Space and the Chiral Molecule

Author(s):  
Robin Le Poidevin

According to classical stereochemistry, the molecules of some substances have doubles, in the sense of incongruent mirror-image counterparts. This is the phenomenon of optical isomerism, first identified 150 years ago by Pasteur. In some cases, the double occurs naturally; in others, it has to be artificially synthesized. These molecules thus share a geometrical feature with such familiar objects as our hands, and, indeed, it is this connection that gives the feature its technical name: chirality (from the Greek for hand, kheir). Instances of chirality in chemistry are numerous, especially in living things: examples of chiral molecules include adrenaline, glucose, and DNA. Optical isomerism is interesting, both historically—it played a crucial role in the emergence of structural chemistry and in the attempt to link chemistry with physics— and, I believe, philosophically. I should like to take this opportunity to revisit the scene of an earlier article of mine (Le Poidevin, 1994) in which I examined the implications optical isomerism has for a philosophical debate concerning the nature of space. In that article I argued that chirality in chemistry reinforces a conclusion that Graham Nerlich (1994), in a brilliant reconstruction of a famous argument of Kant’s, had derived from more visible instances of chirality: that we should be realists about the geometrical properties of space. I did not, however, want to follow Nerlich (and Kant) in drawing a more radical conclusion: that we should be realists about the existence of space. That may sound paradoxical, but it is possible (or so I thought) to regard space as a logical construction from its contents and still think of it, qua construction, as possessing certain intrinsic properties that we do not merely impose on it by convention. Since then, I have become more sympathetic to Nerlich’s position. Chirality is best understood by thinking of space as an entity in its own right. So chemistry has some lessons for the philosophy of space. But the pedagogical relation goes the other way, too: the philosophy of space has interesting implications for chemistry.

The development of laser-based polarimetric detectors for high-performance liquid chromatography (HPLC) (Yeung et al . 1980; Bobbitt & Yeung 1986) with noise levels in the range of 0.1-10 p° has provided a significant advance in the quantitation of chiral molecules. We have designed an instrument based on an 820 nm diode laser which has the advantages of low source flicker noise and compact design (Lloyd et al . 1989). Detection limits were found to be in the range 0.1-2 pg, dependent on the specific rotation of the chiral molecule and the chromatographic peak width (Goodall et al. 1990).


Molecules ◽  
2019 ◽  
Vol 24 (5) ◽  
pp. 853 ◽  
Author(s):  
Emilija Petronijevic ◽  
Concita Sibilia

Nanomaterials can be specially designed to enhance optical chirality and their interaction with chiral molecules can lead to enhanced enantioselectivity. Here we propose periodic arrays of Si nanowires for the generation of enhanced near-field chirality. Such structures confine the incident electromagnetic field into specific resonant modes, which leads to an increase in local optical chirality. We investigate and optimize near-field chirality with respect to the geometric parameters and excitation scheme. Specially, we propose a simple experiment for the enhanced enantioselectivity, and optimize the average chirality depending on the possible position of the chiral molecule. We believe that such a simple achiral nanowire approach can be functionalized to give enhanced chirality in the spectral range of interest and thus lead to better discrimination of enantiomers.


