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Fluorinated organic compounds stand as an important class of organic molecules and play a key role in both academic and industrial communities due to the unique nature of fluorine. Among...

An unprecedented Pd-catalyzed asymmetric intramolecular cascade cyclization of aryl halides with readily available arylboronic acids proceeds through a Heck-type dearomative cyclization terminated with arylation in the presence of Pd2(dba)3 (10 mol %), Cu2O (5 mol %), and Cs2CO3 (2.0 equiv) in 1,2-dichloroethane (1.0 mL) at 100 °C for 15 h in air using BINOL-based phosphoramidite as the chiral ligand. This dearomative Heck protocol, which tolerates a broad variety of functional groups, is amenable to the generation of optically active indoline derivatives bearing all-carbon quaternary stereogenic centers in one step in moderate to excellent yields, with excellent diastereoselectivities (>20:1) and enantioselectivities (up to >99% ee). It is worth mentioning that no decrease in the enantiopurity of the indoline derivatives was observed during the synthetic transformations of the products.

Disclosed herein is a cross-dehydrogenative-coupling reaction of N-heterocycles including 1,2,4-triazine-3,5(2H, 4H)-diones and quinoxaline-2(1H)-ones with N-methylanilines to form C(sp2)-C(sp3) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)3Cl2·6H2O serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted N-heterocycles with extensive functional group compatibility in 40-86% yields.

A mixed oxide supported bimetallic catalyst Ni25.38Co18.21/MgO–0.75Al2O3 was readily prepared and found to be efficient in the hydrogenation of valeronitrile (VN) to amylamine (AA) under atmospheric pressure. Under the optimal conditions: H2 to VN molar ratio of 4:1, NH3 to VN molar ratio of 3:1, reaction temperature of 130 °C and residence time of 5 s, the conversion of VN reached 100% with a AA yield of 70.8%, and a diamylamine (DAA) yield of 25.9%. This catalyst was also active in the hydrogenation of other low carbon aliphatic nitriles to their corresponding primary amines. The characterization results revealed that the catalyst had the properties of large surface area, uniform and fine dispersion of metal particles in the form of Ni/Co alloy with synergy effect between the two metals, which endowed the catalyst with good catalytic performances in the hydrogenation reaction of aliphatic nitriles.

Direct sulfonamidation of quinoxalin-2(1H)-one derivatives has been developed using a readily available Cu salt as the catalyst and inexpensive ammonium persulfate as the oxidant in moderate conditions. Owing to the feature of handy operation and good functional group tolerance, this method provides a convenient and efficient access to curative 3-sulfonamidated quinoxalin-2(1H)-one scaffolds.

A novel Lewis acid-catalyzed, highly efficient, practical, and atom-economical protocol for the synthesis of functionalized 1,2-dihydropyridine-3-carbonitrile derivatives in the presence of Bi(OTf)3 (10 mol %) in tetrahydrofuran (2.0 mL) at 80 °C for 8 h in air is described, starting from readily accessed propargylic alcohols and (E)-3-amino-3-phenylacrylonitriles. This cycloaddition protocol, which is scalable and proceeds under mild conditions, is amenable to the gram-scale construction of valuable 1,2-dihydropyridine-3-carbonitriles. Furthermore, the good functional group compatibility and broad scope of this strategy were demonstrated by a broad range of propargylic alcohols and (E)-3-amino-3-phenylacrylonitriles, with yields ranging from 34 to 96%.

A silver-catalyzed formal [3 + 3] annulation of 3-methyleneisoindolin-1-one with alkynol for the synthesis of 1,5-dihydroindolizin-3(2H)-one derivatives is disclosed. The protocol allows practical synthesis of N-heterocyclic scaffolds with a broad scope of functional groups and could be efficiently scaled up to gram scale, which incarnates a potential application of this methodology. In addition, a range of chlorine anion substitution of alkenes can be constructed by adjusting the structure of the alkynol substrates with the use of TMSCl.

