMo12O40)](NO3)·H2O (Ag4PMo), and [Ag3(Htba)2(tba)(PW12O40)0.5](NO3)0.5·13H2O (Ag3PW), were prepared with a 3-(4H-1,2,4-triazol-4-yl)benzoic acid (Htba) ligand, Keggin-type anions ([PMo12O40]3-/[PW12O40]3-), and a silver ion (Ag+). The structural features of these compounds are particularly different from the multinuclear subunits, which are [Ag3(tba)3] clusters in Ag3PMo, [Ag4(tba)3] chains in Ag4PMo, and [Ag3(tba)3]2 clusters in Ag3PW, connected by multidonor atom tba ligands and Ag+ ions. Meanwhile, in these compounds, polyanions act as polydentate ligands to link adjacent Ag-tba metal-organic units and expand their spatial dimensions. These compounds, as heterogeneous catalysts, exhibit high stability and excellent catalytic activity to construct benzimidazoles. Ag3PMo could efficiently catalyze the condensation of benzene-1,2-diamines and benzaldehydes and produce benzimidazoles in good yields. In addition, Ag3PMo could be reused up to 7 times and was suitable for gram-scale reactions.

Diagnosis and treatment of post-cholecystectomy diarrhoea.

The incidence of cholecystitis is relatively high in developed countries and may usually be attributed to gallstones, the treatment for which involves complete surgical removal of the gallbladder (cholecystectomy). Bile acids produced following cholecystectomy continue to flow into the duodenum but are poorly absorbed by the colon. Excessive bile acids in the colon stimulate mucosal secretion of water and electrolytes leading, in severe cases, to diarrhoea. Bile acid diarrhoea (BAD) is difficult to diagnose, requiring a comprehensive medical history and physical examination in combination with laboratory evaluation. The current work reviews the diagnosis and treatment of BAD following cholecystectomy.

Two-Fold Interpenetrated Binuclear Nickel Metal-Organic Framework as a Heterogeneous Catalyst for N-Heterocycle Synthesis.

A binuclear Ni(II)-based metal-organic framework {[Ni2(btb)1.333(H2O)3.578(py)1.422]·(DMF)(H2O)3.25}n (Nibtb) was solvothermally synthesized (H3btb = 1,3,5-tri(4-carboxylphenyl)benzene, py = pyridine, DMF = N,N-dimethylformamide). Nibtb shows a rare 2-fold interpenetrating (3,4)-connected 3D network with a point symbol of (83)4(86)3 based on binuclear Ni(II) clusters. Nibtb as a heterogeneous catalyst combines the high stability of MOFs and excellent catalytic activity of nickel, which exhibits excellent catalytic activity for the synthesis of benzimidazoles and pyrazoles under mild conditions. Moreover, the catalyst can be easily separated and reused for seven successive cycles and maintains high catalytic activity.

Complete mitochondrial genome of Ctenophthalmus quadratus and Stenischia humilis in China provides insights into fleas phylogeny.

Fleas (Order Siphonaptera) are common blood-feeding ectoparasites, which have important economic significance. Limited mitochondrial genome information has impeded the study of flea biology, population genetics and phylogenetics. The Ctenophthalmus quadratus and Stenischia humilis complete mt genomes are described in this study. The samples were collected from Jianchuan, Yunnan plague foci, China. The mt genomes of C. quadratus and S. humilis were 15,938 bp and 15,617 bp, respectively. The gene arrangement of mt genome was consistent with that of other fleas, which include 22 tRNA genes, 13 protein-coding genes, and two rRNA genes, with a total of 37 genes. The relationship between C. quadratus and S. humilis in fleas was inferred by phylogenetic analysis of mt genome sequence datasets. Phylogenetic analyzes showed that the C. quadratus and S. humilis belonged to different species in the same family, and were closely related to Hystrichopsylla weida qinlingensis in the same family; and revealed that the family Hystrichopsyllidae is paraphyletic, supporting the monophyly of the order Siphonaptera. This study decodes the complete mt genomes of the C. quadratus and S. humilis for the first time. The results demonstrate that the C. quadratus and S. humilis are distinct species, and fleas are monophyletic. Analysis of mt genome provides novel molecular data for further studying the phylogeny and evolution of fleas.

Separation of C2H2/C2H4/C2H6 and C2H2/CO2 in a Nitrogen-Rich Copper-Based Microporous Metal-Organic Framework.