CNS Spectrums ◽  
2002 ◽  
Vol 7 (S1) ◽  
pp. 8-13 ◽  
Author(s):  
Joseph Gal

ABSTRACTSingle-isomer drugs are of great importance in modern therapeutics. In this article, the basics of the underlying phenomenon are explained. Some molecules are chiral, ie, their mirror image is not superposable on the original. The most common element producing molecular chirality is a chiral center, typically a carbon atom carrying four different groups. The mirror-image molecules are termed enantiomers, but the less specific terms stereoisomers and isomers are also used. A substance consisting of only one of the two enantiomers is a single enantiomer or single isomer, and the 1:1 mixture of the enantiomers is the racemic mixture or racemate. A graphical convention that conveys the three-dimensional aspects of chiral molecules drawn in two dimensions, as well as two nongraphical conventions, based on optical rotation and configuration, are used to identify enantiomers. Optical rotation is a physical property of single enantiomers and involves rotation of the plane of plane-polarized light, each pure enantiomer rotating with equal magnitude but in the opposite direction (dextro and levo). Configuration is the actual arrangement in space of the atoms of chiral molecules. Two systems of indicating configuration are in use. One employs D and L to denote the respective enantiomers, and is applicable only to α-amino acids and carbohydrates. The other is a universal system using R and S as descriptors for the two possible arrangements, respectively, of the atoms around the chiral center. Interest in chiral drugs stems from the frequently observed biological differences between enantiomers. Such enantioselectivity is the result of different interactions of the drug enantiomers with target receptors that are themselves chiral and single-enantiomeric.


1995 ◽  
Vol 28 (4) ◽  
pp. 473-507 ◽  
Author(s):  
L. Keszthelyi

Molecules built up from a given set of atoms may differ in their three-dimensional structure. They may have one or more asymmetric centres that serve as reference points for the steric distribution of the atoms. Carbon atoms, common to all biomolecules, are often such centres. For example, the Cα atom between the carboxyl and amino groups in amino acids is an asymmetric centre: looking ON ward (i.e. from the carbOxyl to the amiNo group, with the Cα oriented so that it is above the carboxyl and amino groups) the radical characterizing the amino acid may be to the right (D-molecules) or to the left (L-molecules). Nineteen of the 20 amino acids occurring in proteins have such a structure (the exception is glycine, where the radical is a hydrogen atom). These pairs of molecules cannot be brought into coincidence with their own mirror image, as is the situation with our hands. The phenomenon has therefore been named handedness, or chirality, from the Greek word cheir, meaning hand. The two forms of the chiral molecules are called enantiomers or antipodes. They differ in rotating the plane of the polarized light either to the right or to the left. The sense of rotation depends on the wavelength of the measuring light, but at a given wavelength it is always opposite for a pair of enantiomers. Chirality may also occur when achiral molecules form chiral substances during crystallization (for example, quartz forms D-quartz or Lquartz). A detailed theoretical treatment of molecular chirality is given by Barron (1991).


2019 ◽  
Vol 205 ◽  
pp. 02001
Author(s):  
Yoichi Harada ◽  
Eisuke Haraguchi ◽  
Keisuke Kaneshima ◽  
Taro Sekikawa

Circularly polarized high harmonic generation from a chiral molecule was found to significantly depend both on the chirality and on the rotating direction of the circularly polarized counter-rotating two-color driving laser fields.


Research ◽  
2020 ◽  
Vol 2020 ◽  
pp. 1-9 ◽  
Author(s):  
Jiaxin Bao ◽  
Ning Liu ◽  
Hanwei Tian ◽  
Qiang Wang ◽  
Tiejun Cui ◽  
...  

Chiral molecules that do not superimpose on their mirror images are the foundation of all life forms on earth. Chiral molecules exhibit chiroptical responses, i.e., they have different electromagnetic responses to light of different circular polarizations. However, chiroptical responses in natural materials, such as circular dichroism and optical rotation dispersion, are intrinsically small because the size of a chiral molecule is significantly shorter than the wavelength of electromagnetic wave. Conventional technology for enhancing chiroptical signal entails demanding requirements on precise alignment of the chiral molecules to certain nanostructures, which however only leads to a limited performance. Herein, we show a new approach towards enhancement of chiroptical effects through a Fabry–Pérot (FP) cavity formed by two handedness-preserving metamirrors operating in the GHz region. We experimentally show that the FP cavity resonator can enhance the optical activity of the chiral molecule by an order of magnitude. Our approach may pave the way towards state-of-the-art chiral sensing applications.


