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This study explored the feasibility of a totally percutaneous approach to perform in situ microneedle puncture fenestration during thoracic endovascular aortic repair (TEVAR) via access from the left subclavian artery (LSA). In total, 23 patients with either thoracic aortic dissection or thoracic aortic aneurysm were treated with in situ LSA fenestration during TEVAR. The procedure was technically successful in all the patients. No serious complications occurred during a mean 9-month follow-up period. In situ microneedle puncture fenestration during TEVAR via the LSA is a feasible and effective method for LSA reconstruction. [ABSTRACT FROM AUTHOR]

Based on the Hard-Soft-Acid-Base theory, we developed and synthesized a unique crystalline adsorbent called MIL-101(Cr)-SMA-ED-PMG (SMA: styrene maleic anhydride; ED: ethylenediamine; PMG: N,N -di(phosphonomethyl)glycine). This adsorbent consists of polymer chains that are abundant in carboxyl and phosphate Lewis hard base groups. This was performed to enhance the efficient recuperation of electrophilic Lewis hard acid rare earth elements. The Neodymium(III) (Nd3+) and Europium(III) (Eu3+) ions reached adsorption equilibrium in the MIL-101(Cr)-SMA-ED-PMG material after 6 h at pH 5. The adsorption of Nd3+ and Eu3+ follows the pseudo-second-order kinetic and Langmuir models. The maximum adsorption capabilities were 102.7 mg/g for Nd3+ and 110.4 mg/g for Eu3+. In addition, when applying a concentration of 0.3 mol/L of HNO 3 or HCl, the adsorbent was nearly completely desorbed, and it remained stable for five cycles. The order of adsorption for the different REE ions was as follows: Eu3+ > Nd3+ > Ce3+ > La3+. The MIL-101(Cr)-SMA-ED-PMG compound demonstrated a remarkable 84 % selectivity in adsorbing Eu3+ compared to the other metal ions in the mixture (Na+, Mg2+, Co2+, Ni2+, and Zn2+). Furthermore, the adsorption of Eu3+ was not significantly influenced by changes in the aqueous conditions. The experiment conducted on a zinc ore simulated leachate exhibited the material remarkable capacity for Eu3+ separation and enrichment. MIL-101(Cr)-SMA-ED-PMG exhibits strong adsorption properties, exceptional selectivity, effective desorption, and significant potential for the recovery of rare earth elements (REEs). [Display omitted] • MIL-101(Cr)-SMA-ED-PMG is prepared by radical polymerization and post-synthetic modifications on MIL-101(Cr). • The adsorption capacity is 102.7 mg/g for Nd3+ and 110.4 mg/g for Eu3+. • The adsorbent exhibits 72.4-85.1% reusability and 84% selectivity for Eu3+. • The cation exchange and coordination are the main adsorption mechanisms. [ABSTRACT FROM AUTHOR]

Purpose: To retrospectively compare the safety and efficacy of a covered self-expandable metal stent (CSEMS) with a transhepatic fixation string and a large-bore catheter for benign biliary anastomotic stricture after hepatobiliary surgery.Materials and Methods: From March 2012 to June 2017, 49 patients with benign biliary anastomotic strictures, untreatable with endoscopy, were included. Twenty-three patients (catheter group) were treated with a large-bore catheter (with progressive catheter upsizing to 16-18 Fr), whereas 26 patients (stent group) were treated by CSEMS (10-mm stent) placement. Technical success, clinical success, primary patency, recurrent strictures, complication rate, and catheter or stent indwelling time were compared between the groups.Results: Technical success and clinical success were achieved in all patients. In the stent group, stent retrieval was successful in all patients. The overall complication rate was 24.5% (catheter group vs. stent group, 30.4% vs. 19.2%; P = .363). Stent migration occurred in 1 patient during follow-up (1/26, 3.8%). The mean indwelling time was 10.3 ± 3.0 months (range, 8-16 months; median, 10 months) in the catheter group and 4.0 ± 1.2 months (range, 3-7 months; median, 4 months) in the stent group (P < .001). Recurrent strictures occurred in 10 (43.5%) patients in the catheter group and 4 (15.4%) patients in the stent group (P = .030). The 1- and 3-year primary patency rates were 82.6% and 69.3% in the catheter group and 92.3% and 84.4% in the stent group (P = .042).Conclusions: Percutaneous placement of a retrievable CSEMS showed superior intermediate-term outcomes over a large-bore catheter in patients with benign biliary anastomotic strictures. [ABSTRACT FROM AUTHOR]

