Aqueous zinc-ion batteries (ZIBs) have emerged as a highly promising candidate for next-generation energy storage systems, owing to their inherent cost-effectiveness, exceptional safety, and environmental benignity. However, the sluggish development of high-performance cathode materials remains a critical bottleneck hindering the practical application of ZIBs. Herein, we report the rational design and successful synthesis of a novel high-entropy oxide, (FeMnAlCrTi)3O4 (denoted as FMACTO), and systematically evaluate its electrochemical performance as a cathode material for ZIBs. Benefiting from the unique multi-cation synergistic effect and lattice distortion inherent in FMACTO, the material exhibits significantly enhanced electronic conductivity and accelerated zinc-ion diffusion kinetics. As a result, FMACTO delivers a high specific capacity of 238.6 mAh g⁻¹ at a current density of 0.2 A g⁻¹ and excellent cycling stability with 70.1

The development of new fungicide molecules is a crucial task for agricultural chemists to enhance the effectiveness of fungicides in agricultural production. In this study, a series of novel fluoroalkenyl modified succinate dehydrogenase inhibitors were synthesized and evaluated for their antifungal activities against eight fungi. The results from the in vitro antifungal assay demonstrated that compound 34 exhibited superior activity against Rhizoctonia solani with an EC50 value of 0.04 mu M, outperforming commercial fluxapyroxad (EC50 = 0.18 mu M) and boscalid (EC50 = 3.07 mu M). Furthermore, compound 34 showed similar effects to fluxapyroxad on other pathogenic fungi such as Sclerotinia sclerotiorum (EC50 = 1.13 mu M), Monilinia fructicola (EC50 = 1.61 mu M), Botrytis cinerea (EC50 = 1.21 mu M), and also demonstrated protective and curative efficacies in vivo on rapeseed leaves and tomato fruits. Enzyme activity experiments and protein-ligand interaction analysis by surface plasmon resonance revealed that compound 34 had a stronger inhibitory effect on succinate dehydrogenase compared to fluxapyroxad. Additionally, molecular docking and DFT calculation confirmed that the fluoroalkenyl unit in compound 34 could enhance its binding capacity with the target protein through p-pi conjugation and hydrogen bond interactions.

Bio-catalysis represents a highly efficient and stereoselective method for the synthesis of valuable chiral compounds, however, the poor stability and limited reaction types of free enzymes restrict their wide application in industrial production. In this work, to overcome these problems, a multifunctional photoenzymatic nanoreactor CALB@COF-Ir was developed through the encapsulation of Candida antarctica lipase B (CALB) in a photosensitive covalent organic framework COF-Ir . This bio-nanocluster serves as efficient catalysts in asymmetric dynamic kinetic resolution (DKR) of secondary amines to give a series of chiral amines in high yields (up to 99 %) and enantioselectivities (up to 99 % ee). The well-designed COF-Ir not only acts as safety cover to prevent CALB from deactivation but promotes racemization of secondary amines via photo-induced hydrogen atom transfer (HAT) process. Photoelectric characterization and TDDFT calculation revealed that (ppy) 2 Ir units in COF-Ir play crucial role in this photocatalytic system which enhance its photo-redox properties through facilitating the separation between photoelectrons (e − ) and holes (h + ). Furthermore, the heterogeneous photoenzymatic nanoreactor could be recycled for five rounds with slight decline of catalytic reactivity.

In this work, we reported a method for construction of difluorocyclopropanes through visible light-promoted [1+2] cycloaddition reaction of aryl diazo esters with gem-difluoroalkenes. The reaction proceeds under mild conditions, encompasses a wide range of substrates (36 examples), exhibits good tolerance to various substituents, and demonstrates a diastereoselectivity of >20:1. Additionally, antifungal activity evaluation revealed that these derivatives exhibited certain activity, the EC50 values for the products towards Botrytis cinerea and Rhizoctonia solani were measured to be 1.51 and 1.36 mu M, respectively, which are significantly lower than those of commercial fungicides Hymexazol and Azoxystrobin. This work not only provides an efficient method for the synthesis of difluorocyclopropanyl derivatives, but reveals their potential applications in fungicide creation.

原子力显微镜技术是用于表征表面纳米级形貌的一种重要手段,对于纳米纤维膜等聚合物表面分析具有一定的优势.本文详细叙述了原子力显微镜的基本原理及操作步骤,研究了扫描模式、测试参数、探针类型等因素对较大粗糙度的纳米纤维膜测试结果的影响.结果表明,高长径比探针比常规探针更能真实的反应表面的形貌信息.

