Search results for "Optical Rotation"
showing 10 items of 24 documents
Absolute Chiral Sensing in Dielectric Metasurfaces Using Signal Reversals.
2020
Sensing molecular chirality at the nanoscale has been a long-standing challenge due to the inherently weak nature of chiroptical signals, and nanophotonic approaches have proven fruitful in accessing these signals. However, in most cases, absolute chiral sensing of the total chiral refractive index has not been possible, while the strong inherent signals from the nanostructures themselves obscure the weak chiroptical signals. Here, we propose a dielectric metamaterial system that overcomes these limitations and allows for absolute measurements of the total chirality, and the possibility for a crucial signal reversal that enables chirality measurements without the need for sample removal. As…
Synthetic transformation of hydroxymatairesinol from Norway spruce (Picea abies) to 7-hydroxysecoisolariciresinol, (+)-lariciresinol and (+)-cyclolar…
2003
We have developed a method for the transformation of hydroxymatairesinol to optically pure (+)-lariciresinol and (+)-cyclolariciresinol via the hitherto unreported lignan 7-hydroxysecoisolariciresinol. The two naturally occurring isomers of hydroxymatairesinol were reduced with LiAlH4 to a mixture of two epimers of 7-hydroxysecoisolariciresinol, which were further selectively transformed to (+)-lariciresinol and (+)-cyclolariciresinol by an acid catalysed intramolecular cyclisation reaction. The structure of the major isomer of 7-hydroxysecoisolariciresinol was confirmed by X-ray crystallography and thereby also the absolute configurations of the two isomers of hydroxymatairesinol were unam…
A Dendrimer Chiroptical Switch Based on the Reversible Intramolecular Photoreaction of Anthracene and Benzene Rings
2010
A series of Fréchet-type dendrimers with 9-benzyloxymethylanthracene cores were synthesized and characterized. The chiral source for the dendrimers was an (S)-2-methyl-1-butoxy group in the 3-position of the benzene ring. Irradiation at 366 nm of a dilute benzene solution led to the formation of two diastereomers (1:1) through a quantitative intramolecular [4pi+4pi] cycloaddition between the central anthracene ring and the neighboring benzene ring. The process can be reversed with 254 nm UV light or heat. The benzene rings in the dendrons work as a light-harvesting system. The optical rotation values measured for the reversible process showed fatigue resistance. Thus, a promising new type o…
Conservation of optical purity of amino acids: a principal problem in biochemical and proto-biochemical systems.
1981
Dor L-amino acids, regardless of their state (peptide-bound or free, in the solid state or in aqueous solution), tend to racemize. In a living cell this racemization is usually compensated by specific degradation and replacement of the unwanted polypeptides that contain the wrong enantiomers. But a few long-lived proteins that are synthesized at or near birth are never replaced. Well investigated is the racemization of L-aspartic acid at a rate of 0.1 to 1.14 per cent per year in proteins from lenses and dentine. Increased racemization of eye lens proteins has been related to a form of human eye disease known as brunescent cataracts. Also quite well investigated is the racemization of amino…
Molecule non-radiative coupling to a metallic nanosphere: an optical theorem treatment.
2009
The non-radiative coupling of a molecule to a metallic spherical particle is approximated by a sum involving particle quasistatic polarizabilities. We demonstrate that energy transfer from molecule to particle satisfies the optical theorem if size effects corrections are properly introduced into the quasistatic polarizabilities. We hope that this simplified model gives valuable information on the coupling mechanism between molecule and metallic nanos-tructures available for, e.g., surface enhanced spectroscopy signal analysis.
Light-induced polarization effects in atoms with partially resolved hyperfine structure and applications to absorption, fluorescence, and nonlinear m…
2009
The creation and detection of atomic polarization is examined theoretically, through the study of basic optical-pumping mechanisms and absorption and fluorescence measurements, and the dependence of these processes on the size of ground- and excited-state hyperfine splittings is determined. The consequences of this dependence are studied in more detail for the case of nonlinear magneto-optical rotation in the Faraday geometry (an effect requiring the creation and detection of rank-two polarization in the ground state) with alkali atoms. Analytic formulas for the optical rotation signal under various experimental conditions are presented.
Surface Plasmon Platform for Angle-Resolved Chiral Sensing
2019
Chiral sensitive techniques have been used to probe the fundamental symmetries of the universe, study biomolecular structures, and even develop safe drugs. As chiral signals are inherently weak and...
Origin invariant calculation of optical rotation without recourse to London orbitals
2004
We propose an inherently origin invariant formulation of specific optical rotation obtained from the conventional velocity gauge expression by subtracting the static limit from the electric dipole-magnetic dipole polarizability: ããpâ,LâããÏâããpâ,LâããÏ-ããpâ,Lâãã0. London (gauge including) atomic orbitals are therefore not needed to ensure origin invariance and, consequently, this modified velocity gauge formulation may be employed in conjunction with variational and non-variational quantum chemical methods alike. Sample calculations on S-propylene oxide and 3,4- methylenedioxymethamphetamine using self-consistent field and coupled cluster wave functions…
Twist angle determination in liquid crystal displays by location of local adiabatic points
1998
In this work we present a method for the determination of the twist angle of an arbitrary twisted nematic liquid crystal spatial light modulator. The method is based on the location of local adiabatic points, i.e., situations in which the liquid crystal SLM acts only as a rotation device. For these cases, the rotation induced on the polarization of the incident beam is equal to the twist angle. Consequently, the twist angle can be determined with high precision. We show that local adiabatic regime may be achieved in two ways, either by changing the incident beam wavelength, or by applying a voltage to the electrodes of the display. However, the simple model that describes the SLM in the off…
Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using cholesky dec…
2004
A new implementation of the approximate coupled cluster singles and doubles CC2 linear response model using Cholesky decomposition of the two-electron integrals is presented. Significantly reducing storage demands and computational effort without sacrificing accuracy compared to the conventional model, the algorithm is well suited for large-scale applications. Extensive basis set convergence studies are presented for the static and frequency-dependent electric dipole polarizability of benzene and C60, and for the optical rotation of CNOFH2 and (−)-trans-cyclooctene (TCO). The origin-dependence of the optical rotation is calculated and shown to persist for CC2 even at basis set convergence. …