The design and development of low-cost, abundant reserves, high catalytic activity and durability bifunctional electrocatalysts for water splitting are of great significance. Here, simple hydrothermal and hydrogen reduction methods were used to fabricate a uniform distribution of Fe-doped MoO 2 /MoO 3 sheets with abundant oxygen vacancies and heterojunctions on etched nickel foam (ENF). The Fe– MoO 2 /MoO 3 /ENF exhibited a small overpotential of 36 mV at 10 mA cm−2 for hydrogen evolution reaction (HER), an excellent oxygen evolution reaction (OER) overpotential of 310 mV at 100 mA cm−2 and outstanding stabilities of 95 h and 120 h for the HER and OER, respectively. As both cathode and anode catalysts, the heterogeneously structured Fe– MoO 2 /MoO 3 /ENF required a low cell voltage of 1.57 V at 10 mA cm−2. Density functional theory (DFT) calculations show that Fe doping and MoO 2 /MoO 3 heterojunctions can significantly reduce the band gap of the electrode, accelerate electron transport and reduce the potential barrier for water splitting. This work provides a new approach for designing metal ion doping and heterostructure formation that may be adapted to transition metal oxides for water splitting. Image 1 • Improve the adhesion of the materials by etching nickel foam (NF). • Two-step reaction simultaneously achieves iron doping and heterojunctions. • DFT calculations confirm that Fe doping increased the conductivity. • In situ grown heterojunctions greatly reduce the potential barrier. [ABSTRACT FROM AUTHOR]

Highlights • Enantioseparation of sulfinamides on polysaccharide chiral stationary phases is reported. • All of 12 sulfinamides can be resolved with three columns, eleven for both OD-H and AD-H. • A valuable guide for chiral HPLC study or technology related to chiral sulfinyl compounds. Abstract Chiral sulfinamides are increasingly recognizedfor their extensive potential applications in chemistry, medicine and material science, yet chromatographic study on these compounds is seldom. In this article, we describe the enantioseparation of twelve closely related chiral sulfinamide derivatives on polysaccharide-based chiral stationary phases (CSPs). We investigated the factors affecting separation, such as the types of chiral columns, the concentration of polar alcohol and the column temperature. The acyclic sulfinamide derivatives—with the exception of a cyclic sulfinamide compound—were effectively resolved with a Chiralcel OD-H column and a mixture of n-hexane:isopropyl alcohol (90:10) as the mobile phase. All compounds except N-benzylidene-2-methylpropane-2-sulfinamide are baseline resolved on the Chiralpak AD-H column, but only eight compounds are resolved on a Chiralpak AS-H column under the given chromatographic conditions. This study offers valuable guidance for future chiral HPLC studies related to chiral sulfinamides. [ABSTRACT FROM AUTHOR]

[Display omitted] Allylic compounds are widely used in pharmaceutical, chemical and other industries, such as allyl indole derivatives widely present in alkaloids, allylylated derivatives of the antiviral drug acyclovir, and chiral allyl acinolides for the preparation of chiral amino acids. In recent years, vinylcyclopropanes has developed rapidly in organic synthetic chemistry. Activated vinylcyclopropanes are an important raw material for the synthesis of functionalized heterocyclic compounds or allyl derivatives. Transition metal-catalyzed allylation reaction of vinyl cyclopropanes can form new bonds with extensive nucleophiles containing C, N, O, Si, P and S centers. Progress on transition metal-catalyzed allylation of activated vinylcyclopropanes reviewed in this Digest Article. [ABSTRACT FROM AUTHOR]