In this work, an efficient visible light promoted aerobic dehydro-coupling of amines, oxidation of thioethers and hydroxylation of arylboronic acids under benign conditions by using pyrene-based donor-acceptor (D-A) conjugated organic molecules was described. Donor-acceptor structure influences their π-conjugation and band gap a lot, and thereby enhances their visible light absorption ability, single electron transfer and oxidative behaviors. Alkynyl units in PS-IV play a crucial role in the catalyst which could serve as electron transferring bridge to strengthen electron delocalization, thus facilitating the single electron transfer from photosensitizer to substrates, and making it an efficient ⋅O2 - generator. While PS-III without alkynyl units tends to produce 1 O2 . Therefore, these molecules can serve as efficient catalysts for different kinds of visible-light-induced aerobic organic reactions. More importantly, the simply structured molecule is insoluble and stable in various solvents, and thus could be recycled as heterogeneous catalyst for many rounds with slight catalytic activity degradation. Besides, large scale (1 mol) reaction of benzylamine coupling proceeded smoothly under the standard conditions.

Circular dichroism (CD) spectroscopy is a well-established biophysical technique used to measure protein and its secondary structure and to detect changes in secondary and higher orders of structure for applications in research and the quality control of protein products such as biopharmaceuticals. However, objective comparison of spectra is challenging because of a limited quantitative understanding of the sources of error in the measurement. Statistical methods can be used for comparisons but do not provide a mechanism for dealing with systematic and random, errors. CD measurements in any two instruments may often present slight differences in spectral magnitude or wavelength, even for the same sample under comparable conditions. The small disparities between the polarization of the incident light from each instrument, light source, and final lamp output are examples of the variables that can produce such differences. On the other hand, the structural information acquired with the CD method can sometimes be hampered by the poor quality of the original CD data, and CD deconvolution analysis strongly depends on the spectral intensity. Here a helix predominate protein-cytochrome C was taken as the experimental object, and CD spectroscopy was used to measure the concentration of 0.05 mg.mL(-1) cytochrome C aqueous solution after instruments were typically calibrated using standards. And then, a measurement model for CD spectroscopy of 0.05 mg.mL(-1) Cytochrome C aqueous solution was presented, incorporating the principal sources of uncertainty to derive an uncertainty budget of spectral magnitude in wavelength 222 nm. The uncertainties of spectral magnitude were from measurement repeatability, concentration uncertainty of calibration solution and protein solution, the uncertainty of cell length of the cuvette, etc. After calibrating the instrument, these sources of uncertainty were comprehensively considered, and the magnitude uncertainty of 0.05 mg.mL(-1) cytochrome C aqueous solution at the wavelength of 222 nm was (-4.53 +/- 0.54) mdeg, k=2. The uncertainty, evaluation found that the uncertainty of 1 mm cuvette cell length and the solution preparation process account for a significant part of the uncertainty component. Eliminating or reducing the impact of these factors can improve the measurement method to analyze the measurement process to achieve an objective comparison of CD spectra and improve the comparability and reliability of CD spectra. This work also provides an experimental reference for the interlaboratory comparison of circular dichroism measurement.

Chiral pyrrolidinyl units are important building blocks in biologically active natural products and drugs, and the development of efficient methods for the synthesis of diverse structured pyrrolidine derivatives is of great importance. Meanwhile, incorporating fluorine containing groups into small molecules often changes their activities to a great extent due to the special physicochemical properties of fluorine atoms. Herein, we report an efficient route to obtain enantioenriched 3,3-difluoro- and 3,3,4-trifluoropyrrolidinyl derivatives by Cu(i)-catalysed enantioselective 1,3-dipolar cycloaddition of azomethine ylides with less active 1,1-difluoro- and 1,1,2-trifluorostyrenes. A series of new fluorinated pyrrolidines have been prepared in high yields (up to 96%) and with excellent stereoselectivities (up to >20 : 1 dr and 97% ee), and these unique structural blocks could be readily introduced into some natural compounds and pharmaceuticals. Additionally, antifungal activity investigation against four common plant fungi showed that some products possess general and high biological activities; comparison with the low antifungal activities of corresponding nonfluorinated compounds revealed that the fluorine atoms at the pyrrolidinyl rings play a crucial role in the antifungal activity.

Comprehensive chemical characterization for two isomers of camphorsulfonic acid (CSA), occasionally used in the manufacture of active pharmaceutical ingredients (APIs), was performed by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectroscopy in negative electrospray ionization mode and gas chromatography/mass spectrometry (GC/MS) in electron ionization mode. Electronic circular dichroism (ECD) spectra together with quantum chemical calculations using time-dependent density functional theory (TD-DFT) were used to assign the stereochemistry for CSA for the first time and these assignments were then confirmed by single-crystal X-ray diffraction. As crystals were grown under the same conditions of high supersaturation using a mixed solvent without water removal, the crystal structures of the two enantiomers contained one ordered molecule of water in the asymmetric unit. The crystals of the (+)-enantiomer have a 1S,4R configuration and the H atom of the sulfonic acid group combines with the water molecule to form a hydronium ion, namely, hydronium (1S,4R)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonate, H3O+·C10H15O4S-. The crystals of the (-)-enantiomer have a 1R,4S configuration. The determination of the optical purity of CSA using NMR spectroscopy with a chiral solvating agent, (1R,2R)-1,2-diphenylethane-1,2-diamine, and GC/MS with a chiral column has been well explored. The results showed that the examined samples of these two isomers of CSA proved to be enantiomerically pure. In particular, for (1R)-(-)-10-camphorsulfonic acid, this is, to our knowledge, the first description on its spectral characterization in a scientific context.

