Ultrabroadband Optical Superchirality in a 3D Stacked‐Patch Plasmonic Metamaterial Designed by Two‐Step Glancing Angle Deposition

Low‐cost and large‐scale fabrication of 3D chiral metamaterials is highly desired for potential applications such as nanophotonics devices and chiral biosensors. One of the promising fabrication methods is to use glancing angle deposition (GLAD) of metal on self‐assembled dielectric microsphere array. However, structural handedness varies locally due to long‐range disorder of the array and therefore large‐scale realization of the same handedness is impossible. Here, using symmetry considerations a two‐step GLAD process is proposed to eliminate this longstanding problem. In the proposed scheme, the unavoidable long‐range disorder gives rise to microscale domains of the same handedness but of slightly different structural geometries and ultimately contributes to a broad‐band response. Experimentally, a record‐breaking superchiral response of circular dichroism signal of ≈11° is demonstrated and an average polarization rotation angle of 27° in the visible region on ≈1 cm² sample is observed. Computer‐aided geometric reconstruction with experimental parameters unambiguously reveal the presence of strong structural anisotropy and chirality in the prepared stacked‐patch plasmonic chiral metamaterial; microscopic spectral analyses combined with full‐wave electromagnetic simulations coherently provide deeper insights into the measured circular dichroism and optical activity. The observed chiroptical response can also be flexibly controlled by adjusting the deposition parameters for various potential applications.     

氨基酸作为手性源在有机合成中的应用

综述了近年来以氨基酸为手性源在合成手性生物碱、手性氨基醇、手性氨基醛和手性催化剂等化合物中的研究现状,并对氨基酸作为手性源在有机合成中的应用前景进行了展望。     

Visual Appearance of Chiral Nematic Cellulose‐Based Photonic Films: Angular and Polarization Independent Color Response with a Twist

Hydroxypropyl cellulose (HPC) is a biocompatible cellulose derivative capable of self‐assembling into a lyotropic chiral nematic phase in aqueous solution. This liquid crystalline phase reflects right‐handed circular polarized light of a specific color as a function of the HPC weight fraction. Here, it is demonstrated that, by introducing a crosslinking agent, it is possible to drastically alter the visual appearance of the HPC mesophase in terms of the reflected color, the scattering distribution, and the polarization response, resulting in an exceptional matte appearance in solid‐state films. By exploiting the interplay between order and disorder, a robust and simple methodology toward the preparation of polarization and angular independent color is developed, which constitutes an important step toward the development of real‐world photonic colorants.     

毛细管电泳法手性拆分橙皮苷对映体

通过考察电泳缓冲液pH、环糊精种类和浓度、有机溶剂浓度及操作电压和温度对分离的影响,建立了一种简便快捷的高效毛细管电泳拆分橙皮苷对映体的方法。实验结果表明,以12mmol/L的羟丙基-β-环糊精为手性选择剂,200mmol/L的硼酸/甲醇(V:V=7:3,pH9.7)为电泳缓冲溶液,23kV的分离电压,在30℃下可使橙皮苷对映体达到基线分离,分离度为1.50。分析方法快速简单。     

顺式和反式氯氰菊酯对映体的制备及其纯度鉴定

目的 获取重量为10 g以上且纯度高于98%的顺式和反式氯氰菊酯对映体, 用于后续不同对映体体内选择性代谢试验和体外细胞毒性对比试验。方法 采用定制涂敷型β-环糊精填料的手性制备柱, 通过高压制备色谱分别对顺式、反式氯氰菊酯工业品进行手性拆分, 收集各对映体馏分, 减压蒸馏、冻干, 制备重量为10 g以上的4个对映体; 采用正相手性高效液相色谱、气相色谱质谱、手性气相色谱质谱联用等技术分别对制备的4个对映体进行定性鉴定和纯度鉴定。结果 该方法制备的顺式氯氰菊酯2个对映体构型分别为1R-cis-αS和1S-cis-αR, 纯度分别为98.4%和99.0%; 反式氯氰菊酯2个对映体构型分别为1R-trans-αS和1S-trans-αR, 纯度分别为98.6%和99.0%。所制备的4个对映体重量均超过了10 g。 结论 该方法可成功分离顺式和反式氯氰菊酯对映体, 所制备的对映体重量为10 g以上且纯度均在98%以上, 达到了标准品的要求, 能满足后续体内代谢试验和体外细胞试验的需求。     

