REAL‐t1, an Effective Approach for t1‐Noise Suppression in NMR Spectroscopy Based on Resampling Algorithm

Summaryof main observation and conclusionIn multidimensional(nD)NMR spectroscopy,t1noise usually appears as ridges along indirect dimen-sions,and affects observation of weak signals.The main source of t1noise is instrumental instability,which causes random variation of FID amplitude during data acquisitions and introduces random noise-like peaks into spectrum after Fourier transformation.A number of efforts have been devoted,in order to develop new method or to improve existing approaches for suppressing t1noise.Herein,we propose a novel t1noise suppression method based on resampling algorithm for data processing,shortenedas REAL-t1.The method was verified using simulated 2D spectra,and NOESY spectra of sucrose and protein GB1,showing that the spectral quality was improved in all cases.The performance of REAL-t1was also compared with another recently pro-posed method,which showed that these two methods provided similar performance while REAL-t1cost much shorter experimental time.     

Palladium‐Catalyzed Asymmetric [4+3]‐Cyclization Reaction of Fused 1‐Azadienes with Amino‐trimethylenemethanes: Highly Stereoselective Construction of Chiral Fused Azepines

Summary of main observation and conclusion A Pd-catalyzed asymmetric aromative[4+3]-cyclization reaction of amino-trimethylenemethanes(TMM,1d,ip3-oles)with fused 1-azadienes has been developed.This method enables access to the synthetically importance and biologically active benzofuran fused azepines and indeno-azepines in excellent efficiency and stereoselectivity(up to 95%yield,99%ee,>19:1 dr).     

A biomass carbon material with microtubule bundling and natural O-doping derived from goldenberry calyx and its electrochemical performance in supercapacitor

A promising biomass carbon material,manufactured by the carbonation of Physalis peruviana L.calyx at 700℃,is presented in this wo rk.Morphology characterization shows that the carbon material possesses long microtubule bundling and above 30%natural O-atom component on the surface.After KOH chemical etching,the materials maintain the oxygen content but exhibit more micropores and higher specific surface area up to 1732.6 m^2/g.Using as an electrode material for supercapacitor,the active carbon material exhibits high specific capacitance up to 339.7 F/g at 0.5 A/g in 3 mol/L KOH aqueous solution through three-electrode system.The active carbon material also exhibits excellent cycling stability(97%retention)by 10,000 cycles at 10 A/g.The outstanding electrochemical performances are attributing to the unique long microtubule bundling with much more pores and the abundant Oelement on the surface.This biomass carbon material with excellent electrochemical properties could be a useful material for multiple applications.     

浙江新高考化学加试题难度研究*

在对已有试题难度量化工具进行改进的基础上,建构了化学加试题难度评估工具。对2015年至2019年国家新高考实验区浙江省的8次化学选考加试题的难度进行了量化评价。结果表明,8次化学加试题整卷难度变化较大,但同一学年、有相同学生可能参与的2次化学选考的整体难度相近;加试题能力特征和难度差异明显,“有机化学基础”加试题(第32题)难度相对稳定,而第30题(化学反应原理)与第31题(实验化学)加试题难度却表现出一定的波动性。在对8次化学加试题的难度及相关因素进行分析的基础之上,也对如何提高加试题的编制质量,提出了可行性建议。     

二茂铁骨架系列三齿配体的合成及其在铱催化不对称氢化中的应用

本文主要介绍了一系列基于二茂铁骨架的三齿配体:f-amphox、f-ampha、f-amphol和f-amphamide的合成及其应用。这四类手性膦氮配体的铱络合物可以高活性(TON高达1 000 000)、高转化率(>99%)、高对映选择性(>99% ee)地催化(官能团化)酮等底物的不对称氢化反应。该系列配体成功地应用于地诺帕明、苯福林和沙丁胺醇等手性医药中间体的不对称合成。与传统路线相比,这些合成方法更高效,副产物更少,“三废”排放量更低。     

