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At least 19 recordsLinked to original sources
PubMed2006

Rotationally resolved optical rotation and circular dichroism effects for symmetric top molecules induced by a resonant circularly polarized pumping optical field.

The rotationally resolved laser-induced optical activity including the laser-induced optical rotation (LIOR) and laser-induced circular dichroism (LICD) effects of an IR probing light pumped by a collinear intense resonant circularly polarized light dependent on the third-order susceptibility due to the pure electric dipole interaction for achiral symmetric top molecules in the gas phase is discussed theoretically. The laser-induced optical activity contains four distinct contributions named A, B, C, and D terms: the B term of the LIOR and LICD arising from the rotational wave function perturbed by the pumping light is deduced using the semiclassical perturbation theory, and the expressions for A, C, and D terms, respectively, due to the ac Stark effect, the Boltzmann statistical redistribution, and the alteration of occupation polability, are obtained from previous results [Zheng, R.-H.; Chen, D.-M.; Wei, W.-M.; He, T.-J.; Liu, F.-C. J. Chem. Phys. 2004, 121, 6835]. The microwave-IR double resonant spectrum is proposed to detect the LIOR and LICD effects. As an example, the LIOR and LICD for the HCF(3) molecules in the conditions of 298.15 K and 0.3 Torr when the IR probing light sweeps over the rotational-vibrational transition of the v(5) and v(1) modes and the right circularly polarized microwave pumping light with the intensity of 1 kW cm(-2) at the resonant frequency 40.84 GHz are calculated on the basis of the B3LYP/6-311++G* computations. The theoretical results indicate that the B term can be of the same order of magnitude as the A and D terms, and the LIOR and LICD can be measurable in comparison to the rotationally resolved MVCD. The laser-induced optical activity may provide useful new information and form a basis for a different kind of optical activity spectroscopy.

Circular Dichroism↗
PubMed1997

The optical rotator.

The optical rotator is an unbiased, local stereological principle for estimation of cell volume and cell surface area in thick, transparent slabs. The underlying principle was first described in 1993 by Kiêu & Jensen (J. Microsc. 170, 45-51) who also derived an estimator of length. In this study we further discuss the methods derived from this principle and present two new local volume estimators. The optical rotator benefits from information obtained in all three dimensions in thick sections but avoids over-/ underprojection problems at the extremes of the cell. Using computer-assisted microscopes the extra measurements demand minimal extra effort and make this estimator even more efficient when it comes to estimation of individual cell size than many of the previous local estimators. We demonstrate the principle of the optical rotator in an example (the cells in the dorsal root ganglion of the rat), evaluate its efficiency and compare it with other unbiased, local stereological principles available for estimation of cell volume and surface area.

Animals↗
PubMed2002

Low-loss ultrabroadband 90 degree optical rotator with collinear input and output beams.

An achromatic device to rotate optical polarization by 90 degrees is described. This is based on a series of reflecting surfaces that rotates incoming light about the optical axis and translates it such that the exiting light is collinear. Polarization rotation is achieved by rotation of the optical beam, as opposed to the more common approach of phase retardation by use of birefringent elements. For broadband operation from the UV to the near infrared, the device was constructed by use of total internal reflection in three fused-silica glass components. Losses are minimized with interstitial surfaces designed to be angled close to Brewster's angle.

Journal Article↗
PubMed1989

[An empirical correlation between optical rotation and absolute configuration of optically active alpha-methylbutyrylphloroglucinols and its synthesis].

Fourteen new compounds were synthesized of which twelve are (S)-(+)-alpha-methylbutyrylphloroglucinols. On the basis of optical rotation data and theoretical analysis, an empirical correlation between optical rotation and absolute configuration of optically active alpha-methylbutyrylphloroglucinols has been established by means of Brewster's rule of atomic asymmetry. It can be served as a means of absolute configuration assignment of optically active alpha-methylbutyrylphloroglucinols.

Molecular Conformation↗
PubMed2006

Specific anion effects on the optical rotation of glucose and serine.

