磷酸酯类前药的合成方法与应用

磷酸酯类前药与原药相比,不仅能够提高药物靶向性、稳定性和生物利用度,减少药物毒副作用,还能掩蔽药物不适气味、提高水溶性从而改善给药途径。含羟基药物的磷酸酯化是该类药物前药设计的重要方法之一。本文根据中心磷原子的价态和化合物结构进行分类,综述了各种P(Ⅴ)四配位分子、P(Ⅲ)三配位分子和H-亚磷酸酯类化合物作为磷酸酯化试剂在磷酸酯类前药合成方法中的研究进展,并阐述了这些磷酸酯类药物的应用,最后总结了各类磷酸酯化试剂的优势与局限,并结合连续流反应技术应用案例展望了其发展趋势。     

Fabrication of Microporous Metal–Organic Frameworks in Uninterrupted Mesoporous Tunnels: Hierarchical Structure for Efficient Trypsin Immobilization and Stabilization

Hierarchically porous metal–organic frameworks (HP-MOFs) are promising in various applications. Most reported HP-MOFs are prepared based on the generation of mesopores in microporous frameworks, and the formed mesopores are connected by microporous channels, limiting the accessibility of mesopores for bulky molecules. A hierarchical structure is formed by constructing microporous MOFs in uninterrupted mesoporous tunnels. Using the confined space in as-prepared mesoporous silica, highly dispersed metal precursors for MOFs are coated on the internal surface of mesoporous tunnels. Ligand vapor-induced crystallization is employed to enable quantitative formation of MOFs in situ, in which sublimated ligands diffuse into mesoporous tunnels and react with metal precursors. The obtained hierarchically porous composites exhibit record-high adsorption capacity for the bulky molecule trypsin. The thermal and storage stability of trypsin is improved upon immobilization on the composites.     

Synthesis of Axially Chiral Styrenes through Pd-Catalyzed Asymmetric C−H Olefination Enabled by an Amino Amide Transient Directing Group

The atroposelective synthesis of axially chiral styrenes remains a formidable challenge due to their relatively lower rotational barriers compared to the biaryl atropoisomers. Herein, we describe the construction of axially chiral styrenes through Pd^II-catalyzed atroposelective C−H olefination, using a bulky amino amide as a transient chiral auxiliary. Various axially chiral styrenes were produced with good yields and high enantioselectivity (up to 95 % yield and 99 % ee). Carboxylic acid derivatives of the resulting axially chiral styrenes showed superior enantiocontrol over the biaryl counterparts in Co^III-catalyzed enantioselective C(sp³)−H amidation of thioamide. Mechanistic studies suggest that C−H cleavage is the enantioselectivity-determining step.     

Origins of Boosted Charge Storage on Heteroatom-Doped Carbons

Although tremendous efforts have been devoted to understanding the origin of boosted charge storage on heteroatom-doped carbons, none of the present studies has shown a whole landscape. Herein, by both experimental evidence and theoretical simulation, it is demonstrated that heteroatom doping not only results in a broadened operating voltage, but also successfully promotes the specific capacitance in aqueous supercapacitors. In particular, the electrolyte cations adsorbed on heteroatom-doped carbon can effectively inhibit hydrogen evolution reaction, a key step of water decomposition during the charging process, which broadens the voltage window of aqueous electrolytes even beyond the thermodynamic limit of water (1.23 V). Furthermore, the reduced adsorption energy of heteroatom-doped carbon consequently leads to more stored cations on the heteroatom-doped carbon surface, thus yielding a boosted charge storage performance.     

溶剂比对Mn-ZnO复合纳米线形貌及吸附脱硫研究

采用水热法合成了Mn-ZnO复合纳米线,通过改变溶剂比来考察其对Mn-ZnO形貌的影响,并用等体积浸渍法负载金属Ni,制备反应吸附脱硫剂,以正庚烷/噻吩为模拟油并在固定床反应器装置上评价反应吸附脱硫性能.通过XRD、BET、SEM等方法对该催化剂进行表征;研究表明:溶剂比不同可导致Mn-ZnO复合物形貌的不同,从而影响脱硫性能.以乙醇溶液为溶剂制备的脱硫催化剂脱硫率可达99;左右,并且具有良好的稳定性.     

