Borenium ions have attracted significant attention in organic transformations due to their strong Lewis acidity. The reported borenium ions are often stabilized by sterically demanding substituents and strong coordination bonds. Herein, we have synthesized a small steric borenium-equivalent NHBHOTf and subjected it to the exhaustive reduction of a carboxylic functional group to a methyl group, which shows broad functional group tolerance.
View Article and Find Full Text PDFHerein, we report a method for the regioselective alkylation and phosphonation of quinoline C4-H via a BH-mediated nucleophilic addition of Turbo Grignard reagents and phosphine oxide anions to quinolines bearing different substituents, affording the 4-alkyl and 4-phosphoryl quinolines and tetrahydroquinolines after one-pot oxidation or reduction. The results indicate that coordination of the BH group can activate substrates toward a potential 1,4-dearomative addition and subtly control the regioselectivity by preventing the 1,2-dearomative addition.
View Article and Find Full Text PDFImproved methods for the synthesis of BH and a series of -heterocycle-coordinated BH complexes (-Het·BH) have been developed with readily obtained KBH as the starting material. Oxidation of KBH could provide BH in over 90% yield. Then, the -Het·BH complexes were prepared from the as-synthesized BH through in situ multistep reactions by reacting with NaH, -heterocycles, and dilute hydrochloric acid.
View Article and Find Full Text PDFThere exists an interplay between borane and a Lewis base in their adducts. However, studies on these adducts so far have mainly focused on the different reactions of B-H bonds with limited attention given to the influence of borane on the chemistry of the Lewis base, except for BF and BAr. Herein, we have synthesized novel borane adducts with pyridine derivatives, Py·BH, in which the coordination of BH efficiently achieved the intra-molecular charge transfer.
View Article and Find Full Text PDFBy using an external injection locking method, for what we believe to be the first time, we experimentally demonstrate continuous ultra-wideband signal regeneration in random optoelectronic oscillators, achieving more adaptable signal processing capabilities than self-oscillation methods. Supported by theoretical analysis and experimental evidences, this system can regenerate any signal with sufficient gain in a random-feedback cavity, independent of cavity filters. Remarkably, enhanced phase noise performance with over 35.
View Article and Find Full Text PDFThe reduction mechanism of aldehyde/ketones with M(BH) is not fully understood, even though the hydroboration mechanism of weak Lewis base borane complexes is known to involve a four-membered ring transition state. Herein, the reduction mechanism of M(BH) in aprotic solvents has been elucidated for a six-membered ring, in which hydride transfer to the C atom from the B atom, formation of an L·BH adduct, and disproportionation of (BH(OR)) borane are involved. The metal cations and solvents participate in and significantly influence the reaction procedure.
View Article and Find Full Text PDFThe Friedel-Crafts alkylation of arenes is an important part of electrophilic aromatic substitution reactions. However, the reactivity of arenes is weakened by electron-withdrawing substituents, leading to limited substrate scopes and applications. Herein, we developed an efficient HOTf-promoted Friedel-Crafts alkylation reaction of broad arenes with α-aryl-α-diazoesters under metal-free and solvent-free conditions.
View Article and Find Full Text PDFA highly efficient Pd-catalyzed B(9)-H/B(9)-H oxidative dehydrogenation coupling of carboranes to synthesize 9,9'-bis--carboranes has been developed. The properties and derivatization of 9,9'-bis--carborane were also examined, which provided diverse bis--carborane derivatives and bis--carborane.
View Article and Find Full Text PDFBackground: Cyclooxygenase (COX)-2 is a rate-limiting enzyme in the biosynthesis of prostanoids, which is mostly inducible by inflammatory cytokines. The participation of COX-2 in the maturation of megakaryocytes has been reported but barely studied in primary immune thrombocytopenia (ITP).
Methods: The expressions of COX-2 and Caspase-1, Caspase-3 and Caspase-3 p17 subunit in platelets from ITP patients and healthy controls (HC), and the expressions of COX-2 and CD41 in bone marrow (BM) of ITP patients were measured and analyzed for correlations.
In this work, we developed a facile and controllable electrophilic aromatic nitration method with commercially available 68% HNO as the nitrating reagent and trifluoromethanesulfonic acid (HOTf) as the catalyst in hexafluoroisopropanol or under solvent-free conditions. The electrophilic nitration products of different arenes can be obtained in almost quantitative yields by tuning the loading of HOTf. The strong acidity and water absorbing property of HOTf allowed this transformation to reach completion in a short time at room temperature.
View Article and Find Full Text PDFHerein, we present a chemically robust and efficient synthesis route for B(9)-OH--carboranes by the oxidation of -carboranes with commercially available 68% HNO under the assistance of trifluoromethanesulfonic acid (HOTf) and hexafluoroisopropanol (HFIP). The reaction is highly efficient with a wide scope of carboranes, and the selectivity of B(9)/B(8) is up to 98:2. The success of this transformation relies on the strong electrophilicity and oxidizability of HNO, promoted through hydrogen bonds of the Brønsted acid HOTf and the solvent HFIP.
