可见光驱动丰产金属卟啉类配合物催化的二氧化碳选择性还原反应

随着能源短缺和环境问题日益突出, 寻找清洁和可再生能源来替代化石燃料是本世纪科学家面临的最紧迫的任务之一. 为了实现我国“双碳”战略目标, 利用太阳能将二氧化碳(CO₂)转化为清洁燃料和化学品是实现社会可持续发展的途径之一. 催化剂是CO₂光还原技术的核心组成部分, 其可以吸附气态CO₂分子, 在可见光照射下将CO₂还原为一氧化碳(CO)、 甲酸(HCOOH)、 甲醇(CH₃OH)或甲烷(CH₄)等能源小分子. 目前, 新型CO₂还原光催化体系的开发取得了很好的进展. 本文综合评述了近年来均相及非均相丰产金属卟啉类催化剂在光催化CO₂还原中的研究进展, 并对在金属卟啉均相催化剂作用下, CO₂光还原为CO或CH₄的反应机理分别进行了介绍, 还讨论了金属卟啉基多孔有机聚合物与卟啉有机金属框架在光催化CO₂方面的重要应用. 最后, 对可见光驱动卟啉类金属配合物催化的CO₂还原的发展前景进行了展望.     

Analysis of the Magnetic Coupling in a Mn(II)-U(V)-Mn(II) Single Molecule Magnet

[{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA=tris(2-pyridylmethyl)amine and Mesaldien=N,N’-(2-aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014 , 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d–5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g-factors of the monomers are interconnected. The central magnetic unit [U^VO₂]⁺ is described by a Kramers Doublet (KD) with negative g-factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)-U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component J_Z twice larger as the perpendicular one J_⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the J_Z/J_⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g-factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding g^S-values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d–5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [U^VO₂]⁺ 5 f orbitals.     

Labile Base-Stabilized Silyliumylidene Ions. Non-Metallic Species Capable of Activating Multiple Small Molecules

Several base-stabilized silyliumylidene ions ( 2 and 3 ) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene- and sulfide-supported one ( 2-H and 3 a ) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO₂ and H₂. Moreover, HBPin adduct of 3 a ( 8-C ) catalyzes the hydroboration of pyridine. Of particular interest, silylene-supported silyliumylidene complex 2-H is one of the rare species able to activate two H₂ molecules.     

Magnetic Modulation in Heteroallene and Heterocumulene Based tert-butyl Nitroxide Diradicals: Spin Delocalization and Conformation Play Crucial Roles

We have theoretically investigated the magnetic properties of heteroallene (>C=C=X−) and heterocumulene (>C=C=C=X−) based tert-butyl nitroxide diradicals (X is P/As). Calculation of magnetic exchange coupling constant (J) shows ferromagnetic interaction in heteroallene based diradicals. Whereas, in heterocumulene based diradicals, tuning of J value from antiferro- to ferro-magnetic state is observed from Z- to E- isomer. Delocalization of spin density from radical site to the coupler (in planar arrangement) is observed in spin distribution analysis which is also advocated by molecular orbital analysis. The typical feature of tert-butyl nitroxide radical creates spin delocalization along with spin polarization within the coupler. The J values of all the diradicals strongly depend on the dihedral angle between radical center and coupler. Magneto-structural correlation shows that the change in dihedral angle tunes the magnetic property for both the Z- and E- isomers of heterocumulenes depending on the spin accumulation on two nearby magnetic centers. The extent of spin delocalization and conformation of spin centers on the molecular axis are important for the different J values observed in our designed systems.     

Reaction Behaviors of S-, O-, and N-containing Aliphatic Molecules with a Propyl Moiety on Ge(100) Surface

The reaction pathways of 1-propanethiol, 1-propanol, and propylamine molecules, containing a propyl moiety, on a Ge(100) surface were investigated using high-resolution photoemission spectroscopy (HRPES) experiments and density functional theory (DFT) calculations. Upon analysis of the HRPES data, the adsorption of 1-propanethiol and 1-propanol was found to occur through a dissociation reaction, whereas that of propylamine took place via N dative bonding at room temperature. On the basis of our DFT results, adsorption geometries and transition states for each of these molecules on the Ge(100) surface were confirmed. Systematic studies of S-, O-, and N-containing molecules, composed of an identical propyl moiety, on the Ge(100) surface provide insight into the adsorption mechanism of aliphatic molecules containing alkyl chains on the Ge(100) surface.     