旋涂法制备掺杂BiOX薄膜及光催化性能研究

采用旋涂的方法在基底材料表面原位生长BiOX(X=C1、Br、I)薄膜材料.样品的晶体结构和光学性质等通过X射线粉末衍射(XRD)、透射电子显微镜(TEM)、紫外可见漫反射光谱(UV-Vis)进行了表征.结果表明旋涂法制备的BiOX薄膜是纯净的,无其他杂质,均匀性好.通过对BiOX薄膜材料的光催化性能和瞬态表面光电压技术(TPV)进行了研究,发现卤素掺杂的BiOBr0.48I052具有较好的光催化性能.其结果表明催化性能提高的原因可能是BiOBr0.48I0.52薄膜在光照下可以产生更强的光生载流子并具有更长的光生载流子寿命.     

Effect of C60 nanoparticles on elasticity of small unilamellar vesicles composed of DPPC bilayers

The interaction between C60 nanoparticles and biomembranes has been of great interest in researches over the past decades due to their novel applications as well as potential cytotoxicity.In this work,we study the deformation of the small unilamellar vesicles composed of dipalmitoylphosphatidylcholine(DPPC)lipid bilayers infiltrated with C60 nanoparticles of different molecular concentrations through coarse-grained molecular dynamics simulations.By employing the Helfrich spontaneous curvature model,the bending modulus and the spontaneous curvature of the vesicles with C60 nanoparticles of different concentrations are obtained according to the simulation data.The results show that the bending modulus and the spontaneous curvature of pure DPPC vesicle membranes are approximately 1.6×10^-19J and 1.4 nm^-1,respectively.Both of them increase linearly approximately as the C60 concentration increases from 0 to 16.3%.The density profiles of vesicles,the order of lipid packing and the diffusion characteristics of DPPC and C60 are also investigated.     

NO分子宏观气体热力学性质的理论研究

采用量子统计系综理论,研究了基态NO分子宏观气体摩尔熵、摩尔内能、摩尔热容等热力学性质.首先应用课题组前期建立的变分代数法(variational algebraic method, VAM)计算获得了基态NO分子的完全振动能级,得到的VAM振动能级作为振动部分,结合欧拉-麦克劳林渐进展开公式的转动贡献,应用于经典的热力学与统计物理公式中,从而计算得到了1000-5000 K温度范围内NO宏观气体的摩尔内能、摩尔熵和摩尔热容.将不同方法计算得到的摩尔热容结果分别与实验值进行比较,结果表明基于VAM完全振动能级获得的结果优于其他方法获得的理论结果.振动部分采用谐振子模型对无限能级求和计算热力学性质的方法有一定的局限性,应当使用有限的完全振动能级进行统计求和.     

气体压强对纳秒激光诱导空气等离子体特性的影响

环境气体的压强对激光诱导等离子体特性有重要影响.基于发射光谱法开展了气体压强对纳秒激光诱导空气等离子体特性影响的研究,探讨了气体压强对空气等离子体发射光谱强度、电子温度和电子密度的影响.实验结果表明,在10-100 kPa空气压强条件下,空气等离子体发射光谱中的线状光谱和连续光谱依赖于气体压强变化,且原子谱线和离子谱线强度随气体压强的变化有明显差别.随着空气压强增大,激光击穿作用区域的空气密度增加,造成激光诱导击穿空气几率升高,从而等离子体辐射光谱强度增大.空气等离子体膨胀区域空气的约束作用,增加了等离子体内粒子间的碰撞几率以及能量交换几率,并且使离子-电子-原子的三体复合几率增加,因此造成原子谱线OⅠ777.2 nm与NⅠ821.6 nm谱线强度随着气体压强增大而增大,在80 kPa时谱线强度最高,随后谱线强度缓慢降低.而离子谱线N Ⅱ 500.5 nm谱线强度在40 kPa时达到最大值,气体压强大于40 kPa后,谱线强度随压强增加而逐渐降低.空气等离子体电子密度均随压强升高而增大,在80 kPa后增长速度变缓.等离子体电子温度在30 kPa时达到最大值,气体压强大于30 kPa后,等离子体电子温度逐渐降低.研究结果可为不同海拔高度的激光诱导空气等离子体特性的研究提供重要实验基础,为今后激光大气传输、大气组成分析提供重要的技术支持.     

Surface Modification of ZrO2–3Y2O3 with Highintensity Pulsed N2+ Ion Beams

Russian Physics Journal -