The purification of industrially valuable C2H2 and C2H4 from multicomponent mixtures represents a crucial process in the chemical industry. In this study, we present a copper-based metal-organic framework (L-py-Cu) built on a nitrogen-rich organic linker that is capable of separating C2H2/C2H4/C2H6 and C2H2/CO2 mixtures, therefore producing highly pure C2H4 and C2H2, respectively. L-py-Cu exhibits favorable adsorption of C2H2 and C2H6 over C2H4 and thus achieves one-step C2H4 purification from C2H2/C2H4/C2H6 ternary mixtures, as verified by multicomponent breakthrough measurements. In addition, it can also extract C2H2 from C2H2/CO2 binary mixtures.

DKADE: a novel framework based on deep learning and knowledge graph for identifying adverse drug events and related medications.

Adverse drug events (ADEs) are common in clinical practice and can cause significant harm to patients and increase resource use. Natural language processing (NLP) has been applied to automate ADE detection, but NLP systems become less adaptable when drug entities are missing or multiple medications are specified in clinical narratives. Additionally, no Chinese-language NLP system has been developed for ADE detection due to the complexity of Chinese semantics, despite ˃10 million cases of drug-related adverse events occurring annually in China. To address these challenges, we propose DKADE, a deep learning and knowledge graph-based framework for identifying ADEs. DKADE infers missing drug entities and evaluates their correlations with ADEs by combining medication orders and existing drug knowledge. Moreover, DKADE can automatically screen for new adverse drug reactions. Experimental results show that DKADE achieves an overall F1-score value of 91.13%. Furthermore, the adaptability of DKADE is validated using real-world external clinical data. In summary, DKADE is a powerful tool for studying drug safety and automating adverse event monitoring.

Efficient C2H2-selective separation in a microporous Zn(II)-based metal-organic framework via the dual-ligand strategy.

Implementing the dual-ligand strategy, a microporous Zn-based MOF 1 with nitro and amino groups was effectively produced. The activated interconnected pores of 1 exhibited high C2H2 uptake capacity and preferential adsorption behaviour for C2H2 over CO2, as identified by the experiments and simulations. This work provides a new approach for designing and synthesizing the MOFs with desired structures and properties by optimizing their pore environment via the dual-ligand strategy.

Ameliorating Adsorption Performance for Poisonous Methylene Blue through the Amino Functionalization of Metal-Organic Frameworks.

Amino (-NH2)-functionalized metal-organic frameworks (MOFs) are widely applied to improve the properties of materials owing to the rich host-guest chemical properties of amino groups. In this work, the amino-functionalization strategy was thus employed to improve the sorption performance of methylene blue (MB). The introduction of -NH2 groups in AOBTC-Zn did not reduce the pore size of the framework but rather modulated and optimized the host-guest interactions of MOFs. The MB+ sorption result was significantly improved by the NH2-functionalized NH2-AOBTC-Zn. The results showed that the maximum sorption capacity of NH2-AOBTC-Zn is much higher (1623 mg/g) than that of AOBTC-Zn (204 mg/g), which was comparable with that of MIL-68(Al) (1666 mg/g). The adsorption kinetics and isothermal models indicated that the MB+ sorption processes of both MOFs were consistent with the Langmuir isothermal and pseudo-second-order kinetic models. The single-group and multicomponent sorption experiments showed that the sorption behavior was the result of π-π interaction, electrostatic interaction, hydrogen bonding interaction, and pore size interaction. In particular, NH2-AOBTC-Zn exhibits a higher adsorption capacity than AOBTC-Zn due to the additional hydrogen bonding interactions it provided. These may guide the design of porous MOFs with side group modification for liquid phase sorption/separation.

Self-Assembly of a U(VI)-Containing Polytungstate Tetramer with Lewis Acid-Base Catalytic Activity for a Dehydration Condensation Reaction.

A novel U(VI)-containing polytungstate (U-POW) tetramer, {K1.37Na26.63[K2(UO2)4Cl0.5(OH)5.5(γ-SiW10O36)4]}·ca66H2O (U4), was synthesized using the Keggin-type precursor [γ-SiW10O36]8- and UO2(NO3)2. U4 was further characterized by single-crystal X-ray diffraction, FT-IR, Raman spectroscopy, solid-state diffuse reflection spectroscopy, ICP-OES, ESI-MS, TGA, and PXRD. The central {K2(UO2)4Cl0.5(OH)5.5} chromophore was constructed dexterously from four uranyl, four halves of K ions, 5.5 bridging µ2-OH, and disordered Cl ions, and was further stabilized by four {γ-SiW10} moieties to construct the tetramer [K2(UO2)4Cl0.5(OH)5.5(γ-SiW10O36)4]28-. Notably, U4 could work as an effective bifunctional Lewis acid-base catalyst for the synthesis of pyrazoles via the condensation of hydrazines with 1,3-diketones under mild conditions, which is attributed to the synergetic effect of the Lewis acidity of U(VI) and the Lewis basicity of {γ-SiW10}.

