Search results for "chirality"
showing 10 items of 188 documents
Orientation-Dependent Handedness of Chiral Plasmons on Nanosphere Dimers: How to Turn a Right Hand into a Left Hand
2016
Optical activity, which is used as a discriminator of chiral enantiomers, is demonstrated to be orientation dependent on individual, and nominally achiral, plasmonic nanosphere dimers. Through measurements of their giant Raman optical activity, we demonstrate that L/R-handed enantiomers can be continuously turned into their R/L-handed mirror images without passing through an achiral state. The primitive uniaxial multipolar response, with demonstrable broken parity and time reversal symmetry, reproduces the observations as resonant Raman scattering on plasmons that carry angular momentum. The analysis underscores that chirality does not have a quantitative continuous measure and recognizes t…
Synthesis, crystal structure and Hirshfeld analysis of a crystalline compound comprising a 1/1 mixture of 1-[(1R,4S)- and 1-[(1S,4R)-1,7,7-trimethyl-…
2020
A racemic mixture of (R)- and (S)-camphor thiosemicarbazone, which crystallizes in the centrosymmetric space group C2/c, is reported.
Spontaneous Resolution of an Electron‐Deficient Tetrahedral Fe4L4cage
2015
A highly electron-deficient C3-symmetric tris(bipyridyl) ligand was prepared in four steps and used for the coordination of Fe(OTf)2, thereby resulting in the homochiral assembly of a new family of robust tetrahedral M4L4 cages. This homochiral T-symmetric cage containing a relatively large cavity of 330 A(3) is capable of encapsulating an anionic guest, as was determined by mass spectrometry, (19)F NMR spectroscopy, and finally shown from its crystal structure. Moreover, crystallization of the cage from CH3CN led to crystals containing both (ΔΔΔΔ and ΛΛΛΛ) enantiomers, while crystallization from CH3 OH resulted in crystals containing only the right-handed (ΔΔΔΔ) cage. The difference in the…
A Tunable, Fullerene‐Based Molecular Amplifier for Vibrational Circular Dichroism
2019
Abstract Vibrational circular dichroism (VCD) studies are reported on a chiral compound in which a fullerene C60 moiety is used as an electron acceptor and local VCD amplifier for an alanine‐based peptide chain. Four redox states are investigated in this study, of which three are reduced species that possess low‐lying electronic states as confirmed by UV/Vis spectroelectrochemistry. VCD measurements in combination with (TD)DFT calculations are used to investigate (i) how the low‐lying electronic states of the reduced species modulate the amplification of VCD signals, (ii) how this amplification depends on the distance between oscillator and amplifier, and (iii) how the spatial extent of the…
What Contributes to the Measured Chiral Optical Response of the Glutathione-Protected Au25 Nanocluster?
2023
The water-soluble glutathione-protected [Au25(GSH)18]−1 nanocluster was investigated by integrating several methodologies such as molecular dynamics simulations, essential dynamics analysis, and state-of-the-art time-dependent density functional theory calculations. Fundamental aspects such as conformational, weak interactions and solvent effects, especially hydrogen-bonds, were included and found to play a fundamental role in assessing the optical response of this system. Our analysis demonstrated not only that the electronic circular dichroism is extremely sensitive to the solvent presence but also that the solvent itself plays an active role in the optical activity of such system, formin…
On the physicochemical properties of pyridohelicenes.
2014
A comprehensive study on the physicochemical properties of a series of mono- and diaza[5]helicenes as well as mono- and diaza[6]helicenes is reported. Through the use of both computational and experimental methods, these helically chiral pyridohelicenes with the nitrogen atom(s) in various positions are characterised according to their inversion barriers, protonation constants and redox potentials. By using DFT calculations, kinetic measurements, UV/Vis titrations, cyclic voltammetry and EPR spectroscopy, a self-contained picture of their behaviour under conventional treatment by heat, acids and oxidising/reducing agents is provided.
Domain formation in monolayers
1995
For phospholipids at the air/water interface we demonstrate that molecular chirality in some, but not in all, cases influences the domain shapes. In other cases chirality in the head group region can cause a chiral structure considering the tail arrangement. This indicates head group ordering. Minute changes of the molecular structure may change domain morphology from circular to dendritic. This can be related to slight changes of the lattice structure. In case of a dendritic domain the chains are more tilted, the deviation from hexagonal symmetry is more pronounced, and hence the lattice anisotropy is larger. This can be understood also in view of recent simulations considering diffusion-l…
Amino-Acid-Based Polymerizable Surfactants for the Synthesis of Chiral Nanoparticles
2016
Amino-acid-based chiral surfactants with polymerizable moieties are synthesized, and a versatile approach to prepare particles thereof with a chiral surface functionality is presented. As an example of an application, the synthesized particles are tested for their ability as nucleating agents in the enantioselective crystallization of amino acid conglomerate systems, taking rac-asparagine as a model system. Particles resulting from chiral surfactants with different tail groups are compared and the results demonstrate that only the chiral nanoparticles made of the polymerizable surfactant are able to act efficiently as nucleation agent in enantioselective crystallization.
Prediction of properties of chiral compounds by molecular topology
1998
Abstract A common assumption in chemistry is that chiral behavior is associated with 3-D geometry. However, chiral information is related to symmetry, which allows the topological handling of chiral atoms by weighted graphs and the calculation of new descriptors that give a weight to the corresponding entry in the main diagonal of the topological matrix. In this study, it is demonstrated that, operating in this way, chiral topological indices are obtained that can differentiate the pharmacological activity between pairs of enantiomers. The 50% inhibitory concentration (IC50) values of the D2 dopamine receptor and the σ receptor for a group of 3-hydroxy phenyl piperidines are specifically pr…
Enantioselective transport of amino acid through supported chiral liquid membranes
1993
Abstract Two chiral alcohols, nopol and (2S)-(−)-methyl-1-butanol, immobilized in the pores of a polyethylene film were used for the anantioselective transport of amino acid hydrochloride. The degree of stereoselectivity of the permeation process varied from 0.39 to 1.52 depending on both the type of the chiral membrane phase and the properties of the amino acid. The evaluation of the membrane ability to separate stereoisomers was performed by the step-by-step analysis by considering the effect of amino acids' hydrophobicity, polarity and degree of chirality. For the purpose of this paper, the chirality measure was introduced. It was demonstrated that the enantioselectivity was affected mai…