Uncatalyzed Hydroamination of Electrophilic Organometallic Alkynes: Fundamental,Theoretical, and Applied Aspects

Simple reactions of the most used functional groups allowing two molecular fragments to link under mild, sustainable conditions are among the crucial tools of molecular chemistry with multiple applications in materials science, nanomedicine, and organic synthesis as already exemplified by peptide synthesis and “click” chemistry. We are concerned with redox organometallic compounds that can potentially be used as biosensors and redox catalysts and report an uncatalyzed reaction between primary and secondary amines with organometallic electrophilic alkynes that is free of side products and fully “green”. A strategy is first proposed to synthesize alkynyl organometallic precursors upon addition of electrophilic aromatic ligands of cationic complexes followed by endo hydride abstraction. Electrophilic alkynylated cyclopentadienyl or arene ligands of Fe, Ru, and Co complexes subsequently react with amines to yield trans‐enamines that are conjugated with the organometallic group. The difference in reactivities of the various complexes is rationalized from the two‐step reaction mechanism that was elucidated through DFT calculations. Applications are illustrated by the facile reaction of ethynylcobalticenium hexafluorophosphate with aminated silica nanoparticles. Spectroscopic, nonlinear‐optical and electrochemical data, as well as DFT and TDDFT calculations, indicate a strong push–pull conjugation in these cobalticenium– and Fe– and Ru–arene–enamine complexes due to planarity or near‐planarity between the organometallic and trans‐enamine groups involving fulvalene iminium and cyclohexadienylidene iminium mesomeric forms.     

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

Fluorescence emission of wild‐type green fluorescent protein (GFP) is lost in the S65T mutant, but partly recovered in the S65T/H148D double mutant. These experimental findings are rationalized by a combined quantum mechanics/molecular mechanics (QM/MM) study at the QM(CASPT2//CASSCF)/AMBER level. A barrierless excited‐state proton transfer, which is exclusively driven by the Asp148 residue introduced in the double mutant, is responsible for the ultrafast formation of the anionic fluorescent state, which can be deactivated through a concerted asynchronous hula‐twist photoisomerization. This causes the lower fluorescence quantum yield in S65T/H148D compared to wild‐type GFP. Hydrogen out‐of‐plane motion plays an important role in the deactivation of the S65T/H148D fluorescent state.     

茶叶中乙酰甲胺磷及甲胺磷对映体的气相色谱法分离与测定

建立了乙酰甲胺磷、甲胺磷对映体在茶叶基质中的手性拆分与定量方法。比较了2种手性柱对乙酰甲胺磷及甲胺磷对映体的分离效果,并对分离效果较优的BGB-176手性柱进行色谱条件优化。茶叶样品经改良QuEChERS法处理后,气相色谱测定,外标法定量。在0.04,0.08,0.4 mg/kg 3个加标水平下,甲胺磷、乙酰甲胺磷的回收率分别为58.3%~66.4%和50.8%~57.6%,相对标准偏差(n=5)均小于7%。方法检出限为0.003~0.01 mg/kg。该方法简便、可靠,满足分析要求。通过实际样品的检测,发现乙酰甲胺磷、甲胺磷对映体在茶树上存在一定的降解差异。     

原子荧光法测定茶叶中的硒含量

采用原子荧光法测定茶叶中的硒含量,对样品消解温度及仪器条件进行了优化。还原剂为1.0%硼氢化钾–0.5%氢氧化钾溶液,载流液为3%盐酸溶液。在优化条件下,硒的质量浓度在0~20 ng/mL范围内与荧光强度呈良好的线性关系,相关系数r=0.999,检出限为0.8 ng/mL。该法的加标回收率为88.08%~101.39%,测定结果的相对标准偏差为2.03%~4.84%(n=6)。该方法实际操作性强,准确度高,适用于日常检验工作中对批量茶叶中硒含量的测定。     

Green synthesis of bis-coumarin derivatives using Fe(SD)3 as a catalyst and investigation of their biological activities

A convenient, practical, green, and environmentally friendly method was developed for the synthesis of biscoumarins and corresponding tetrakis products from the reaction of 4-hydroxycoumarin and various aldehydes. The bis-coumarins were synthesized in high yield under mild reaction conditions. Products were obtained in the presence of in situ prepared Fe(SD)₃ [Iron(III) dodecyl sulfate] as a combined Lewis acid–surfactant catalyst (LASC) in water in short reaction times. Also, the antibacterial activity of compounds was screened against Pseudomonas aeruginosa and Escherichia coli as Gram-negative bacteria and Micrococcus luteus and Staphylococcus aureus as Gram-positive bacterial strains. Products 3g , 3k–l were most active than cefotaxime against E. coli and also compounds 3c and 3g were most active than cefotaxime against S. aureus.     

