Photochemistry with Circularly Polarized Light

The reactions induced by circularly polarized light are reviewed and a general discussion of the induction of optical activity by circularly polarized light is presented. It is concluded that three different mechanisms, or their combinations, can cause asymmetric induction. In each case the optical yield is dependent on the optical anisotropy factor g, the ratio between the circular dichroism (Δ?) and the extinction coefficient (?). The results are discussed in terms of the presumed mechanisms, and particular attention is paid to the asymmetric synthesis of helicenes. It is concluded that this kind of photochemistry may have analytical importance.     

Solution-State 2D NMR Spectroscopy of Mixtures HyperpolarizedUsing Optically Polarized Crystals

The HYPNOESYS method (Hyperpolarized NOE System), which relies on the dissolution of optically polarized crystals, has recently emerged as a promising approach to enhance the sensitivity of NMR spectroscopy in the solution state. However, HYPNOESYS is a single-shot method that is not generally compatible with multidimensional NMR. Here we show that 2D NMR spectra can be obtained from HYPNOESYS-polarized samples, using single-scan acquisition methods. The approach is illustrated with a mixture of terpene molecules and a benchtop NMR spectrometer, paving the way to a sensitive, information-rich and affordable analytical method.     

Illumination of Cellulose with Linearly Polarized Visible Light

Summary: Aqueous suspensions of cellulose of long polysaccharide chains, were illuminated with visible polarized light (VPL) for 20 and 50 hrs. Crystal structure, thermal properties with Differential Scanning Calorimetry (DSC) and degree of polymerization (DP) of the samples were determined. Additionally, kinetic of enzymatic as well as acid-catalyzed hydrolysis of cellulose was estimated. Illumination of cellulose with VPL for 50 hrs increased its DP by 15%. X-ray diffraction patterns revealed that the illumination resulted in an increase in the amount of cellulose crystalline phase. The DSC measurements indicated differences in the water molecules distribution depending on the sample treatment confirming an increase in the crystallinity of the illuminated cellulose. After prolonged illumination, cellulose was resistant to oxidation and had lower susceptibility to enzymatic and acid-catalyzed hydrolysis.     

Charge-Transfer Complex Doped Photothermal Hydrogels for Discriminating Circularly Polarized Near-Infrared Light

Hydrogels behave as potential candidates to investigate circularly polarized light (CP)-matter interaction, which however suffer from small sensitivity towards circular polarization. Here we report a general protocol to build hydrogels from π-conjugated amino acids with coassembled charge-transfer (CT) complexes, covering a wide scope of donors and acceptors, which were incorporated into stable hydrogel matrices. CT complexes formed block coassemblies with gelators, induced the emergence of macroscopic chiral helices, where efficient chirality transfer occurs to realize tunable Cotton effects from visible light to NIR-I region depending on the structures of CT pairs. The hybrid hydrogels showed tunable photothermal performances with excellent heating-cooling cycling durability. Circularly polarized NIR light selectively triggered gel-solution phase transition at different timescales. Left- and right-CP illumination generates up to 2.5 folds difference in gel collapse time that allows for direct discrimination by naked eyes.     

液晶光取向技术

光取向技术是一种非接触式液晶取向方法,它具有无污染,不产生静电、易实现分区取向等优点,因而引起广大科技工作者的关注。本文综述了液晶光取向的最新研究进展,包括液晶光取向研究所选用的,各种材料有一定的光照条件下发生的分子结构的变化以及对液 取向方式的影响等。     

Microdetermination of Proteins by Enhanced Rayleigh Light Scattering Spectroscopy with Thorin

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手性有机光电功能材料及其圆偏振光发射与探测

手性有机半导体由于其新颖的性质引起了有机光电领域极大的研究兴趣. 将手性引入有机半导体材料不仅可以调控聚集态结构影响载流子输运进而影响光电器件的性能, 而且催生了圆偏振光直接发射与探测材料与器件的产生与发展. 手性材料与圆偏振光之间的相互作用使得其在3D显示、量子通讯、信息存储与处理等领域展示出广泛的应用前景. 本综述总结近年来手性有机光电材料及器件的研究进展, 主要围绕手性对有机半导体材料性质与器件性能的影响展开, 聚焦于手性有机半导体的圆偏振光直接发射与探测等研究, 旨在进一步为手性有机光电子领域的发展提供系统的认识.     

