Publisher Summary Circular dichroism (CD) is a spectroscopic method which depends on the fact that certain molecules interact differently with right and left circularly polarized light. Circularly polarized light is chiral—that is, it occurs in two nonsuperimposable forms that are mirror images of one another. To discriminate between the two chiral forms of light, a molecule must be chiral, including the vast majority of biological molecules. A method that can discern the subtle differences between non superimposable mirror image molecules (enantiomers) must be highly sensitive to the three-dimensional features of molecules—that is, to conformation. Binding of ligands or protein-protein and protein–DNA interactions can also alter the circular dichroism spectrum of the protein and/or nucleic acid. These changes in CD can be used to determine equilibrium constants, and they can also provide evidence for conformational changes. Thus, CD can provide information about the secondary structure of proteins and nucleic acids and about the binding of ligands to these types of macromolecule.

[4] Circular dichroism

This article aims to show the identity of “circularly polarized luminescent active simple organic molecules” as a new concept in organic chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and non-aggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented.

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Circularly Polarized Luminescence from Simple Organic Molecules

Chiral π-conjugated molecules provide new materials with outstanding features for current and perspective applications, especially in the field of optoelectronic devices. In thin films, processes s...

Chiroptical Properties in Thin Films of π-Conjugated Systems.

Circularly-polarized luminescence (CPL) has received new attention on the rise of applications to generate devices and biologically active probes. These applications require fluorophores that are not only chiral but also provide strong fluorescence intensity in aggregated state. Thus, a new research branch has opened up a few years ago, which allows CPL-active fluorophores to be emissive in aggregated-state. As a result, reports on the combination of the CPL property with the aggregation-induced emission (AIE) phenomenon have emerged. Herein the early design principles that have been reported until now to generate CPL-active AIE-active fluorophores (AIEgens) are summarized. In this regard the alignment of monomeric emitters in a chiral fashion, either in supramolecules, polymers or liquid crystals has been proven to be a successful approach. Additionally, first reports have appeared that demonstrate how to tackle the daunting task to furnish individual CPL-active AIEgens.

Circularly-Polarized Luminescence (CPL) from Chiral AIE Molecules and Macrostructures

Fluorescent imaging of single helicene molecules is applied to study the optical activity of chiral fluorophores. In contrast to the previous report by Hassey et al. (Science 2006, 314, 1437), the dissymmetry factors of single chiral fluorophores are found not to differ significantly from the bulk value of |g| < 10(-4) at 457 nm. Linear dichroism and birefringence of the dichroic mirror inside the fluorescence microscope change the polarization state of the incoming laser beam significantly; i.e., circular polarized light sent into the microscope becomes highly elliptically polarized after reflection from the dichroic mirror. Compensation for this effect should be made to avoid artifacts brought by linear dichroism in single immobilized molecules.

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Limits on fluorescence detected circular dichroism of single helicene molecules.

The fluorescence detected circular dichroism (FDCD) and circular polarization of luminescence (CPL) of rigid systems is related to molecular parameters. It is found that FDCD can yield the CD for light incident along the direction of the fluorescence transition moment. The average CD can also be measured as in a fluid medium. From CPL measurements one can evaluate the optical activity for light incident along the direction of the absorption transition moment. Thus, photoselection provides a method for measuring the direction dependent CD or optical activity of a molecule without actually orienting the molecule.

Fluorescence detected circular dichroism and circular polarization of luminescence in rigid media: Direction dependent optical activity obtained by photoselection

B. Ehrenberg

Papers

Fluorescence detected circular dichroism and circular polarization of luminescence in rigid media: Direction dependent optical activity obtained by photoselection