Green,rapid, and highly efficient syntheses of α,α′-bis[(aryl or allyl)idene]cycloalkanones and 2-[(aryl or allyl)idene]-1-indanones as potentially biologic compounds via solvent-free microwave-assisted Claisen–Schmidt condensation catalyzed by MoCl5

A new, green, and highly efficient protocol for the expeditious preparation of some α,α′-bis[(aryl or allyl)idene]cycloalkanones and 2-[(aryl or allyl)idene]-1-indanones via a simple microwave-assisted Claisen–Schmidt condensation reaction catalyzed by MoCl₅ was successfully developed. Outstanding features of the current methodology include the use of solvent-free conditions, simple operation, use of a very inexpensive and available catalyst, low catalyst loading, short reaction times, high yields of the pure products, no harmful by-products, easy workup, and also the applicability of microwave irradiation as a clean source of energy. Furthermore, a gram-scale reaction was successfully conducted, proving the scalability of this current Claisen–Schmidt condensation reaction.     

计算机分子模拟在分子印迹技术中的应用

传统的分子印迹技术对模板分子、功能单体、交联剂、致孔剂等的筛选往往依靠经验,常通过反复实验对合成条件进行优化,存在实验周期长、耗材量大等问题。计算机分子模拟技术的应用在实验过程中起到可预见性指导作用,可以实现精准识别位点的裁制、识别驱动力的设计,通过结合能等物化特征参数计算优化识别体系的稳定性,从而合理选择模板分子、功能单体、交联剂、致孔剂,优化聚合条件,以提高聚合物识别特异性和亲和力,缩短实验周期,更符合绿色化学的理念。本文简单介绍了计算机分子模拟技术,重点对其在分子印迹技术中的指导作用进行了综述,并对其在分子印迹技术中的应用进行了展望。     

新型绿色有机合成反应设计:Pd/β-环糊精催化的纯水相铃木-宫浦偶联反应*

以环境友好的β-环糊精代替毒性膦配体、纯水代替有机溶剂,设计了4-溴苯乙酮和苯硼酸的绿色铃木-宫浦偶联反应。通过单因素实验,探讨了氯钯酸钠用量、氯钯酸钠/β-环糊精配比、苯硼酸用量、反应温度以及反应时间等对产率的影响。通过引导学生对β-环糊精结构的认识和机理探讨,让学生深刻感受到了绿色化学在有机合成中的重要性,并激发了他们对科学研究的兴趣。该实验环境友好,反应条件温和,反应时间短,产率高,重复性好,适宜于本科实验教学。     

Ruthenium-Catalyzed Hydrogenative Degradation of End-of-Life Poly(lactide) to Produce 1,2-Propanediol as Platform Chemical

The chemical recycling of end-of-life polymers can add some value to a future circular economy. In this regard, the hydrogenative degradation of end-of-life PLA was investigated to produce 1,2-propanediol as product, which is a useful building block in polymer chemistry. In more detail, the commercially available Ru-MACHO-BH complex was applied as catalyst to degrade end-of-life PLA efficiently to 1,2-propanediol under mild conditions. After investigations of the reaction conditions a set of end-of-life PLA goods were subjected to degradation.     

Selective Oxidation of Ethane to Acetic Acid Catalyzed by a C-Scorpionate Iron(II) Complex: A Homogeneous vs. Heterogeneous Comparison

The direct, one-pot oxidation of ethane to acetic acid was, for the first time, performed using a C-scorpionate complex anchored onto a magnetic core-shell support, the Fe₃O₄/TiO₂/[FeCl₂{κ³-HC(pz)₃}] composite. This catalytic system, where the magnetic catalyst is easily recovered and reused, is highly selective to the acetic acid synthesis. The performed green metrics calculations highlight the “greeness” of the new ethane oxidation procedure.