Author(s):  
Stephen Gauthier

We report here on the characterization of two types of chiral molecules deposited onto a silicon surface. Chiral molecules are non­superimposable mirror images of each other. Other than the way they interact with biological systems, chiral molecules have the same physical properties which make them hard to  separate. Since many important drug molecules are chiral, effective separation methods are required by  industry. We are building a model system to study one separation method called chiral chromatography. In chiral chromatography, separation is achieved by immobilizing a chiral compound along a column and  passing the desired chiral mixture through. One of the mirror image molecules of the mixture has a higher  attraction to the immobilized phase which causes it to exit the column at a later time. In the model being  studied, propranolol is the sample drug molecule and phenylethylpropylurea (PEPU) is the selector  molecule. Derivatives of these compounds were deposited onto a flat silicon surface. The resulting  samples were studied in order to gain insight into the surface morphology and characteristics of the assembled layers. Using a combination of infra red (IR) spectroscopy and computational analysis it was possible to infer the average bulk molecular orientation of the deposited propranolol molecules. Atomic force microscopy was used to ensure a uniform deposition as well as to quantify the surface roughness. Through X­ray photoelectron spectroscopy (XPS) analysis it was shown that an average layer thickness of  four molecules was deposited onto the silicon


2021 ◽  
Vol 51 (1) ◽  
Author(s):  
Ron Naaman ◽  
Yossi Paltiel ◽  
David H. Waldeck

Chirality in life has been preserved throughout evolution. It has been assumed that the main function of chirality is its contribution to structural properties. In the past two decades, however, it has been established that chiral molecules possess unique electronic properties. Electrons that pass through chiral molecules, or even charge displacements within a chiral molecule, do so in a manner that depends on the electron's spin and the molecule's enantiomeric form. This effect, referred to as chiral induced spin selectivity (CISS), has several important implications for the properties of biosystems. Among these implications, CISS facilitates long-range electron transfer, enhances bio-affinities and enantioselectivity, and enables efficient and selective multi-electron redox processes. In this article, we review the CISS effect and some of its manifestations in biological systems. We argue that chirality is preserved so persistently in biology not only because of its structural effect, but also because of its important function in spin polarizing electrons. Expected final online publication date for the Annual Review of Biophysics, Volume 51 is May 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.


1984 ◽  
Vol 39 (3) ◽  
pp. 254-261 ◽  
Author(s):  
G. Wagnière

AbstractA static magnetic field parallel to the direction of propagation of an incident light beam causes a small shift in the value of the refractive index and, correspondingly, of the absorption coefficient of a chiral molecule. This shift is opposite for enantiomers. However, it occurs for arbitrarily polarized light and is therefore not a circular differential effect.


Nanophotonics ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 797-824
Author(s):  
Vera Kuznetsova ◽  
Yulia Gromova ◽  
Marina Martinez-Carmona ◽  
Finn Purcell-Milton ◽  
Elena Ushakova ◽  
...  

AbstractChirality is one of the most fascinating occurrences in the natural world and plays a crucial role in chemistry, biochemistry, pharmacology, and medicine. Chirality has also been envisaged to play an important role in nanotechnology and particularly in nanophotonics, therefore, chiral and chiroptical active nanoparticles (NPs) have attracted a lot of interest over recent years. Optical activity can be induced in NPs in several different ways, including via the direct interaction of achiral NPs with a chiral molecule. This results in circular dichroism (CD) in the region of the intrinsic absorption of the NPs. This interaction in turn affects the optical properties of the chiral molecule. Recently, studies of induced chirality in quantum dots (QDs) has deserved special attention and this phenomenon has been explored in detail in a number of important papers. In this article, we review these important recent advances in the preparation and formation of chiral molecule–QD systems and analyze the mechanisms of induced chirality, the factors influencing CD spectra shape and the intensity of the CD, as well as the effect of QDs on chiral molecules. We also consider potential applications of these types of chiroptical QDs including sensing, bioimaging, enantioselective synthesis, circularly polarized light emitters, and spintronic devices. Finally, we highlight the problems and possibilities that can arise in research areas concerning the interaction of QDs with chiral molecules and that a mutual influence approach must be taken into account particularly in areas, such as photonics, cell imaging, pharmacology, nanomedicine and nanotoxicology.


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