Investigation of mononuclear,dinuclear, and trinuclear transition metal (II) complexes derived from an asymmetric Salamo‐based ligand possessing three different coordination modes

A new asymmetric Salamo‐based ligand H₂L was synthesized using 3‐tert‐butyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H₂L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}₂], and [{Ni(L)(CH₃COO)(CH₃CH₂OH)}₂Ni] with the ligand H₂L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H₂L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

Hitherto-Unexplored Photodynamic Therapy of Ag2S and Enhanced Regulation Based on Polydopamine In Vitro and Vivo

Given their superior penetration depths, photosensitizers with longer absorption wavelengths present broader application prospects in photodynamic therapy (PDT). Herein, Ag₂S quantum dots were discovered, for the first time, to be capable of killing tumor cells through the photodynamic route by near-infrared light irradiation, which means relatively less excitation of the probe compared with traditional photosensitizers absorbing short wavelengths. On modification with polydopamine (PDA), PDA-Ag₂S was obtained, which showed outstanding capacity for inducing reactive oxygen species (increased by 1.69 times). With the addition of PDA, Ag₂S had more opportunities to react with surrounding O₂, which was demonstrated by typical triplet electron spin resonance (ESR) analysis. Furthermore, the PDT effects of Ag₂S and PDA-Ag₂S achieved at longer wavelengths were almost identical to the effects produced at 660 nm, which was proved by studies in vitro. PDA-Ag₂S showed distinctly better therapeutic effects than Ag₂S in experiments in vivo, which further validated the enhanced regulatory effect of PDA. Altogether, a new photosensitizer with longer absorption wavelength was developed by using the hitherto-unexplored photodynamic function of Ag₂S quantum dots, which extended and enhanced the regulatory effect originating from PDA.     

Liquid chromatography‐tandem mass spectrometry assay for the simultaneous determination of three major flavonoids and their glucuronidated metabolites in rats after oral administration of Artemisia annua L. extract at a therapeutic ultra‐low dose

The traditional antimalarial herb Artemisia annua L., from which artemisinin is isolated, is widely used in endemic regions. It has been suggested that artemisinin activity can be enhanced by flavonoids in A. annua; however, how fast and how long the flavonoids are present in the body remains unknown. In the present study, a rapid and sensitive liquid chromatography with tandem mass spectrometry method was developed and validated for the simultaneous determination of three major flavonoids components, i.e. chrysosplenol D, chrysoplenetin, and artemetin and their glucuronidated metabolites in rats after oral administrations of A. annua extracts at a therapeutic ultra‐low dose. The concentration of the intact form was determined directly, and the concentration of the glucuronidated form was assayed in the form of flavonoids aglycones, after treatment with β‐glucuronidase/sulfatase. The method was linear in the range of 0.5–300.0 ng/mL for chrysoplenetin and artemetin, and 2–600 ng/mL for chrysosplenol D. All the validation data conformed to the acceptance requirements. The study revealed a significantly higher exposure of the flavonoid constituents in conjugated forms in rats, with only trace intact from. Multiple oral doses of A. annua extracts led to a decreased plasma concentration levels for three flavonoids.     

基于LS -DYNA公路桥车桥耦合的车辆模型研究

研究公路桥梁在移动车辆荷载作用下的动力响应,建立合理的车辆模型非常重要。为更真实地体现桥梁在车载作用下的动力响应,基于LS-DYNA程序,结合常用重型车辆的结构特性及参数,对车辆的橡胶轮胎、轮胎内气体压力、车轮转动和车辆悬架系统进行模拟,使车辆模型更接近实际车辆。通过车辆轴重和动力特性初步验证车辆有限元模型的有效性;同时,以一座混凝土简支空心板梁桥为算例,验证车轮转动和车桥相互接触力,并将LS-DYNA计算结果与桥梁实测结果进行对比,进一步验证车辆有限元模型的有效性。研究结果表明,基于LS-DYNA建立的三维车辆有限元模型是可行的,可以用于研究车桥相互作用。     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

椭球粒子声辐射力计算及分析

针对水下椭球粒子,以声散射理论为基础,采用分波序列的方法,建立了椭球粒子声辐射力的理论计算模型。进而根据声辐射力计算公式,以刚性椭球粒子和液体椭球粒子为例,计算并分析不同Bessel波束作用下椭球粒子的轴向声辐射力函数特征。数值仿真计算结果表明,对于刚性椭球粒子,扁平椭球粒子相对于细长椭球粒子更有助于激发负声辐射力；对于液体椭球粒子,细长椭球粒子相对于扁平椭球粒子更加容易产生负声辐射力；对于不同介质的椭球粒子,不同的入射波束激发的负声辐射力的效果也存在明显的差异。该结果为复杂的尺寸和介质粒子声操控技术提供了理论的可行性。     

Semiconducting Polymer Dots with Dual-Enhanced NIR-IIa Fluorescence for Through-Skull Mouse-Brain Imaging

Fluorescence probes in the NIR-IIa region show drastically improved imaging owing to the reduced photon scattering and autofluorescence in biological tissues. Now, NIR-IIa polymer dots (Pdots) are developed with a dual fluorescence enhancement mechanism. First, the aggregation induced emission of phenothiazine was used to reduce the nonradiative decay pathways of the polymers in condensed states. Second, fluorescence quenching was minimized by different levels of steric hindrance to further boost the fluorescence. The resulting Pdots displayed a fluorescence QY of ca. 1.7 % in aqueous solution, suggesting an enhancement of ca. 21 times in comparison with the original polymer in tetrahydrofuran (THF) solution. Small-animal imaging by using the NIR-IIa Pdots exhibited a remarkable improvement in penetration depth and signal to background ratio, as confirmed by through-skull and through-scalp fluorescent imaging of the cerebral vasculature of live mice.     

中空介孔SiO2纳米球的制备、改性及其对Al3+荧光识别研究

中空介孔SiO2由于中空多孔的结构而常用作功能材料的基底.将中空介孔SiO2进行官能团修饰,并应用为荧光传感材料是中空介孔SiO2一个重要的研究领域.本论文采用聚丙烯酸(PAA)为中空模板,聚醚F127为造孔剂,正硅酸乙酯(TEOS)为硅源,氨水为催化剂在乙醇体系中制备了中空介孔SiO2纳米球.系统研究了搅拌速度和聚醚F127引入量对中空介孔SiO2纳米球形貌及比表面积的影响.通过透射电镜、N2-等温吸附脱附曲线等表征说明该合成方法具有很好的普适性,通过调节F127的引入可以实现对比表面积的有效控制.通过氨基化、席夫碱反应进行荧光修饰,进一步研究表明荧光修饰后的中空介孔SiO2纳米球在水溶液中能够实现对Al3+的有效检测,检测限为1.19×10 -7M.