“Parallel factor analysis of multi-excitation ultraviolet resonance Raman spectra for protein secondary structure determination”

Protein secondary structural analysis is important for understanding the relationship between protein structure and function, or more importantly how changes in structure relate to loss of function. The structurally sensitive protein vibrational modes (amide I, II, III and S) in deep-ultraviolet resonance Raman (DUVRR) spectra resulting from the backbone C–O and N–H vibrations make DUVRR a potentially powerful tool for studying secondary structure changes. Experimental studies reveal that the position and intensity of the four amide modes in DUVRR spectra of proteins are largely correlated with the varying fractions of α-helix, β-sheet and disordered structural content of proteins. Employing multivariate calibration methods and DUVRR spectra of globular proteins with varying structural compositions, the secondary structure of a protein with unknown structure can be predicted. A disadvantage of multivariate calibration methods is the requirement of known concentration or spectral profiles. Second-order curve resolution methods, such as parallel factor analysis (PARAFAC), do not have such a requirement due to the “second-order advantage.” An exceptional feature of DUVRR spectroscopy is that DUVRR spectra are linearly dependent on both excitation wavelength and secondary structure composition. Thus, higher order data can be created by combining protein DUVRR spectra of several proteins collected at multiple excitation wavelengths to give multi-excitation ultraviolet resonance Raman data (ME-UVRR). PARAFAC has been used to analyze ME-UVRR data of nine proteins to resolve the pure spectral, excitation and compositional profiles. A three factor model with non-negativity constraints produced three unique factors that were correlated with the relative abundance of helical, β-sheet and poly-proline II dihedral angles. This is the first empirical evidence that the typically resolved “disordered” spectrum represents the better defined poly-proline II type structure.     

Methoxy and Methyl Group Rotation: Solid‐State NMR 1H Spin‐Lattice Relaxation,Electronic Structure Calculations,X‐ray Diffractometry,and Scanning Electron Microscopy

We report solid‐state ¹H nuclear magnetic resonance (NMR) spin‐lattice relaxation experiments, X‐ray diffractometry, field‐emission scanning electron microscopy, and both single‐molecule and cluster ab initio electronic structure calculations on 1‐methoxyphenanthrene ( 1 ) and 3‐methoxyphenanthrene ( 2 ) to investigate the rotation of the methoxy groups and their constituent methyl groups. The electronic structure calculations and the ¹H NMR relaxation measurements can be used together to determine barriers for the rotation of a methoxy group and its constituent methyl group and to develop models for the two coupled motions.     

Study of the forced degradation behavior of prasugrel hydrochloride by liquid chromatography with mass spectrometry and liquid chromatography with NMR detection and prediction of the toxicity of the characterized degradation products

Prasugrel was subjected to forced degradation studies under conditions of hydrolysis (acid, base, and neutral), photolysis, oxidation, and thermal stress. The drug showed liability in hydrolytic as well as oxidative conditions, resulting in a total of four degradation products. In order to characterize the latter, initially mass fragmentation pathway of the drug was established with the help of mass spectrometry/time‐of‐flight, multiple stage mass spectrometry and hydrogen/deuterium exchange data. The degradation products were then separated on a C₁₈ column using a stability‐indicating volatile buffer method, which was later extended to liquid chromatography‐mass spectrometry studies. The latter highlighted that three degradation products had the same molecular mass, while one was different. To characterize all, their mass fragmentation pathways were established in the same manner as the drug. Subsequently, liquid chromatography‐nuclear magnetic resonance (NMR) spectroscopy data were collected. Proton and correlation liquid chromatography with NMR spectroscopy studies highlighted existence of diastereomeric behavior in one pair of degradation products. Lastly, toxicity prediction by computer‐assisted technology (TOPKAT) and deductive estimation of risk from existing knowledge (DEREK) software were employed to assess in silico toxicity of the characterized degradation products.     