Disclosed herein is a cross-dehydrogenative-coupling reaction of

Cyanobacterial blooms (CBs) in eutrophic lakes can cause various harmful issues to both humans and animals, disturb drinking water supply, and devastate lake ecosystems. Although great progresses have been made in many lakes from China and abroad on CBs prevention, mitigation and control, systematic research on the influencing factors of CBs in hypereutrophic plateau Lake Dianchi over a long time span is so far unavailable. This study comprehensively generalized both meteorological and water quality changes in Lake Dianchi during 1990–2015 on both yearly and monthly basis, separated Caohai from Waihai of Lake Dianchi regarding water quality variations, and investigated the individual and joint influencing meteorological and water quality factors on CBs using Spearman correlation, principal component analysis, and multivariate linear stepwise regression. Four specific lake regions, i.e. Caohai, northern Waihai, central Waihai, and southern Waihai, were respectively analyzed due to significant water quality heterogeneity. Results indicated that mild temperatures, low wind velocities, and hypereutrophic water conditions all favor CBs in Lake Dianchi, and the significant temperature rising trend may exacerbate severer CBs in the future. Despite configuration differences, the first principal components on CBs in the four sub-regions of Lake Dianchi were all consisted of meteorological factors, while water quality parameters especially total phosphorus concentrations contributed to the second principal component. Quantification of joint meteorological and water quality influencing factors on CBs needs further improvement, and largely relies on the accuracy of future weather forecasts, in order to set the goal of water quality improvement in each specific lake region for effective CBs management.

A novel Lewis acid-catalyzed, highly efficient, practical, and atom-economical protocol for the synthesis of functionalized 1,2-dihydropyridine-3-carbonitrile derivatives in the presence of Bi(OTf)

A novel base-mediated direct difluoroalkylation of 1,6-enynes involving a CF2 radical process has been developed. In the absence of metal catalysts, two different difluoroalkylated cyclization products have been synthesized with good functional group applicability and high stereoselectivity. Notably, the properties of a base have been shown to play a crucial role in the generation selectivity of this transformation.

A Bronsted acid-mediated formal [3+3] cascade annulation of propargylic alcohols with 1,3-diketones proceeds through a sequential Meyer-Schuster rearrangement/1,2-addition. This protocol, which has a wide scope and is conducted under an ambient atmosphere, enables access to a broad array of valuable chromenone derivatives related to many natural products in satisfactory yields under mild conditions. This method could be scaled up to the gram scale, which highlights the latent applicability of this transformation.

A novel copper(II) trifluoromethanesulfonate-catalyzed, high-efficiency, and atom-economical synthesis of valuable organophosphorus compounds via cascade annulation of propargylic alcohols with diphenylphosphine oxide is described. This protocol, which has a good functional-group compatibility and insensitivity to an ambient atmosphere, provides a simple and direct pathway to the products, organophosphorus compounds, in good yields under mild conditions. The method could be efficiently scaled up to gram scale, thus highlighting a potential application of this methodology.

A highly diastereoselective, atom-economical, and palladium-catalyzed Heck protocol for the assembly of structurally diverse indoline scaffolds with vicinal tertiary as well as quaternary stereocenters is described, starting from readily available N-halobenzoyl o-haloaniline derivatives and phenylboronic acids. This cascade annulation reaction, which is scalable and conducts under an ambient atmosphere, provides the valuable tetracyclic indoline derivatives in an efficient and straightforward way.

A copper-catalyzed oxidative cyclization procedure has been developed for the production of 2-sulfonated 9H-pyrrolo[1,2-a]indol-9-ones via the direct sulfonylation of N-propargyl-substituted indoles with sulfonylhydrazides and tert-butyl hydroperoxide (TBHP). This novel protocol, which tolerates a broad range of functional groups, offers a simple, efficient, and atom-economical route to a series of fluorazones in good yields under mild conditions.

An unprecedented Copper (II) trifluoromethanesulfonate-catalyzed [4+2] cascade annulation of propargylic alcohols with benzo[d]isoxazoles proceeds through a sequential ring opening/Meyer−Schuster rearrangement/intermolecular cyclization. This protocol, which tolerates a broad variety of functional groups, offers versatile, modular and atom-economical access to a new class of fascinating quinoline derivatives in good yields under mild conditions. The transformation could be scaled up to gram scale efficiently, thus highlighting the synthetic utility of this methodology.

