Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering

Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)₃²⁺ for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts.

Artificial metalloenzyme visible light photocatalysts possess enhanced optical properties and are competent towards single electron and energy transfer organic transformations.     

A Double-Site Chemodosimeter for Selective Fluorescence Detection of a Nerve Agent Mimic

A novel two-site chemodosimeter (SWJT-4) based on fluorescein skeleton to detect diethyl chlorophosphate (DCP) was designed and synthesized. It is a turn-on fluorescent probe for DCP with good selectivity and obvious color change in aqueous solution. Interestingly, the two oxime groups of SWJT-4 as dual response sites initiated different reactions with DCP to form a cyano group and an isoxazole ring, respectively. The corresponding mechanism was confirmed by ¹H NMR, MS and DFT calculation. Moreover, SWJT-4 could be used as a fluorescent test paper to detect DCP vapor.     

Effects of High-Intensity Ultrasound Pretreatment on Structure,Properties, and Enzymolysis of Walnut Protein Isolate

The purpose of this paper was to investigate the effect of high-intensity ultrasonication (HIU) pretreatment before enzymolysis on structural conformations of walnut protein isolate (WPI) and antioxidant activity of its hydrolysates. Aqueous WPI suspensions were subjected to ultrasonic processing at different power levels (600–2000 W) and times (5–30 min), and then changes in the particle size, zeta (ζ) potential, and structure of WPI were investigated, and antioxidant activity of its hydrolysates was determined. The particle size of the particles of aqueous WPI suspensions was decreased after ultrasound, indicating that sonication destroyed protein aggregates. The ζ-potential values of a protein solution significantly changed after sonication, demonstrating that the original dense structure of the protein was destroyed. Fourier transform infrared spectroscopy indicated a change in the secondary structure of WPI after sonication, with a decrease in β-turn and an increase in α-helix, β-sheet, and random coil content. Two absorption peaks of WPI were generated, and the fluorescence emission intensity of the proteins decreased after ultrasonic treatment, indicating that the changes in protein tertiary structure occurred. Moreover, the degree of hydrolysis and the antioxidant activity of the WPI hydrolysates increased after sonication. These results suggest that HIU pretreatment is a potential tool for improving the functional properties of walnut proteins.     

平行排列液晶器件的波前调制特性

设计了一种新型的平行排列液晶相位调制器(LC PM),可在纯相位的模式下进行相位调制,研究了液晶相位调制器的光学特性,理论上给予了分析．对畸变波前进行了调制,在1 cm2的校正面积上,调制后的准确度PV(peak to valley)值接近λ／15(λ=0.6328 μm),RMS(Root Means Square)可达到λ／100,斯特列尔比SR (Strehl Ratio)达到0.989．改变了传统的扭曲向列液晶器件难于进行纯相位调制和得到高准确度调制的缺点,达到了理想的效果.     

缺陷态透射率可调的三缺陷层的一维光子晶体

利用传输矩阵方法,从理论上研究了三缺陷层一维光子晶体的光学性质.在缺陷层间距足够大以致于出现缺陷态简并的情况下,调节第一或第三个缺陷层的光学厚度,光子晶体缺陷态的透射率会发生最大程度的变化.这种结构可同时具有窄带滤波器和光开关的功能,据此提出了一种低阈值光开关的设计.把折射率可调的向列型液晶作为晶体的第三个缺陷层,并用4×4传输矩阵方法计算了其缺陷态透射率与电场电压的关系.     

采用光纤和YAP晶体的小型γ相机的蒙特卡罗模拟

基于波长位移光纤(WSF)耦合YAP晶体中的光子传输特性,用GEANT4软件包建立了一个蒙特卡罗模拟程序.对采用波长位移光纤耦合平板式YAP晶体的小型单管γ相机的性能进行了计算机模拟.采用波长位移光纤耦合光电倍增管光阴极面的读出方式,和晶体直接耦合光电倍增管光阴极面相比,在相同的晶体面积大小条件下,PSPMT光阴极面积可大大缩小,使费用降低.模拟结果表明：γ射线与晶体发生作用的地方所对应的光纤输出的平均光子数最少为15个,位置灵敏光电倍增管完全可以探测到.说明采用闪烁晶体－WSF－位置灵敏光电倍增管的读出方式是可行的;在用硅油耦合波长位移光纤和YAP晶体的情况下,获得的空间分辨率为1.28 mm(FWHM).模拟结果也说明了增加平均光子数对提高空间分辨率的重要性.     

基于分步式压印光刻的激光干涉仪纳米级测量及误差研究

针对在未做隔离保护处理的环境中,基于Michelson干涉原理的激光干涉仪测量系统存在严重的干扰误差,不适合分步式压印光刻纳米级对准测量的要求.采用Edlen公式的分析及计算,不仅在理论上揭示出环境温度、湿度、气压等变化对激光干涉仪测量准确度的影响,而且证明影响测量准确度的最大干扰源是空气流动的结果.通过气流隔离措施和系统测量反馈校正控制器,能够实时补偿激光干涉仪两路信号的相差.最终,测量漂移误差在10 min内由13 nm降低到5 nm以内,满足压印光刻在100 mm行程中达到20 nm定位准确度要求.     

上转换发光免疫试纸条扫描检测系统研究

研制了一种以上转换发光材料作为标记物的扫描检测系统,有别于传统的测量方法,可做出定量和多重分析.扫描检测系统以扫描方式逐点测量经生物反应而结合上去的UCP颗粒的含量,记录整个免疫试纸条的信息,计算出被测样品中特定生物分子的浓度.实验结果表明,该系统对兔抗鼠疫免疫球蛋白（IgG）标准样品的检测灵敏度达到百ng/mL量级,且具有变异系数小于6%的重复性,符合生物免疫测定的要求.     

环形光纤声发射传感器的相位调制特性研究

提出了一种基于光纤Sagnac干涉仪的环形传感器,用于固体表面传播的超声波的检测.这种传感器的特点是能够精确地检测由固体表面传播的超声波产生的微弱振动.当超声波信号通过光纤传感器的两个臂到达探测器时,干涉仪的输出光强度受到了超声信号的调制.通过检测干涉仪的输出光强度并利用Fourier变换,测得了超声信号的振幅和频率.而且对传感系统的位相调制特性进行了仿真,并对实验结果进行了分析,结果表明该系统可用于固体表面传播的超声波频率特征的识别.