A DFT Study on the Binuclear Copper(I)-Catalyzed Synthesis Mechanism of 1,2,3-Triazolo[1,5-c]Pyrimidine via Interrupted Click and Ketenimine Rearrangement

In this paper, the mechanism of the full catalytic cycle for binuclear Cu(I)-catalyzed sulfonyl azide-alkyne cycloaddition reaction for the synthesis of triazolopyrimidines was rationalized by density functional theoretical (DFT) calculations. The computed reaction route consists of: (a) formation of dicopper intermediates, including C−H activation of terminal alkyne, 3+2 ring cycloaddition and ring-reducing reaction and transmetalation, (b) interrupted CuAAC reaction, including di-copper catalyzed ring-opening of 2H-azirines and C−C bond formation to generate the copper-triazoles and -ketenimines, (c) two-step C−N cross-coupling and following (d) multi-step hydrogen transfer by the hydrogen bonding chain of water to promote the C−N formation and another C−N cleavage through the removal of p-tolyl sulfonamides. Our DFT results indicate that the multi-step hydrogen transfer process is the rate-determining step along the potential energy surface profile. The explicit water model was used for systematic determination of barrier for C−C cross-coupling, C−N bond formation and cleavage, and p-tolylsulfonamide removal. A critical insight in the interrupted CuAAC reaction was proposed. Further prediction interprets H₂O hydrogen bond chain plays an important role in C−N bond formation and cleavage, and the removal of p-tolylsulfonamide. This may have fundamental guidance on the design of 1, 5-herterocyclic functionalized triazolopyrimidines via interrupted CuAAC rearrangement reaction, as well as hydrogen bond chain of water.     

Preparation of flower-like molybdenum disulfide for solid-phase extraction of N-nitrosoamines in environmental water samples

In this paper, a flower-like molybdenum disulfide material was prepared by hydrothermal method and was first used as adsorbents in the solid-phase extraction process for enriching N-nitrosoamines. Molybdenum disulfide exhibited three-dimensional petal-like microspheres with about 500 nm in diameter. The relevant analyte extraction and elution parameters (sample volumes, solution pH, washing solvents, elution solvents, and elution volumes) were optimized to improve the solid-phase extraction efficiency. The solid-phase extraction process coupled with high-performance liquid chromatography-tandem mass spectrometry for determining N-nitrosoamines in environmental water samples was established. The limits of detection were in the range of 0.01–0.05 ng/mL. The satisfactory recoveries (68.9–106.1%) were obtained at three different spiked concentrations (2, 5, and 8 ng/mL) in water samples, and the relative standard deviations were between 1.96 and 8.38%. This proposed method not only showed high sensitivity and good reusability but also provided a new adsorbent for enriching trace N-nitrosoamines in environmental water samples.     

热熔灌输法制备三维骨架支撑金属锂复合负极

金属锂因具有极高的理论比容量(3860 mAh/g)和最低的电化学势(相对于标准氢电极为-3.04 V),被认为是下一代高比能锂离子电池的首选负极材料。然而,金属锂负极在电池循环过程中发生的刺状枝晶生长和体积变化等问题严重阻碍了其产业化应用进程。近年来研究表明,通过在金属锂中引入具有三维(3D)结构的宿主骨架,不但能有效抑制锂枝晶的生长,而且可以缓解金属锂负极的体积变化,从而提高金属锂电池的循环性能与安全性。因此,设计3D骨架/金属锂复合负极被认为是一种能有效解决金属锂问题的新兴策略。本文综述了热熔灌输法制备3D骨架/金属锂复合负极的研究进展。首先讨论了当前基于3D骨架的预存金属锂技术,然后着重分析了热熔灌输策略中3D骨架锂润湿性的影响因素,以及不同3D骨架修饰特征和改性方法。最后对3D骨架/金属锂复合负极和热熔灌输策略现存问题进行了总结并提出未来的发展方向。     

新型吡唑肟衍生物的设计、合成与杀虫活性研究

为寻找高效与低毒的吡唑肟活性物质,设计合成了9个未见文献报道的新型吡唑肟化合物,通过¹H NMR、¹³C NMR及元素分析等方法确证了其目标物的结构。初步生物活性测试数据显示,在500µg/mL浓度下,目标化合物6a~6i对粘虫均有较好的杀虫效果,其杀死率均为100%,与对照药啶虫丙醚的防效相当,值得进一步深入研究。     

Spatiotemporally-regulated multienzymatic polymerization endows hydrogel continuous gradient and spontaneous actuation

There are several natural materials which have evolved functional gradients,ingeniously attaining maximal efficacy from limited components.Herein,we utilized the spatiotemporal distribution of initiator acetylacetone to regulate the multienzyme polymerization and fabricate a chitosan-polymer hydrogel.The temporal priority order of acetylacetone was higher than phenolmodified chitosan by density functional theory calculation.The acetylacetone within the gelatin could gradually diffuse spatially into the chitosan hydrogel to fabricate the composite hydrogel with gradient network structure.The gradient hydrogel possessed a transferring topography from the two-dimensional pattern.A continuously decreased modulus along with acetylacetone diffusion was confirmed by atomic force microscope-based force mapping experiment.The water-retaining ability of various regions was confirmed by low-field nuclear magnetic resonance(NMR)and thermogravimetric analysis(TG)analysis,which led to the spontaneous actuation of gradient hydrogel with maximum 1821°/h curling speed and 227°curling angle.Consequently,the promising gradient hydrogels could be applied as intelligent actuators and flexible robots.     