It is a very important task of searching for novel hole-transporting materials (HTMs), along with effective building blocks, on the way towards commercialization of the perovskite solar cells (PSCs). 9,10-Dihydrophenanthrene (DHP) is a rigid conjugated system, whose skeleton is closely analogous to the widely used fluorene unit in developing HTMs. Herein, for the first time, DHP employed as a promising building block in the construction of HTMs for PSCs is presented. Two readily-available DHP-cored small molecules, namely K-DHP-1 and K-DHP-2, were synthesized and characterized. An attractive bridged ketal pattern of the two molecules was revealed by the X-ray crystallography of K-DHP-2. Afterwards, the two compounds were applied as HTMs in conventional PSCs with a FA0.9MA0.1Pb(I0.9Br0.1)3 • 0.05 CsI perovskite, respectively. Thereinto, the champion device based on doped K-DHP-1 exhibits a power conversion efficiency (PCE) of up to 20.52% with Jsc of 23.96 mA/cm2, Voc of 1.09 V and FF of 78.6%, rivalling the performance of device fabricated with spiro-OMeTAD (20.97%). More encouragingly, the K-DHP-1-based PSC displays good long-term stability, remaining 88% of its original performance after storing in atmosphere (30%∼50% relative humidity) for 45 d without encapsulation, which is better than the spiro-OMeTAD-based PSC. These results indicate that K-DHP-1 can be an effective HTM to realize high efficiency and stable PSCs, and furthermore DHP can serve as an excellent building block for the development of new HTMs in the future.

An unprecedented Lewis acid catalyzed, protection-free, and high-efficiency synthesis of valuable 3,4-dihydro-2H-2,4-methanochromans via cycloaddition of propargylic alkynols with 2-vinylphenol is described. This cycloaddition protocol, which tolerates a wide variety of functional groups, provides practical, versatile, and atom-economical access to a new class of appealing bridged-ring products in satisfactory yields. Compared with the reported reaction conditions for bridged-ring skeletons synthesis, the present reaction conditions are neutral, mild, and without any additives.

A photoredox-/copper-catalyzed decarboxylative difluoroacetylation reaction of α,β-unsaturated carboxylic acids has been developed. This reaction produces a variety of difluoroalkylated alkenes in moderate to excellent yields and exhibits satisfactory stereoselectivity and a broad substrate scope at ambient temperature. Furthermore, this decarboxylative difluoroacetylation protocol provides efficient and environment friendly access to the difluoroalkylated alkenes.

Chronic hepatitis B (CHB) is a worldwide infectious disease caused by hepatitis B virus (HBV). HBV mainly damages liver cells through immune response. The purpose of this study was to determine whether there were dynamic changes of Treg and Th17 cells and to judge the value of these indicators to antiviral treatment. Twenty-two CHB patients and selected 30 healthy adults were enrolled. Results showed that the expression of Treg (5.72±0.46 vs. 4.42±0.17, p=0.0019) and Th17 (3.94±0.64 vs. 2.66±3.12, p=0.0436) cells was significantly increased in CHB patients, as well as the level of interleukin-17 (IL-17) (16.88±5.37 vs. 8.59±3.31; p=0.004). Then, we monitored longitudinally the impact of the treatment with interferon-α and found that the suppression of viral replication induced by interferon-α resulted in a decrease in Treg, Th17 cells, and IL-17; we also found that the percentage of Treg and Th17 cells went up without clear evidence of clinical autoimmune disease at the end of treatment. Thus, Treg and Th17 cells might play an important role in interferon-α treatment to eliminate HBV. The level of changes may be served to determine the antiviral efficacy of interferon-α therapy.