C5a受体拮抗剂W-54011的合成

以7-甲氧基-1-萘满酮为原料,经Wittig反应、去甲基化、烯醇互变和Jones氧化反应等制得关键中间体7-甲氧基-1,2,3,4-四氢化萘-1-羧酸(4); 4-异丙基苯胺和4-(二甲基胺基)苯甲醛经过还原胺化反应得(E)-4-{[(4-异丙基苯基)亚胺基]甲基}-N,N-二甲基苯胺(6); 4转化为相应的酰氯后与6反应合成N-[4-(二甲基氨基)苄基]-N-(4-异丙基苯基)-7-甲氧基-1,2,3,4-四氢化萘-1-甲酰胺(W-54011),总收率24%,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI）表征。      

Recent Progress on 2D Transition Metal Compounds-based Electrocatalysts for Efficient Nitrogen Reduction

Ammonia is a commodity chemical with high added value. Electrochemical reduction of nitrogen has great promise for the sustainable synthesis of ammonia in recent years. Because of its rich resources and unique electronic structure and characteristics, 2D transition metal compounds have been used as electrocatalysts for electrochemical reduction of nitrogen for clean and sustainable production of ammonia. This review outlines the latest development in the use of 2D transition metal compounds as high-efficiency electrocatalysts for nitrogen reduction reaction(NRR). First, we introduce the N₂ reduction mechanism, and briefly summarize the performance indicators of the catalyst. Then, we focused on the functionalization of unique 2D materials to design high-performance 2D electrocatalysts in respect of simulation calculation and experimental development. Finally, the current challenges and future opportunities for NRR electrocatalysts are introduced.     

Multivalent Aptamer-modified DNA Origami as Drug Delivery System for Targeted Cancer Therapy

In spite of great development in nanoparticle-based drug delivery systems(DDSs)for improved therapeutic efficacy,it remains challenging for effective delivery of chemotherapeutic drugs to targeted tumor cells.In this work,we report a triangle DNA origami as targeted DDS for cancer therapy.DNA origami shows excellent biocompatibility and stability in cell culture medium for 24 h.In addition,the DNA origami structures conjugated with multivalent aptamers enable for efficient delivery of anticancer drug doxorubicin(Dox)into targeted cancer cell due to their targeting function,reducing side effects associated with nonspecific distribution.Moreover,we also demonstrated that the multivalent aptamer-modified DNA origami loading Dox exhibits prominent therapeutic efficacy in vitro.Accordingly,this work provides a good paradigm for the development of DNA origami nanostructure-based targeted DDS for cancer therapy.     

Regiodivergent Intramolecular Nucleophilic Addition of Ketimines for the Diverse Synthesis of Azacycles

Azacycles such as indoles and tetrahydroquinolines are privileged structures in drug development. Reported here is an unprecedented regiodivergent intramolecular nucleophilic addition reaction of imines as a flexible approach to access N‐functionalized indoles and tetrahydroquinolines, by the control of reaction at the N‐terminus and C‐terminus, respectively. Using ketimines derived from 2‐(2‐nitroethyl)anilines with isatins or α‐ketoesters, the regioselective N‐attack reaction gives N‐functionalized indoles, while the catalytic enantioselective C‐attack reaction affords chiral tetrahydroquinolines featuring an α‐tetrasubstituted stereocenter. Mechanistic studies reveal that hydrogen‐bonding interactions may greatly facilitate such unusual N‐attack reactions of imines. The utility of this protocol is highlighted by the catalytic enantioselective formal synthesis of (?)‐psychotrimine, and the construction of various fused aza‐heterocycles.     

On‐Demand Electrochemical Epoxidation in Nano‐Electrospray Ionization Mass Spectrometry to Locate Carbon–Carbon Double Bonds

Reported here is the first on‐demand electrochemical epoxidation incorporated into the standard nano‐electrospray ionization mass spectrometry (nanoESI‐MS) workflow for double‐bond identification. The capability lies in a novel tunable electro‐epoxidation of double bonds, where onset of the reaction can be controlled by simply tuning the spray voltage. On‐demand formation of mono‐/multiple epoxides is achieved at different voltages. The electro‐epoxidized products are then fragmented by tandem MS to generate diagnostic ions, indicating the double bond position(s). The process is completed within seconds, holding great potential for high‐throughput analysis. The rapid switch‐on/off electro‐epoxidation of a single sample, the low sample consumption, the demonstrated applicability to complex lipids containing multiple double bonds, and the advantage of not requiring extra apparatus make this method attractive for use in lipid‐related biological studies.