Samarium (Sm), as one of the lanthanide elements, has a broad application prospect in the synthesis of samarium cobalt permanent magnet materials with high temperature stability, corrosion resistance and oxidation resistance. Due to the unlimited demand of Sm(III), recycling of Sm(III) waste is an effective method to balance economy and supply. In this paper, three novel morpholine carboxylic acid ionic liquids (ILs) were rationally designed and successfully synthesized for the extraction of Sm(III). The effects of alkyl chain length of the ionic liquids, solution acidity, contact time, extractant concentration and temperature were tested in terms of the extraction performances. The results revealed that [(CH 2) 7 COOHmor][NTf 2 ] had the optimal extraction capacity, as well as the extraction efficiency of Sm increased with the increase of pH, reaching >99.9% when the pH was 1.8. In addition, the extraction equilibrium could be achieved within 1 min. Moreover, the slope analysis and FTIR spectral studies proposed a cation exchange extraction mechanism for Sm(III) by [(CH 2) 7 COOHmor][NTf 2 ]. The loaded Sm(III) in organic phase was easy to strip with 0.05 mol/L of HNO 3 , and the [(CH 2) 7 COOHmor][NTf 2 ] remained stable after 5 cycles. The research of transition metal extraction revealed that Sm(III) could be selectively separated from Ni(II) and Co(II) by adjusting the pH value of the solution. Finally, under the optimized extraction conditions, Sm 2 O 3 with 83.9% yield was obtained by the extraction-stripping-precipitation-calcination process, through the large-scale recovery applications of the simulated waste liquid. • The novel carboxyl-functionalized morpholine ionic liquids were designed and fabricated as novel extraction solvents. • The stripping ratios of Sm from ILs reached 99.9% via the back extraction. • The extraction performance of [(CH 2) 7 COOMor][Tf 2 N] maintained stable after 5 cycles. • Via adjusting the initial acidity of the aqueous phase, [(CH 2) 7 COOMor][Tf 2 N] could selectively separate Sm(III) from Co(II). [ABSTRACT FROM AUTHOR]

Abstract: The enantioselective oxidation of allyl sulfides with a vanadyl complex of 3,5-diiodosalicylidene tert-leucinol as a catalyst and aqueous hydrogen peroxide as an oxidant afforded chiral allyl sulfoxides with high enantioselectivities of up to 97.3% ee and moderate yields. [Copyright &y& Elsevier]

H8-MonoPhos, a new stable and readily soluble monodentate phosphoramidite ligand, has been facilely prepared from H8-BINOL. The ligand achieved up to 99.9% ee and 96.7% ee in hydrogenation of dehydroalanine and dehydrohomophenylalanine in a S/C ratio of 500:1, respectively, which are among the best results to date. For dehydrophenylalanine derivatives, it gave good to excellent enantioselectivity. Some factors controlling the enantioselectivity and conversion were examined and are discussed. The interesting effects of ligand/rhodium ratio on the enantioselectivity and conversion were observed, which a mechanism was proposed to explain. [Copyright &y& Elsevier]

H8-MonoPhos, a new stable and easily prepared monodentate phosphoramidite ligand, has been synthesized from H8-BINOL. The ligand showed extremely highly enantioselectivity of higher than 99.9% e.e. in the asymmetric Rh-catalyzed hydrogenation of α-dehydroamino acids. Our study further supports the new concept that there is no gap in efficiency and enantioselectivity between monodentate and chelating ligands for asymmetric catalysis. [Copyright &y& Elsevier]

A C 2 -symmetric, chiral bis-cyclosulfinamide-olefin ligand composed of two 1-oxo-2,3-dihydro-1,2-benzisothiazole moieties with rigid skeletons and a conformationally flexible butenylene chain is disclosed for the first time. HRMS and 1 H NMR analyses verify that the in situ-generated complex of the ligand and [Rh(C 2 H 4 ) 2 Cl] 2 possesses a rhodium (I) center coordinated to the tridentate ligand via two sulfinyl moieties and a CdbndC bond. The chiral ligand provided extremely high enantioselectivity (up to >99%ee) in the Rh-catalyzed asymmetric 1,4-additions of arylboronic acids to cyclohexenone and cyclopentenone. The tridentate ligand gave much higher enantioselectivity than the analogous chiral bidentate ligands. [ABSTRACT FROM AUTHOR]