An efficient [4+2] cycloaddition reaction of fulvenes with aza-o-quinone methides, generated in situ from N-(o-chloromethyl)aryl sulfonamides with the assistance of a base, has been developed to afford a series of tetrahydroquinoline derivatives. The reaction tolerates a wide range of aza-o-quinone methides and fulvenes bearing four- to seven-membered rings to afford the corresponding tetrahydroquinolines in moderate to good yields. Based on a literature analysis, a plausible mechanism for this [4+2] cycloaddition is proposed.

对于手性化学药、蛋白质类药物和中药的研制、开发和质量控制,圆二色(circular dichroism,CD)光谱这种传统光谱技术发挥着重要作用.本文介绍了 CD光谱的工作原理,全面综述在手性化学药物、蛋白类药物和中药实际应用与学术界使用CD光谱的情况,突出CD光谱在这些药物分析中所起的重要作用,如CD光谱可用于测定手性药物的绝对构型(absolute configuration,AC)和对映体过量(enantiomeric excess,ee),可用于蛋白类药物的二级结构预测,可用于中药的构型分析等.此外,对美国药典和欧洲药典中收录CD光谱分析方法的情况进行了介绍,对较新的仪器技术如振动圆二色光谱、固体圆二色光谱、磁圆二色光谱以及蛋白分析的数据处理等进行了说明.本文旨在为CD光谱应用于手性化学药物、蛋白类药物及中药的质量控制及相关研究提供参考.鉴于CD光谱在药物分析中的广泛应用,建议《中华人民共和国药典》加入这种分析方法,确保药品的质量安全.同时,我国亟待制定相应的圆二色光谱仪校准规范,并研制相关标准物质,实现检测结果的互认,不断提升我国的国际竞争力.

目的 测定普乐沙福的波谱学特征,确证其化学结构.方法 利用红外光谱(IR)、紫外光谱(UV)、核磁共振(NMR)、高分辨质谱(MS)、热分析和X-射线粉末衍射(XRD)等技术对普乐沙福进行结构分析.结果 通过解析证实普乐沙福的结构为1,1'-[1,4-亚苯基(亚甲基)]-二-1,4,8,11-四氮杂环十四烷.结论 该方法准确可行,可为普乐沙福的质量控制和结构鉴定提供依据.

An efficient access to chiral pyrrolidine derivatives bearing one trifluoromethylated quaternary stereogenic centers is developed through Cu(I)/(S)-TF-BiphamPhos-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides withtert-butyl 2-(trifluoromethyl)acrylate in moderate to high yields, excellent diastereoselectivities and good enantioselectivities (up to 95% yield, >20 : 1 dr, 89% ee).

目的 建立确证阿昔洛韦化学结构的方法.方法 通过紫外光谱,红外光谱,超高分辨质谱,1D/2D核磁共振,热分析及X-射线粉末衍射对阿昔洛韦的结构进行分析.结果 通过解析证实了阿昔洛韦的化学结构为9-(2-羟乙氧甲基)鸟嘌呤.结论 该方法准确可行,可为阿昔洛韦的结构鉴定提供依据.

目的 确证替格瑞洛的化学结构.方法 通过紫外光谱(UV)、红外光谱(IR)、超高分辨傅里叶变换离子回旋质谱(FT-MS)、1D/2D核磁共振谱(NMR)、差热扫描量热分析(DSC)、热重/差热扫描量热同步综合热分析(TG/DSC)和X-射线粉末衍射(XRD)对替格瑞洛进行结构分析.结果 通过解析证实了替格瑞洛的化学结构为(1S,2S,3R,5S)-3-[7-[[(1R,2S)-2-(3,4-二氟苯基)环丙基]氨基]-5-丙硫基三唑并[4,5-d]嘧啶-3-基]-5-(2-羟乙氧基)-1,2-环戊二醇.结论 该方法准确可行,可为替格瑞洛的结构确证提供依据.

目的 建立利用分析仪器确证盐酸达泊西汀化学结构的方法.方法 利用红外光谱(IR)、紫外光谱(UV)、核磁共振(NMR)、高分辨质谱(FTMS)、X-射线粉末衍射对盐酸达泊西汀进行结构分析.结果 通过解析证实盐酸达泊西汀的结构为(S)-(+)-N,N-二甲基-3-(萘基-1-氧基)-1-苯丙胺盐酸盐.结论 该方法准确可行,可为盐酸达泊西汀的生产和结构鉴定提供依据.

Asymmetric 1,3-dipolar cycloaddition of methyl a-fluoroacrylate with azomethine ylides for the construction of optically active fluorinated pyrrolidines bearing one unique fluorinated quaternary and two tertiary stereogenic centers has been achieved with Cu(CH3CN)(4)BF4/TF-BiphamPhos complexes for the first time. This catalytic system performs well over a broad scope of substrates, providing the synthetically useful adducts in good yields and excellent diastereoselectivities and good to high enantioselectivities.