Safety, Pharmacokinetics/Pharmacodynamics, and Absolute Bioavailability of Dexmedetomidine Hydrochloride Nasal Spray in Healthy Subjects: A Randomized, Parallel, Escalating Dose Study.

Background: The present study evaluated the safety, pharmacokinetics/pharmacodynamics (PK/PD), and absolute bioavailability (Fabs) of Dex nasal spray in healthy adult subjects, which serves as a bridge for the subsequent study in children. Methods: Part 1: a double-blind, placebo-controlled, single ascending dose study was performed on 48 subjects. For 20-/40-µg groups, every 6/2 subjects received either Dex/placebo nasal spray or Dex/placebo injection in two periods. In total, 12/4 subjects each received 100 µg Dex/placebo nasal spray. Part 2: a randomized, double-blind, placebo-controlled study; 12/4 subjects received 150 µg Dex/placebo nasal spray. Part 3: a randomized, open, self-crossover study; 12 subjects received 20 µg and 100 µg Dex nasal spray in two periods alternately. The method of administration was optimized in Part 2 and Part 3. Results: In part 1, Dex nasal spray was well tolerated up to the maximum dose of 100 µg, whereas the Fabs was tolerated to only 28.9%-32.3%. In Part 2 and Part 3, the optimized nasal spray method was adopted to promote the Fabs of Dex nasal spray to 74.1%-89.0%. A severe adverse event was found in Part 2. In Part 3 (100 µg), the Ramsay score increased the most and lasted the longest, whereas the BIS score decreased most significantly. Conclusion: Using the optimized nasal spray method, a single dose of 20/100 µg of the test drug was safe and tolerable, and 100 µg may have approached or reached the plateau of sedation. In addition, it is found that the optimized method can greatly improve the bioavailability of the test drug, leading to its higher reference value.

The largest Se-4f cluster incorporated polyoxometalate with high Lewis acid-base catalytic activity.

A 4p-4f cluster incorporated polyoxometalate (POM), namely, H18{[(H4pic)4Eu10Se13O28(H2O)12](α-GeW9O34)4·40H2O (1-Eu, H4pic = isonicotinic acid), has been first synthesized and characterized. 1-Eu features an interesting four-shell structure, representing the largest Se-4f cluster incorporated POM known to date. Besides, 1-Eu exhibits excellent Lewis acid-base catalytic activity and reusablity in catalyzing the gram-scale dehydration condensation reaction of hydrazines and 1,3-diketones to synthesize polysubstituted pyrazoles.

Lanthanide-Organic Frameworks with Uncoordinated Lewis Base Sites: Tunable Luminescence, Antibiotic Detection, and Anticounterfeiting.

Several new isostructural lanthanide metal-organic frameworks (Ln-MOFs), {[Ln2(L)3DMA4]·2DMA}n (1-Ln, where Ln = Eu, Tb, or EuxTb1-x), were first constructed via the solvothermal reactions of 4,6-di(4-carboxyphenyl)pyrimidine and Ln3+ ions. 1-Ln exhibits a 4-connected two-dimensional framework endowed with uncoordinated Lewis base sites. An exploration of luminescence sensing demonstrated 1-Eu can be used for the selectivity detection of dimetridazole and metronidazole antibiotics in other antibiotics, blood plasma, and urine, acting as an exceptional recyclable luminescent probe. More importantly, the luminescent inks of 1-Ln are invisible, color adjustable, and stabilized, which may greatly improve their anticounterfeiting applications.

Highly Efficient I2 Sorption, CO2 Capture, and Catalytic Conversion by Introducing Nitrogen Donor Sites in a Microporous Co(II)-Based Metal-Organic Framework.

Recently, the development of porous absorbents for efficient CO2 and I2 capture has attracted considerable attention because of severe global climate change and environmental issues with the nuclear energy. Hence, a unique porous metal-organic framework (MOF), {[Co(L)]·DMF·2H2O}n (1, DMF = N,N-dimethylformamide) with uncoordinated N atoms was rationally constructed via using a heterofunctional 4,6-bis(4'-carboxyphenyl)pyrimidine (H2L) linker. Interestingly, 1 exhibits exceptional properties for I2 sorption, CO2 capture, and catalytic conversion. Particularly, I2 can be efficiently removed in both vapor and solution forms, and the adsorption amount can reach 676.25 and 345.28 mg g-1, respectively. Furthermore, complex 1 displays high adsorption capacity for CO2 (53.78 cm3 g-1, 273 K). Consequently, 1 is expected to be a promising and practical material for environmental purification due to its excellent adsorption properties.