Circularly Polarized Light Triggers Biosensing Based on Chiral Assemblies

Chiral assemblies have attracted great interest because of their many potential applications, such as in chiral sensing, asymmetric catalysis, and optical devices. Here, by using specific DNAzymes, a chiral core–satellite assembly consisting of a DNAzyme-driven spiny nanorod dimer core and upconversion nanoparticle (UCNP) satellite was constructed. The chirality of this assembly originates from the geometry chirality. This chiral assembly can be used as a photothermally activated probe for the simultaneous detection of multiple analytes in living cells. Under illumination with 980 nm left circularly polarized (LCP) light, this probe was used to quantify and visualize intracellular metal ions.     

Reversible Handedness Inversion and Circularly Polarized Light Reflection Tuning in Self-Organized Helical Superstructures Using Visible-Light-Driven Macrocyclic Chiral Switches

A series of macrocyclic azobenzene-based chiral photoswitches have been judiciously designed, synthesized, and characterized. In the molecular structures, binaphthyl is covalently linked to ortho-positions of azobenzene, and four different substituents are linked to 6,6′-positions of binaphthyl. The photoswitches show enhanced helical twisting power (HTP) when doping in commercially available achiral liquid crystals to form self-organized helical superstructures, i.e., cholesteric liquid crystals (CLCs). All the photoswitches exhibit reversible photoisomerization driven by visible light of different wavelengths in both organic solvent and liquid crystals. The photoswitches with shorter substituents enable handedness inversion of CLCs upon photoisomerization. These are the first examples of ortho-linked azobenzene-based photoswitches that enable handedness inversion in CLCs. The photoswitches with longer substituents display only HTP values decreasing while maintaining the same handedness.     

Structure and Orientation of 1-(Hydroxyl)-5-(dodecyloxy)-naphthalene LB Films by Polarized Fluorescence Spectroscopy

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手性无机纳米材料圆偏振发光的研究进展

手性无机纳米材料因为具有优异的光物理特性及广泛的应用价值而备受关注。通过采用手性配体对无机纳米材料的表面进行修饰或将无机纳米材料与手性模板进行组装获得的手性结构,可以与光子强烈作用引起偏振态的改变,产生圆偏振光(circularly polarized light, CPL)。从产生机理来讲,CPL主要包括圆偏振荧光和圆偏振散射,在一些情况下这两个机理是共存的。本文总结了硫族半导体纳米材料、金属纳米团簇、钙钛矿、镧系配合物及其他复合纳米材料中CPL的研究进展。此外,还讨论了不同的手性无机纳米材料中CPL的主要来源。本综述得出的结论有望在分子水平上实现对CPL活性材料的各向异性因子进行调控,促进其在量子计算、光学数据存储、信息加密、3D显示器和光学传感等多个领域的发展。     

红外光谱鉴定聚丙烯中受阻胺光稳定剂

本文报道了用红外光谱方法鉴定的高分子和小分子受阻胺光稳定剂。此法包括溶解聚丙烯,接着用H_2SO_4沉淀并萃取,所得水溶液用NaOH中和并用二氯甲烷萃取,除去溶剂后残渣用IR鉴定。     

高聚物球晶偏光织态研究中的厚度性消光与补偿机理

以两维聚环氧乙烷（ＰＥＯ）球晶为对象，探讨了偏光显微法的消光机理，尤其是其中的厚度性消光机理，并对于补偿片的作用原理作了细致的理论分析，运用上述手段对ＰＥＯ球晶的形态进行了研究。     

Polarized Low-Temperature Crystal Spectra of Inorganic Complexes

The electronic spectra of complexes are especially informative if they are recorded for crystals at low temperature or at varying temperature with polarized light. This straightforward technique frequently permits reliable band assignment. Such assignments, being independent of the assumptions of any particular theoretical model, then provide a basis for testing theories of electronic structure.     