消旋氧氟沙星抗体制备及其手性识别特性研究

采用活泼酯法（A）和直接EDC（1-乙基-3-（3-二甲氨丙基）碳二亚胺盐酸盐）法（D）,合成两种包被抗原（OFL-A-OVA和OFL-D-OVA）和两种免疫抗原（OFL-A-BSA和OFL-D-BSA）,然后分别用两种免疫抗原免疫小鼠获得与其对应的多克隆抗体,建立消旋氧氟沙星残留免疫检测方法。研究结果表明：紫外扫描图谱证明四种抗原均合成成功,OFL-A-BSA、OFL-D-BSA、OFL-A-OVA和OFL-D-OVA的偶联比分别为19.67、3.03、1.93和0.99。消旋氧氟沙星的间接竞争ELISA法的线性检测范围为16.35～444.10ng/mL,IC50为5.42ng/mL,最低检测限为6.23ng/mL。消旋氧氟沙星抗体与恩诺沙星、环丙沙星、加替沙星等其他同类药物的交叉反应率较低,表明消旋氧氟沙星抗体具有较高的特异性,且消旋氧氟沙星抗体对左旋氧氟沙星和右旋氧氟沙星的识别并非对等,对左旋的识别能力较大,左旋氧氟沙星对抗体的产生起主要作用。     

高效液相色谱法快速鉴别人工合成虾青素养殖的三文鱼

建立了虾青素手性异构体分离和检测的HPLC 方法。条件：采用手性固定相色谱柱;Pirkle L- 亮胺酸(4.6mm × 25cm,5μm); 流动相：正己烷- 四氢呋喃- 异丙醇- 三乙胺(77:17:3:3,V/V);紫外检测波长：474nm;流速：0.75ml/min。本法可应用于快速鉴别养殖三文鱼是否使用了人工合成虾青素,并可以初步判断是否为野生三文鱼。     

Homochirality of Organic Matter – Objective Law or Curious Incident?

Of the many hypotheses on the origin of biological homochirality on the Earth, the combination of the notion of subatomic particles composing a homochiral pool of primary matter, on the one hand, with the suggestion of the synthesis of chiral organic molecules in the plasma torch generated by super-high-velocity impacts (SHVI) of meteorites, on the other hand, was chosen as the working assumption.     

手性硅宁—卟啉配体的合成与表征

首次合成了３种新的手性硅宁－卟啉配体。它们的结构分别用紫外可见光谱、核磁共振谱、红外光谱和质谱进行了表征。     

Chiral Discrimination Mechanisms by Silylated-Acetylated Cyclodextrins: Superficial Interactions vs. Inclusion

Cyclodextrin derivatives constitute a powerful class of auxiliary agents for the discrimination of apolar chiral substrates. Both host–guest inclusion phenomena and interactions with the derivatizing groups located on the surface of the macrocycle could drive the enantiodiscrimination; thus, it is important to understand the role that these processes play in the rational design of new chiral selectors. The purpose of this study is to compare via nuclear magnetic resonance (NMR) spectroscopy the efficiency of silylated-acetylated α-, β-, and γ-cyclodextrins in the chiral discrimination of 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane (compound B) and methyl 2-chloropropionate (MCP). NMR DOSY (Diffusion Ordered SpectroscopY) experiments were conducted for the determination of the bound molar fractions and the association constants, whereas ROESY (Rotating-frame Overhauser Enhancement SpectroscopY) measurements provided information on the hosts’ conformation and on the interaction phenomena with the guests. Compound B, endowed with fluorinated moieties, is not deeply included due to attractive Si-F interactions occurring at the external surface of the cyclodextrins. Therefore, a low selectivity toward the size of cyclodextrin cavity is found. By contrast, enantiodiscrimination of MCP relies on the optimal fitting between the size of the guest and that of the cyclodextrin cavity.