Optical activity is directly related to molecular conformation through the anisotropic polarizabilities of molecules and the refractive index of materials. L-amino acids and D-sugars are characteristic essential bioactive molecules. Since molecular recognition and enzyme activity are related to the conformation of substrates, the relevance of optical activity to biological processes is evident. Specific ion, or Hofmeister, effects that occur with electrolytes at moderately high concentrations modify the behavior of interfaces, molecular forces between membranes, of bulk solutions, of enzymes, and even of DNA. Such effects are universal. Here we report a study on the change in optical rotation induced by some sodium salts for the enantiomers of serine and glucose in water solution. The optical rotation is shown to depend on the kind of anion and on the salt concentration. To obtain further insights into the mechanism behind the phenomenon, Fourier transform infrared (FTIR) spectral studies of serine and glucose solutions in electrolytes were also carried out. The results suggest that it is the differences in interactions of anions at specific chemical sites of the solutes that are responsible for the effects. These forces depend strongly on anion polarizability in water. Such specific ion preferential interactions can affect conformation and internal field, and result in significant changes in optical rotation.

Anions↗
PubMed2006

Ab initio calculations of nonlinear optical rotation by several small chiral molecules and by uridine stereoisomers.

Expressions for nonlinear optical rotation are presented based on the quantum theory of optical birefringence of Atkins and Barron [Proc. R. Soc. London, Ser. A 304, 303 (1968); 306, 119 (1968)]. As concrete examples, the ordinary and nonlinear optical rotations are calculated with density functional theory (DFT) methodology for some simple single-ring molecules, namely, oxaziridine, diaziridine, and their derivatives, and for two, somewhat more complicated, conformations of uridine. For the single-ring molecules, (1) the angles of the ordinary optical rotation are mostly positive and (2) the contributions of the nonlinear effect to the total optical rotation depend both on the nature of the substituted species and of the host atom located on the ring. For the two conformations of uridine, (1) the signs of nonlinear optical rotation differ even though their ordinary optical rotations have the same sign and (2) whether the molecular structures are geometrically optimized with Hartree-Fock or DFT methodologies has no significant effect on the calculated nonlinear optical rotation when gauge-including atomic orbitals were used, even though the basis sets are small. These studies are expected to be helpful for interpretation of experimental results on nonlinear optical rotation by molecules underway in our research group.

Journal Article↗
PubMed2006

Protocols for the analysis of theoretical optical rotations.

The availability of sophisticated quantum mechanical methods for predicting molecular optical rotations has revolutionized the determination of molecular stereochemistry. However, the objectives and approaches used for the applications of optical rotation vary from one laboratory to the other. With the number of applications of optical rotation increasing at an unprecedented rate, it is considered necessary to discuss the protocols for the general use of optical rotations predicted with quantum mechanical methods. A summary of the quantum mechanical methods for predicting optical rotations and protocols for the use of predicted optical rotations are presented in this article.

Journal Article↗
PubMed2005

Ab initio calculation of optical rotation in (P)-(+)-[4]triangulane.

Optical rotation, the angle through which plane-polarized light rotates when passed through an enantiomerically pure medium, plays a vital role in the determination of the absolute configurations of chiral molecules such as natural products. We describe new quantum mechanical methodology designed to assist in this endeavor by providing high-accuracy computational optical rotatory dispersion data for matching to experimental results. Comparison between theory and experiment for the rigid, helical molecule trispiro[2.0.0.2.1.1]nonane [also known as (P)-(+)-[4]triangulane], recently synthesized with enantiomeric purity, shows that the coupled cluster quantum chemical model provides superb agreement for optical rotation across a wide range of wavelengths (589-365 nm), with errors averaging only 1%.

Journal Article↗
PubMed2001

Optical rotation and structure of ferrielectric smectic phases.

We analyze the measured optical rotation in three- and four-layer smectic ferrielectric phases within the matrix approach to the light propagation. We show that "perfect" three- and four-layer structures with 120 degrees and 90 degrees phase rotation of the director in neighboring layers give negligible optical rotation of polarized light travelling along the normal to the smectic layers. Significant optical rotation is obtained in deformed three- and four-layer smectic phases. The analysis of the measured optical rotatory power clearly shows that three-layer ferrielectric phases of [4-(1-methylheptyloxycarbonylphenyl)-octylbiphenyl-4-carboxylate] and 4-[(4-[[1(*)-methyl]heptycarboxy]phenyl)carboxy]phenyl-4'-decyloxy-1-benzencarbatioate (10OTBBB1M7) are deformed with the deformation angle of 35 degrees-45 degrees. The deformation angle in the four-layer smectic phase of 10OTBBB1M7 is 70 degrees-90 degrees. This is in reasonable agreement with other experiments and suggests the validity of the "deformed clock model."

Journal Article↗
PubMed2003

Conformational effects on optical rotation. 3-substituted 1-butenes.