Dynamic assembly and biocatalysis-selected gelation endow self-compartmentalized multienzyme superactivity

Science China Chemistry - Cellular metabolism in multiple organelles utilizes compartmentalized multienzyme efficient catalysis to realize substance metabolism, energy conversion and immune...     

Develop a stepwise integrated method to screen biomarkers of Baihe-Dihuang Tang on the treatment of depression in rats applying with composition screened,untargeted, and targeted metabolomics analysis

Baihe-Dihuang Tang is a commonly prescribed remedy for depression. In this study, component screening with untargeted and targeted metabolomics was used to identify potential biomarkers for depression in chronic unpredictable mildly stressed rats. Using this novel identification method, the screening of organic acids, lily saponins, iridoids, and other ingredients formed the basis for subsequent metabolomics research. Baihe-Dihuang Tang supplementation in chronic unpredictable mild-stress-induced depression models, increased their body weight, sucrose preference, brain-derived neurotrophic factor deposition, and spatial exploring. Untargeted metabolomics revealed that Baihe-Dihuang Tang exerts its antidepressant effects by regulating the levels of lipids, organic acids, and its derivatives, and benzenoids in the brain, plasma, and urine of the depressed rats. Moreover, it also modulates the d -glutamine and d -glutamate metabolism and purine metabolism. Targeted metabolomics demonstrated significant reduction in l -glutamate levels in the brains of depressed rats. This could be a potential biomarker for depression. Baihe-Dihuang Tang alleviated depression by regulating the levels of l -glutamate, xanthine, and adenine in the brains of depressed rats. Together, these findings conclusively established the promising therapeutic effect of Baihe-Dihuang Tang on depression and also unraveled the underlying molecular mechanism of its potential antidepressant function.     

Targeted isolation of 1,1-diphenyl-2-picrylhydrazyl inhibitors from Saxifraga atrata and their antioxidant activities

Saxifraga atrata is an important traditional Tibetan medicine used to treat cough and pneumonia, and has tremendous medicinal potential. In this study, we devised a technique to separate 1,1-diphenyl-2-picrylhydrazyl inhibitors from a methanol extract of S. atrata. The material was first processed using MCI GEL CHP20P medium-pressure liquid chromatography, yielding 1.1 g of the target fraction Fr2. Subsequently, online hydrophilic interaction liquid chromatography-1,1-diphenyl-2-picrylhydrazyl assay was used to identify prospective 1,1-diphenyl-2-picrylhydrazyl inhibitors, and two 1,1-diphenyl-2-picrylhydrazyl inhibitor fractions (Fr24 and Fr25) were identified from Fr2. Then, medium-pressure preparation was continued using an XIon column to separate two 1,1-diphenyl-2-picrylhydrazyl inhibitor fractions (Fr24 and Fr25). The target compound was concentrated in fractions Fr24 and Fr25 using reverse-phase liquid chromatography during further separation procedures. Finally, the purity, structure, and 1,1-diphenyl-2-picrylhydrazyl inhibitory activity of the isolated 1,1-diphenyl-2-picrylhydrazyl inhibitors were determined. Two 1,1-diphenyl-2-picrylhydrazyl inhibitors (adenosine with the half maximal inhibitory concentration of 66.87 ± 14.33 μM and (-)-4-O-(E)-caffeoyl-l -threonic acid with the half maximal inhibitory concentration of 59.06 ± 5.02 μM) were isolated with purities exceeding 95%. The results showed that this technology is effective in the targeted separation of antioxidants from natural products.     

Isolation of three glucaric acids from Leonurus japonicus Houtt. by using high-speed countercurrent chromatography combined with semi-preparative high-performance liquid chromatography

The isomerism of glucaric acids and the complexity of the composition of Leonurus japonicus Houtt. increased the difficulty of the separation of glucaric acids from the herb. In the present study, three glucaric acids were isolated from Leonurus japonicus Houtt. by using high-speed countercurrent chromatography combined with semi-preparative high-performance liquid chromatography. Cation exchange resin chromatography was applied to remove the alkaloids and enrich the glucaric acid fractions. Preliminary separation of the glucaric acid extract by high-speed countercurrent chromatography was carried out at 45℃ by using an optimized solvent system of ethyl acetate/n-butanol/formic acid/water (1:1:0.01:2, v/v/v/v) with satisfied stationary phase retention and separation factor. The semi-preparative high-performance liquid chromatography was used for further separation and purification of the target fractions, and three monomeric compounds were obtained with purities of 90.0, 91.0, and 95.3%. UV spectroscopy, NMR spectroscopy, and mass spectrometry were employed to identify their structures, which were assigned as 2-syringyl glucaric acid, 2,4-disyringyl glucaric acid, and 3,4-disyringyl glucaric acid, respectively, and 2,4-disyringyl glucaric acid was reported for the first time.     

Ultrafast Decay Dynamics of 2-Hydroxypyridine Excited to S1 Electronic State

The S\begin{document}$_1$\end{document} state decay dynamics of 2-hydroxypyridine following UV excitation at a wavelength range of 276.9\begin{document}$-$\end{document}250.0 nm is investigated using femtosecond time-resolved photoelectron imaging technique. Based on pump wavelength dependence of the decay dynamics, a refined decay picture is proposed. At pump wavelength of 276.9 nm, the S\begin{document}$_1$\end{document} state is depopulated through intersystem crossing to lower triplet state(s). At 264.0 nm, both intersystem crossing to lower triplet state(s) and internal conversion to the ground state are in operation. At 250.0 nm, internal conversion to the ground state becomes dominated.