Analysis of a “3-(Naphthalen-1-ylimino)indolin-2-one” Compound and Its Antimicrobial Assessment Using Lipid-Based Self-Nanoemulsifying Formulations

In recent years, indole derivatives have acquired conspicuous significance due to their wide spectrum of biological activities—antibacterial, antiviral, and anticonvulsant. This compound is derived from naturally grown plants. Therefore, synthesis of a novel “3-(Naphthalen-1-ylimino)indolin-2-one” compound (2) and its analysis using UPLC systems along with antimicrobial assessment was the aim of the current study. Isatin was used as a parent drug for synthesizing compound (2). Liquid Chromatographic analysis was performed using a C18 BEH column (1.7 μm 2.1 × 50 mm) by UPLC systems. Degradation studies were carried out to see whether acid, base, thermal, and oxidizing agents had any impact on the synthesized molecule in stress conditions (100 °C). A lipid-based self-nanoemulsifying formulation was developed and selectivity, specificity, recovery, accuracy, and precision were measured as part of the UPLC system’s validation process. Antimicrobial studies were conducted using gram-positive and gram-negative bacteria. The standard samples were run with a concentration range of 5.0–100.0 μg/mL using the isocratic mobile phase comprising of methanol/water (70/30 %v/v) at 234 nm; good linearity (R² = 0.9998) was found. The lower limits of detection (LOD) and quantitation (LOQ) of the method were found to be 0.81 μg/mL and 2.5 μg/mL, respectively. The coefficients of variation were found to be less than 2%. The antimicrobial study suggests that compound (2) has a substantial growth effect against gram-negative bacteria. It was successfully synthesized and applied to measure the concentrations in lipid-based dosage form, along with potent antimicrobial activities.     

基于多肽识别的电化学生物传感技术

多肽具有分子量小、易于合成、生物兼容性好、稳定性高及序列灵活多样等优点。因此,多肽作为新型生物识别元件,已被广泛应用于生物传感器的构建。电化学分析灵敏度高、准确度好、设备简单、检测范围广且易于操作。本文介绍了基于多肽识别的电化学生物传感器技术,包括多肽的修饰与固定化、多肽与待测物的识别及检测原理;综述了近五年多肽电化学生物传感器对重金属离子、小分子、蛋白质、细菌和病毒的检测;展望了肽基电化学生物传感器的发展趋势。     

溯源辨析“活化分子”概念在化学教材中的角色定位*

“活化分子”作为国内化学教育领域广为人知的科学概念,在各类相关化学教材中都有介绍。然而在国外多种经典化学教材中却完全没有“活化分子”的概念,反映出国内外化学教育领域对化学反应速率理论相关知识点的处理上存在明显的差异与分歧。通过溯源关键历史文献,回顾了“活化分子”概念的形成及其在化学反应速率理论发展过程中的角色演变,指出“活化分子”概念已经退出反应速率理论的舞台,在教材中应更多地呈现其在科学史方面的价值,而不是科学价值。     

17O-核磁共振法研究不同处理方法对液态水缔合结构的影响

水作为人类重要的生产要素,参与了卷烟生产的多个环节。水在自然条件下以分子簇的形式存在,多种处理方式可以改变水分子团簇的大小。本文以¹⁷O-核磁共振法为水分子团簇的表征手段,以自来水为水源,考察了氢气、远红外辐射陶瓷球、反渗透、磁场四种处理方法对水分子簇的影响。结果表明:四种处理方式均能使一定量水分子由氢键结合态变为自由态,从而使水分子簇变小。不同处理方法对液态水缔合结构的影响大小排序为氢气处理>远红外陶瓷球处理>反渗透处理>磁场处理。同时,对氢气处理效果的时效性进行了考察,随着放置时间增加,部分自由态水分子再次转变为氢键结合态,水分子簇尺寸变大,但三天后仍保留了一定处理效果。本研究表明氢气处理为四种处理方式中最优的水处理方式,具有提升烟草行业生产用水品质的潜在应用价值。     

差分收敛法对双原子分子高J值转动谱线的预言

为了更精确地预言转动量子数J ≥ 100时双原子分子R支和Q支的振转跃迁谱线, 本文在考虑了转动能级展开式中高阶小项H_v的前提下重新推导出能更好地预言R支和Q支跃迁谱线的物理解析公式. 另一方面, 通过对差分收敛法计算过程的细致分析, 从物理误差的角度提出了一个在没有实验数据作为参照时仍然能有效收敛的重要物理判据. 应用这些新公式和新判据对TiF和CO分子R支振转跃迁谱线和TiF分子Q支振转跃迁谱线进行了研究. 结果表明: 包含高阶小项H_v的新公式的预言结果精度比原有不含H_v的公式的结果提高了一个数量级; 新判据的使用能更有效地减小预言谱线的可能误差, 提高预言结果精度. 最后通过与最小二乘法计算结果的对比, 进一步说明新公式和新判据在预言R支和Q支振转跃迁谱线数据方面的有效性和准确性.