基于PCAU-Net的快速多通道磁共振成像方法

多通道磁共振成像方法采用多个接收线圈同时欠采样k空间以加快成像速度,并基于后处理算法重建图像,但在较高加速因子时,其图像重建质量仍然较差．本文提出了一种基于PCAU-Net的快速多通道磁共振成像方法,将单通道实数U型卷积神经网络拓展到多通道复数卷积神经网络,设计了一种结构不对称的U型网络结构,通过在解码部分减小网络规模以降低模型的复杂度．PCAU-Net网络在跳跃连接前增加了1×1卷积,以实现跨通道信息交互．输入和输出之间利用残差连接为误差的反向传播提供捷径．实验结果表明,使用规则和随机采样模板,在不同加速因子时,相比常规的GRAPPA重建算法和SPIRiT重建方法,本文提出的PCAU-Net方法可高质量重建出磁共振复数图像,并且相比于PCU-Net方法,PCAU-Net减少了模型参数、缩短了训练时间．     

EPR谱图模拟软件EasySpin的图形用户界面设计

EasySpin是一款较为流行的电子顺磁共振（EPR）谱图模拟和拟合软件,LabVIEW是一种图形化编程语言开发环境．本文介绍了一款使用LabVIEW为EasySpin设计的图形用户界面LV-EasySpin．LV-EasySpin提供了一种直观的操作方法来实现连续波EPR多组分波谱的可视化模拟和拟合．本文辅以各种模式下的实例进行说明,阐述了LV-EasySpin的设计思路与实现方案,最终希望具有简洁、易操作界面的LV-EasySpin可以降低用户使用EasySpin分析EPR谱图的难度．     

Design of a coated thinly clad chalcogenide long-period fiber grating refractive index sensor based on dual-peak resonance near the phase matching turning point

A novel method for designing chalcogenide long-period fiber grating (LPFG) sensors based on the dual-peak resonance effect of the LPFG near the phase matching turning point (PMTP) is presented. Refractive index sensing in a high-refractive-index chalcogenide fiber is achieved with a coated thinly clad film. The dual-peak resonant characteristics near the PMTP and the refractive index sensing properties of the LPFG are analyzed first by the phase-matching condition of the LPFG. The effects of film parameters and cladding radius on the sensitivity of refractive index sensing are further discussed. The sensor is optimized by selecting the appropriate film parameters and cladding radius. Simulation results show that the ambient refractive index sensitivity of a dual-peak coated thinly clad chalcogenide LPFG at the PMTP can be 2400 nm/RIU, which is significantly higher than that of non-optimized gratings. It has great application potential in the field of chemical sensing and biosensors.     

高中化学竞赛中电子效应和空间效应考点分析——以近年全国化学奥林匹克竞赛试题为例

电子效应和空间效应是有机化学的基础,近年来,这部分知识在全国化学奥林匹克竞赛中的考查比例处于上升趋势。因此,以近年全国化学奥林匹克竞赛试题为例,详细说明电子效应和空间效应在竞赛中的考点,帮助辅导化学竞赛的教师和参加化学竞赛的考生了解该部分知识需要达到的教学标准和掌握层次。     

Effects of High Pressure on the Surface Plasmon Resonance of Copper and Silver Nanocrystals

We used a diamond anvil cell(DAC) to control the deformation of synthesized copper nanorods and silver nanoparticles. And we measured the surface plasmon resonance of copper nanorods and silver nanoparticles, which exhibit redshifts or blueshifts. The surface plasmon resonance shows an abnormal blue shift for both copper nanorods and silver nanoparticles. The solvents of copper nanorods and silver nanoparticles are n-hexane and water, where the pressure loads include quasi-hydrostatic and non-hydrostatic.     

Rational Design of Ratiometric Fe3+ Fluorescent Probes Based on FRET Mechanism

As the most abundant transition metal element in mammals, iron(Fe) plays a vital role in life activities. It is of great significance to study the variation of Fe³⁺ level in living organisms. In virtue of the advantages of high sensitivity, good selectivity and low damage to living systems, the fluorescence detection of Fe³⁺ has attracted much attention. Compared with the intensity-based fluorescent probe, the ratiometric fluorescent probe has less interference of environmental and can realize quantitative detection. In this study, four ratiometric Fe³⁺ fluorescent probes, R1, R2, R3 and R4_, were designed and synthesized using fluorescence resonance energy transfer(FRET) mechanism to achieve quantitative detection of Fe³⁺. In the FRET systems, 1,8-naphthalimide fluorophore derivatives were adopted as donors while rhodamine B derivatives were selected as receptors. The connection sites of the donor and acceptor in R3 and R4 are different from those in R1 and R2. All the four probes showed good response and selectivity to Fe³⁺. The energy transfer efficiencies of R3 and R4 were obviously higher than those of R1 and R2. This work provided a promising strategy for the development of fluorescent ratiometic Fe³⁺sensors.