[Display omitted] A facile Brønsted acid-promoted three-component reaction of 2-methoxythiophene, sulfinates and water at room temperature has been discovered. Under the mild conditions, a series of γ- mercapto -β- sulfonyl esters were obtained in moderate to good yields. The control experiments support the reaction mechanism involves in three processes: 1,5-H shift, Michael addition and ring opening in water. [ABSTRACT FROM AUTHOR]

Abstract: A catalyst based on a new biarylphosphine ligand (3) for the Pd-catalyzed cross-coupling reactions of amides and aryl chlorides is described. This system shows the highest turnover frequencies reported to date for these reactions, especially for aryl chloride substrates bearing an ortho substituent. An array of amides and aryl chlorides were successfully reacted in good to excellent yields. [Copyright &y& Elsevier]

Ozone is thought to advance wound healing by inhibiting inflammation, but the mechanism of this phenomenon has not been determined. Although the zebrafish is often used in regeneration experiments, there has been no report of zebrafish treated with ozonated water. We successfully established a zebrafish model of ozonated water treatment and demonstrate that ozonated water stimulates the regeneration of the zebrafish caudal fin, its mechanism, and time dependence. The growth rate of the caudal fin and the number of neutrophils migrating to the caudal fin wound after resection were higher in the experimental (ozonated) group than in the control group, preliminarily confirming that ozone-promoted regeneration is related to the stimulation of an early inflammatory response by ozone. Ozone modulated the expression of tumor necrosis factor-α (TNF-α) in two ways by regulating interleukin 10 (IL-10) expression. Therefore, ozone promotes tissue regeneration by regulating the inflammatory pathways. This effect of ozone in an experimental zebrafish model is demonstrated for the first time, confirming its promotion of wound healing and the mechanism of its effect in tissue regeneration. These results will open up new directions for ozone and regeneration research. [ABSTRACT FROM AUTHOR]

Abstract: Many synthetic methods of racemic N-aryl (including N-(2-haloaryl)) α-amino acid amides have been reported, but there are only a few for eutomers and none for inactivated halo(hetero)arenes. Selective C–N coupling of aliphatic amino group of α-amino acid amides is a direct and valuable method, but still unresolved. Here we disclose a simple and cheap ligand-free CuI-catalyzed selective synthesis of chiral N-(2-halo(hetero)aryl) amino acid amides without obvious racemization. A rational mechanism is proposed. [Copyright &y& Elsevier]

Abstract: Enantioseparation of naproxen was performed on an immobilized polysaccharide-based chiral stationary phase (CSP), Chiralpak IA, in the normal-phase mode. The effects of polar alcohol modifier in mobile phase and column temperature on retention, enantioseparation, and elution order were investigated. Two unusual phenomena were observed. One was solvent-induced reversal of elution order for the two enantiomers. Not only the type but also the content of polar alcohol modifier could induce the reversal. Another uncommon phenomenon was peak deformation under some chromatographic conditions. [Copyright &y& Elsevier]

FeCl 3 -catalyzed three-component aryl-selenylation of alkenes with good to excellent yields has been disclosed. This method is characterized by synthesis of complicated products in a single-step reaction, simple operation and readily available commercially reagents. Finally, a reasonable mechanism of FeCl 3 -catalyzed aryl-selenylation is proposed. [Display omitted] [ABSTRACT FROM AUTHOR]

• A new protocol to synthesize (enantioenriched) benzylic sulfones. • Cu 2 O as a heterogeneous catalyst can be recycled. • The product benzylic sulfones were obtained in good to high yield (75 ~ 96%). • Highly enantioenriched benzylic sulfones (90 ~ 95%ee) can be synthesized when dppf is used as a ligand. A new protocol for the synthesis of (enantioenriched) benzylic sulfones via the Cu 2 O-catalyzed C–S bond cross coupling of alkane-/arene-sulfinates and (enantioenriched) benzylic quaternary ammonium salts has been developed. The product benzylic sulfones were obtained in good to high yields (75–96%). Chiral arylmethyl sulfones with high enantiomeric excess (90–94% ee) were also synthesized in the presence of Cu 2 O and 1,1′-bis-(diphenylphosphino)ferrocene (dppf). [ABSTRACT FROM AUTHOR]