A calculation of the optical rotation of (R)-(-)-3-chloro-1-butene found a remarkably large dependence on the C=C-C-C torsional angle. At tau = 0 degrees, [alpha](D) = +244 degrees, whereas at tau = 180 degrees, [alpha](D) = -526 degrees. The effect of conformation on the optical rotation was confirmed by a study of the temperature dependence of the rotation. An analysis of the data gave the difference in free energy between the low- and high-energy conformers as 1315 cal/mol and gave the optical rotation of the low-energy conformer and the average of the rotations of the higher energy forms. Although a large effect was found, the observed rotations are a factor of 2.6 smaller than the calculated values, independent of both conformation and wavelength from 589 to 365 nm. The effect of replacing Cl with F, CN, and CCH was examined theoretically. The effects of substituents are remarkably small despite large changes in the calculated electronic transition energies.

Journal Article↗
PubMed2006

Solvent effects on the optical rotation of (S)-(-)-alpha-methylbenzylamine.

The optical rotation of (S)-(-)-alpha-methylbenzylamine at 589 nm has been measured in 39 different solvents at five different concentrations: 0.25, 0.50, 1.00, 2.00, and 3.00 M. A correlation of the intrinsic rotations (i.e., extrapolation of specific rotations to zero concentration) with Kamlet's and Taft's solvent parameters (alpha, beta, and pi) is established. The polarity/polarizability, pi, and solvent acidity, alpha, terms are found to have a greater effect upon the optical rotation than the basicity of the solvent, beta. The specific rotation for (S)-(-)-alpha-methylbenzylamine has been calculated with Gaussian03 using a PCM model (B3LYP aug-cc-pVDZ) for all 39 solvated systems. Comparisons between the experimental and calculated values show the importance of hydrogen bonding on specific rotation.

Journal Article↗
PubMed2005

Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations.

In this study, we report theoretical specific rotation values for a series of cis-/trans-alkylated-[5]-ladderanes and cis-/trans-methylated-[n]-ladderanes. Using time-dependent density functional response theory optical rotation calculations, we can assign (+) and (-) optical rotation signs to trans-(S)-alkyl-[5]-ladderane and trans-(R)-alkyl-[5]-ladderane configurations, respectively. In order to qualitatively validate our absolute configuration predictions, we computed optical rotation values at three different levels of theory--B3LYP, RI-BP86, and Hartree-Fock--using the aug-cc-pVDZ basis set. We observe a novel rung-parity-controlled oscillatory optical rotatory phenomenon in our computations, which, to the best of our knowledge, has never been reported or observed before. Furthermore, this preliminary analysis of optical rotation properties in this class of compounds should facilitate the correct absolute stereochemical assignment of natural and synthetic ladderanes, such as the trans-isomer of pentacyclic C(20)-fatty acid methyl ester (pentacycloanammoxic methyl ester), without the need for derivatization, in particular for cases where NMR or X-ray crystal structures are not readily available.

Mathematics↗
PubMed1998

Optical rotation signals recorded from a single skeletal muscle fibre of a frog.

The optical rotation signal of a single frog skeletal muscle fibre was recorded and its properties were examined. To reduce movement of the fibre associated with its excitation, fibre was immersed in Ringer solution made of 90-95% D2O, stretched, and lightly pressed from above with a cylindrical lens. After these procedures no mechanical movements were recognizable under the dissection microscope, and the optical rotation signal appeared consistently as a brief transient increase in dextrorotation with a duration of about 23 ms. The shape and polarity of the signal did not change among preparations and remained unchanged when the direction of impulse conduction along the fibre was reversed. The influence of the birefringence change associated with excitation was found to be small in most preparations. Ryanodine (10 micron) reduced the amplitude of the signal to about half that of the control, and increased the duration slightly. Nitrendipine (10 micron) reduced the duration of the signal to about half that of the control, and reduced the amplitude to about two-thirds of the control. The effects of the chemicals took place within 10 minutes and remained constant for the periods examined. The intracellular action potentials were not appreciably altered by these chemicals. It is concluded that the optical rotation signal of the single muscle fibre reports the molecular conformational change of proteins during the early stage of the contraction process.

Animals↗
PubMed1955

Optical rotation and helical polypeptide chain configuration in collagen and gelatin.