Copper-Containing Polyoxometalate-Based Metal-Organic Frameworks as Heterogeneous Catalysts for the Synthesis of N-Heterocycles.

Three new polyoxometalate-based metal-organic frameworks (POMOFs) [Cu4(µ3-OH)2(tba)3(H2O)5(SiW12O40)0.5](H2SiW12O40)0.5·2.5H2O (CuSiW), [Cu3(µ3-OH)(tba)3(Htba)(H2O)2(HPMo12O40)]·7H2O (CuPMo), and [Cu4(µ3-OH)2(tba)3(H2O)3(PW12O40)0.5]2(PW12O40)·0.5H2O (CuPW) were constructed using multinuclear copper clusters, 3-(4H-1,2,4-triazol-4-yl)benzoic acid (Htba), and Keggin polyoxometalates (POMs). Different POMs regulate the formation of different multinuclear copper clusters ("boat" tetranuclear clusters in CuSiW, trinuclear clusters in CuPMo, and "chair" tetranuclear clusters in CuPW) and different topological structures of CuSiW, CuPMo, and CuPW (3-connected two-dimensional (2D) network for CuSiW, 4-connected 2D network for CuPMo, and (4,6)-connected three-dimensional network for CuPW). CuSiW, CuPMo, and CuPW as heterogeneous catalysts combine the high stability of MOFs in polar solvents and excellent catalytic activity of POMs and could be used for the synthesis of nitrogen-heterocycle compounds. The condensation cyclization reactions of 2-aminophenols/benzenesulfonyl hydrazines with 1,3-diketones produce benzoazoles and pyrazoles in good to excellent yields under the catalysis of CuPMo. Moreover, the catalyst could be reused at least for 7 runs, and this protocol was suitable for gram-scale reactions.

ABC-Net: a divide-and-conquer based deep learning architecture for SMILES recognition from molecular images.

Structural information for chemical compounds is often described by pictorial images in most scientific documents, which cannot be easily understood and manipulated by computers. This dilemma makes optical chemical structure recognition (OCSR) an essential tool for automatically mining knowledge from an enormous amount of literature. However, existing OCSR methods fall far short of our expectations for realistic requirements due to their poor recovery accuracy. In this paper, we developed a deep neural network model named ABC-Net (Atom and Bond Center Network) to predict graph structures directly. Based on the divide-and-conquer principle, we propose to model an atom or a bond as a single point in the center. In this way, we can leverage a fully convolutional neural network (CNN) to generate a series of heat-maps to identify these points and predict relevant properties, such as atom types, atom charges, bond types and other properties. Thus, the molecular structure can be recovered by assembling the detected atoms and bonds. Our approach integrates all the detection and property prediction tasks into a single fully CNN, which is scalable and capable of processing molecular images quite efficiently. Experimental results demonstrate that our method could achieve a significant improvement in recognition performance compared with publicly available tools. The proposed method could be considered as a promising solution to OCSR problems and a starting point for the acquisition of molecular information in the literature.

Two U(VI)-Containing Silicotungstates with Sandwich Structures: Lewis Acid-Base Synergistic Catalyzed Synthesis of Benzodiazepines and Pyrazoles.

Two new U(VI)-containing silicotungstates with similar sandwiched polyanions but different space structures, two-dimensional Na10.5H3.5(H2O)36[Na(UO2)(α-SiW9O34)]2·2.5H2O (1) and three-dimensional Na14(H2O)36[Na(UO2)(α-SiW9O34)]2·4H2O (2), have been synthesized by the reactions of UO2(OAc)2 and Na10[α-SiW9O34]·18H2O in aqueous solution at different pH values. Structure analyses demonstrated that different reaction conditions may provide different self-assembly conditions and result in the different coordination environments of Na(I)-H2O clusters with different disorders, which are the keys to the differences between 1 and 2. Compound 2 was demonstrated to show excellent catalytic activity for the synthesis of 3H-benzo[b][1,4]diazepines and pyrazoles via the intermolecular cyclization reactions, and the yields of the desired products reached 99%. This work illustrates the catalytic properties for U(VI)-containing POMs.