Infrared Diffusion-Ordered Spectroscopy Reveals Molecular Size and Structure**

Inspired by ideas from NMR, we have developed Infrared Diffusion-Ordered Spectroscopy (IR-DOSY), which simultaneously characterizes molecular structure and size. We rely on the fact that the diffusion coefficient of a molecule is determined by its size through the Stokes–Einstein relation, and achieve sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration in an IR-frequency resolved manner. Analogous to NMR-DOSY, a two-dimensional IR-DOSY spectrum has IR frequency along one axis and diffusion coefficient (or equivalently, size) along the other, so the chemical structure and the size of a compound are characterized simultaneously. In an IR-DOSY spectrum of a mixture, molecules with different sizes are nicely separated into distinct sets of IR peaks. Extending this idea to higher dimensions, we also perform 3D-IR-DOSY, in which we combine the conformation sensitivity of femtosecond multi-dimensional IR spectroscopy with size sensitivity.     

圆偏振光在手性聚合物合成与结构调控中的应用

手性是自然界中普遍存在的有趣现象之一,在生命体中手性大分子特有的不对称结构在维持生命过程、新陈代谢和进化等面均起着决定性作用.受此启发,合成具有新型结构的光学活性聚合物,研究其独特的物理化学性质和功能已成为当今高分子领域研究的热点.左旋和右旋的圆偏振光已被广泛应用于氨基酸衍生物的不对称光合成、光分解和去消旋化反应,以及诱导含有偶氮苯或三苯胺等特定功能基团的超分子组装体或无机纳米粒子形成稳定螺旋结构.本文详细地介绍了圆偏振光辐照在手性聚合物合成与螺旋结构调控中的应用,初步揭示了圆偏振光的作用机制以及优势,归纳总结了已取得的研究进展,并对圆偏振光在手性聚合物合成与结构调控中的应用及发展进行了简单的评述和展望.     

等离子体光谱光源技术的进展

光谱光源是光谱仪器和光谱技术的核心,等离子体光源是原子发射光谱技术的活跃领域之一,电感耦合等离子体(ICP)已成功地应用于原子发射光谱和无机质谱仪器。由于ICP光源采用氩气作为工作气体,耗量较大,降低氩气用量成为近些年来原子光谱技术研究和改进的重要目标。为此目的,已研究过各种低耗氩ICP光源,非氩气ICP光源,微波等离子体光源,射频电容耦合等离子体光源等。综述了近年这些等离子体发射光源的结构,分析性能及特点,以及它们所用工作气体情况。并归纳总结出,评价各种等离子体发射光谱光源应包括:等离子体温度(激发温度,气体温度),电子密度,工作气体种类及用量,元素检出限,光源的稳健性及经济方面等。     

偏振式能量色散X射线荧光光谱仪分析高炉渣

在偏振化能量色散型X射线荧光光谱仪上,使用一个HOPG次级靶,成功地对高炉渣中主要成分进行了分析。总的测量时间为120 s。此方法所得分析结果与标样中有关组分的证书值相符,也与工作标样中组分的已知值(化学法测得)一致。     

Circularly Polarized Laser Emission from Homochiral Superstructures based on Achiral Molecules with Conformal Flexibility

Without external chiral intervention, it is a challenge to form homochirality from achiral molecules with conformational flexibility. We here report on a rational strategy that uses multivalent noncovalent interactions to clamp the molecular conformations of achiral D-A molecules. These interactions overcome the otherwise dominant dipole-dipole interactions and thus disfavor their symmetric antiparallel stacking. It in turn facilitates parallel packing, leading to spontaneous symmetry breaking during crystallization and thus the formation of homochiral conglomerates. When this emergent homochirality is coupled with optical gain characteristics of the molecules, the homochiral crystals are explored as excellent circularly polarized micro-lasers with low lasing threshold (16.4 μJ cm⁻²) and high dissymmetry factor g_lum (0.9). This study therefore provides a facile design strategy for supramolecular chiral materials and active laser ones without the necessity of intrinsic chiral element.