The optical rotation phenomena exhibited by a citrate-extracted fraction of ichthyocol (from carp swim bladder), as well as by the parent gelatin derived therefrom, have been studied. Dispersion data for all cases follow a single-term Drude equation, but the variations with state are adequately expressed by simple reference to changes in [alpha](D) as follows:- 1. The native collagen fraction, dispersed in 0.15 M citrate buffer at pH 3.7 in the cold (11 degrees C.), yields a high negative specific rotation, [alpha](D), near -350 degrees . 2. During equilibration at 40 degrees C., which causes conversion to a monodisperse parent gelatin, the rotation drops to about -110 degrees . 3. Gelation at 2 degrees C. results in a partial regain of rotation to around -290 degrees . This mutarotation is reversible, depending on temperature. 4. In the range 0.02 to 0.28 per cent the native ichthyocol and the warm gelatin solutions show little concentration dependence, but with the cold gelatin solutions the specific rotation increases with concentration. Gelatin films formed by cold evaporation yield high specific rotation (ca. -620 degrees ), but those formed by hot evaporation retain low optical activity. 5. Since this same collagen-gelatin system has been investigated physicochemically, it is possible to relate molecular changes to the observed variations in optical rotation. Conclusions are similar to those of Robinson (1953), who studied other gelatins: high negative rotation is believed related to a native collagen polypeptide configuration, herein specified as helical (from x-ray diffraction considerations) and destroyed by heating. The possible roles of intermolecular interactions and of prevalent pyrrolidine constituents in influencing the helical configuration and optical activity are discussed.

Collagen↗
PubMed2004

Density functional study of the optical rotation of glucose in aqueous solution.

Optical rotation values were calculated for the eight most abundant structures of glucose in aqueous solution, following the TD-DFT/GIAO approach for the property and the PCM description for the solvent. The results show that all alpha structures give a large positive contribution to the OR property, while the beta structures give both positive and negative contributions. The good agreement of the calculated OR, obtained as a Boltzmann average of the property of the eight conformers, with experimental data proves the validity of the quantum-mechanical approach and of the solvent modelization.

Glucose↗
PubMed2005

Magnitude of zero-point vibrational corrections to optical rotation in rigid organic molecules: a time-dependent density functional study.

The zero-point vibrational corrections (ZPVCs) to the optical rotation of 22 rigid organic molecules have been calculated using time-dependent density functional theory with the B3LYP hybrid functional. We outline an implementation for calculating ZPVCs that can be applied with a variety of quantum chemistry programs and methods. It is shown that the ZPVCs to optical rotation have a wide range of values and can be quite significant depending on the molecule. On average, it has been determined that vibrational corrections can account for about 20% of the optical rotation for the equilibrium value. It is also concluded that vibrational effects alone cannot be the only factor in improving the calculated values of optical rotation with respect to experimental data measured in solution.

Journal Article↗
PubMed1998

Atomic contributions to the optical rotation angle as a quantitative probe of molecular chirality.

Chiral molecules are characterized by a specific rotation angle, the angle through which plane-polarized light is rotated on passing through an enantiomerically enriched solution. Recent developments in methodology allow computation of both the sign and the magnitude of these rotation angles. However, a general strategy for assigning the individual contributions that atoms and functional groups make to the optical rotation angle and, more generally, to the molecular chirality has remained elusive. Here, a method to determine the atomic contributions to the optical rotation angle is reported. This approach links chemical structure with optical rotation angle and provides a quantitative measure of molecular asymmetry propagation from a center, axis, or plane of chirality.

Bridged Bicyclo Compounds, Heterocyclic↗
PubMed1992

[Determination of the protonation constants of pipecuronium bromide on the basis of optical rotation as a function of pH values].

Pipecuronium bromide molecule contains two slightly basic nitrogen atoms in its two piperazine rings. Their pK values are quite similar to each other in consequence of their almost equivalent surroundings. Although the potentiometric titration used mostly for determination of pK values of organic compounds can be performed in this case too, but the polarimetric titration applied by us is more advantageous. Change of pH considerably influences the values of optical rotation; consequently, the curve obtained in this way is more utilizable than that of potentiometric titration. Protonation of two nitrogen atoms one after the other changes the optical rotation of the molecule in opposite direction. Consequently, a minimum can be seen on the curve of optical rotation versus pH value. The exact pK values were determined on the basis of the estimated parameters of a curve established corresponding to an equation and fitted to the measuring points. The sequence of deprotonation of nitrogen atoms could only be ascertained on the basis of the curves of polarimetric titration of compounds containing one piperazine ring; on the basis of the pK values and of the changing direction of optical rotation.

Androstane-3,17-diol↗