Worldwide extension of hazardous algal blooms (HABs) in lakes has threatened animal and human health, drinking water supply, and aquatic ecosystems. Although both climatic and water quality changes can give rise to HABs, specific contribution of each factor is often lake region dependent. In this study, data from intensive local sampling sites were introduced to identify the key influencing factors of HABs in northern Lake Dianchi, where the bloom is severer than the rest of the lake. Decade-long meteorological and water quality dynamics including HABs community changes at various sites were revealed. Both dry weight of the bloom biomass (DW) and Chlorophyll a concentration (Chl. a) were adopted as indicators to HABs. Spearman correlation analysis and multiple stepwise linear regression were respectively used to identify the individual and joint influencing factors of HABs. Efficiency of a condensed bloom biomass pumping strategy was evaluated on HABs mitigation, and the impact of changing nutrients measurement protocols was also analyzed. Results indicated that Chl. a rather than DW could better represent the extent of HABs among various sampling sites. Although both meteorological and water quality factors are responsible for HABs in northern Lake Dianchi when individually considered, it was water quality and particularly TN and TP that were the “game changer” in HABs mitigation when joint influencing factors were concerned. The “pumping strategy” can only be adopted as an emergency method, and recommendations on nutrients reduction should be based on the conventional measuring protocol that includes particulate nutrients as well.

An unprecedented Lewis acid catalyzed, high-efficiency synthesis of valuable 2-(quinolin-2-yl)prop-2-en-1-ones via dehydrogenative coupling of propargylic alkynols with quinoline N-oxides is described. This protocol, which tolerates a broad range of functional groups, provides a straightforward pathway to the products 2-(quinolin-2-yl)prop-2-en-1-one scaffolds in satisfactory yields. The conversion could be scaled up to gram scale efficiently, which underlines a latent application of this methodology.

A novel and direct synthesis of 1-aryl-5-arylvinyl-tetrazoles from easily prepared propargylic alcohols and TMSN3 is developed in the presence of TMSCl under mild conditions (TMS = trimethylsilyl). The process involves an allenylazide intermediate, followed by a C-C-bond cleavage and C-N-bond formation to afford the desired products. Moreover, this method offers a good functional-group applicability and can be scaled-up to grams (yield up to 85 %).

To compare the cytotoxicity of ex vivo expanded NK cells detected by flow cytometry with 3 different staining methods.NK cells were collected from peripheral blood on the 17The purity of NK cells(CD3CFSE/Annectin-V/7-AAD is able to clearly show human NK cell cytotoxicity against human tumors. Moreover, this staining technique also allows to distinguish different stages of cytotoxic killing as early and late apoptotic phase.

An unprecedented Lewis acid catalyzed, protection-free, and high-efficiency synthesis of valuable 3,4-dihydro-2H-2,4-methanochromans via cycloaddition of propargylic alkynols with 2-vinylphenol is described. This cycloaddition protocol, which tolerates a wide variety of functional groups, provides practical, versatile, and atom-economical access to a new class of appealing bridged-ring products in satisfactory yields. Compared with the reported reaction conditions for bridged-ring skeletons synthesis, the present reaction conditions are neutral, mild, and without any additives.

nanosized copper thin film was prepared on glass substrates by magnetron sputtering. 800 nm pump and 400nm probe technique were used to measure time-resolved reflectivity of copper thin film, and the heat transport processes of copper film were experimentally studied. Thermal transport processes in the copper film were numerically simulated by using Parabolic Two-Step (PTS) model with Finite Difference method. The result of the PTS model can well evaluate the measure date.

Thermal transport process in copper film was numerically simulated with Two-Temperature Model, in which finite difference method was used, and the result shown the temperature change process in electron-lattice system. Some parameters were changed to carry on further simulation. The affect of film thickness on the electronic relaxation time was analyzed. The affect of pump laser beam power on the electron temperature rise was discussed. The influence of electron-lattice coupling factor G on non-equilibrium thermal process was shown in simulations.

An unprecedented Lewis acid catalyzed [4 + 3] cycloaddition reaction is described that provides a straightforward route to polycyclic products containing an imine-based indole azepine scaffold, starting from readily available internal tertiary alkynols and azides. This cycloaddition protocol provides efficient and atom-economical access to a new class of fascinating imine-containing products in satisfactory yields, which has shown good application in the construction of seven-membered N-heterocycles.

A BF3·OEt2–AgSCF3 mediated direct trifluoromethylthiolation/cascade cyclization of propynols involving the SCF3 anion nucleophilic pathway is developed. This protocol also provides an opportunity to construct valuable trifluoromethylthio-substituted 2H-chromene and 1,2-dihydroquinoline systems with high efficiency under mild conditions. Additionally, the developed BF3·OEt2–AgSCF3 reaction system could be scaled up to gram quantities in a satisfactory yield without inert gas protection.