View Article and Find Full Text PDFVital signs have been widely used to assess the disease severity of patients, but there is still a lack of research on their circadian rhythms. The objective is to explore the circadian rhythms of vital signs in critically ill patients and establish an in-hospital mortality prediction model. Study patients from the recorded eICU Collaborative Research Database were included in the present analyses.
View Article and Find Full Text PDFA facile halogenation method for highly selective synthesis of 9-X--carboranes, 9,12-X--carboranes, 9-X-12-X'--carboranes, 9-X--carboranes, 9,10-X--carboranes, and 9-X-10-X'--carboranes (X, X' = Cl, Br, I) has been developed on the basis of our previous work. The success of this transformation relies on the usage of trifluoromethanesulfonic acid (HOTf), the easily available strong Brønsted acid. The addition of HOTf greatly increases the electrophilicity of -haloamides through hydrogen bonding interaction, resulting in the low loading of -haloamides, short reaction time, and mild reaction conditions.
View Article and Find Full Text PDFInt J Environ Res Public Health
November 2022
The populations of some developing countries are aging rapidly, while the average years of schooling for residents are also constantly increasing. However, the question of whether adult children's education affects the longevity of their older parents remains understudied. This study used China Health and Retirement Longitudinal Survey data to estimate the causal impact of adult children's education on their parents' longevity using a truncated regression model.
View Article and Find Full Text PDFThe exploration relevant to the surface changes on optical micro- and nanofibers (MNFs) is still in infancy, and the reported original mechanisms remain long-standing puzzles. Here, by recognizing the combined interactions between fiber heating, mechanically tapering, and high-power pulsed laser guiding processes in MNFs, we establish a general thermal-mechanical-photo-activation mechanism that can explain the surface changes on MNFs. Our proposed activation mechanism can be well supported by the systematical experimental results using high-intensity nanosecond/femtosecond pulsed lasers.
View Article and Find Full Text PDFObjective: The incidence of post-traumatic stress disorder (PTSD) increased among healthcare workers (HCWs) during the outbreak of COVID-19. The purpose of this study was to examine the relationship between eating behavior and PTSD, considering the mediation effect of anxiety, depression and sleep.
Methods: A total of 101 HCWs completed a survey.
Objectives: Immune thrombocytopenia (ITP) is an autoimmune disease characterised by impaired platelet production and increased platelet destruction. However, the involvement of neutrophils in ITP is yet to be explored.
Methods: B-cell activating factor (BAFF) expression and activation markers of neutrophils, as well as activation of platelets in ITP patients and healthy controls were measured.
T-cell acute lymphoblastic leukaemia (T-ALL) is an aggressive haematologic disease that accounts for 15% of childhood and 25% of adult ALL cases. Triptolide (TPL) is an active component of Tripterygium wilfordii and was recently discovered to suppress the growth of some cancers, including ALL, but the underlying mechanism has yet to be elucidated. Dysfunction of the Wnt signalling pathway has been reported to be an important event in the pathogenesis of T-ALL.
View Article and Find Full Text PDFAmination of carboranes has a good application prospect in organic and pharmaceutical synthesis. However, the current methods used for this transformation suffer from limitations. Herein, we report a practical method for a highly regioselective formation of a B-N bond by Pd(II)-catalyzed B(9)-H amination of - and -carboranes in hexafluoroisopropanol (HFIP) with different nitrogen sources under air atmosphere.
View Article and Find Full Text PDFThe B(9)-H halogenation of -carborane and -carborane was achieved with excellent selectivities in hexafluoroisopropanol (HFIP) under simple reaction conditions: single reagent [trichloroisocyanuric acid (TCCA), tribromoisocyanuric acid (TBCA) or -iodosuccinimide (NIS)], catalyst-free, air-/moisture-tolerant, and convenient work-up. With this method, a variety of 9-halogenated -carboranes and -carboranes were obtained in good to excellent yields with broad tolerance of functional groups.
View Article and Find Full Text PDFObjective: Pre-eclampsia (PE) is a pregnancy-associated disease characterized by placental dysfunction and increased oxidative stress. Apocyanin is a potent antioxidant and anti-inflammatory which has shown beneficial effects on PE pathogenesis. Aspirin is recognized as the recommendable drug in PE prevention and therapy.
View Article and Find Full Text PDFSelective reduction of aldehydes and ketones to their corresponding alcohols with KBH, an air- and moisture-stable, nontoxic, and easy-to-handle reagent, in water and THF has been explored under an air atmosphere for the first time. Control experiments illustrated the good selectivity of KBH over NaBH for the reduction of 4-acetylbenzaldehyde and aromatic keto esters.
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