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PubMed1989

Polarimetric detection in high-performance liquid chromatography.

Chiroptical detection for HPLC is particularly useful as a selective detection method for chiral molecules, and in enantiomeric purity determination with partial chiral separation or without chiral separation. The recent development of laser-based polarimeters with microdegree sensitivity has increased the applicability of optical rotation detection in HPLC. The detection limit of these instruments is submicrogram on-column for many chiral compounds in analytical HPLC. A variety of applications of the selective detection of optically active molecules are reviewed. The use of polarimetric detection with partial chiral separation is considered, both as an aid to method development and for enantiomeric purity determination. Finally applications to enantiomeric purity determination without chiral separation are reviewed, with the dual use of nonchirally selective and chiroptical detectors to determine the total amount and optical purity of the analyte. Determinations of chiral purity for samples of high enantiomeric excess are described, which with laser-based instrumentation may give accuracies of better than +/- 1% with sample loadings of 50 micrograms on an achiral column. Applications to the study of enantioselective reactions are also considered, with determination of enantiomeric excess in near-racemates to better than +/- 0.1%.

Chromatography, High Pressure Liquid↗
PubMed1999

Complex spike activity of Purkinje cells in the ventral uvula and nodulus of pigeons in response to translational optic flow.

The complex spike (CS) activity of Purkinje cells in the ventral uvula and nodulus of the vestibulocerebellum was recorded from anesthetized pigeons in response to translational optic flow. Translational optic flow was produced using a "translator" projector: a mechanical device that projected a translational optic flowfield onto the walls, ceiling, and floor of the room and encompassed the entire binocular visual field. CS activity was broadly tuned but maximally modulated in response to translational optic flow along a "best" axis. Each neuron was assigned a vector representing the direction in which the animal would need to translate to produce the optic flowfield that resulted in maximal excitation. The vector is described with reference to a standard right-handed coordinate system, where the vectors, +x, +y, and +z represent, rightward, upward, and forward translation of the animal, respectively. Neurons could be grouped into four response types based on the vector of maximal excitation. +y neurons were modulated maximally in response to a translational optic flowfield that results from self-motion upward along the vertical (y) axis. -y neurons also responded best to translational optic flow along the vertical axis but showed the opposite direction preference. The two remaining groups responded best to translational optic flow along horizontal axes: -x + z neurons and -x-z neurons. In summary, our results suggest that the olivocerebellar system dedicated to the analysis of translational optic flow is organized according to a reference frame consisting of three approximately orthogonal axes: the vertical axis, and two horizontal axes oriented 45 degrees to either side the midline. Previous research has shown that the rotational optic flow system, the eye muscles, the vestibular semicircular canals and the postural control system all share a similar spatial frame of reference.

Animals↗
PubMed2004

Optical microrheology using rotating laser-trapped particles.

We demonstrate an optical system that can apply and accurately measure the torque exerted by the trapping beam on a rotating birefringent probe particle. This allows the viscosity and surface effects within liquid media to be measured quantitatively on a micron-size scale using a trapped rotating spherical probe particle. We use the system to measure the viscosity inside a prototype cellular structure.

Calcium Carbonate↗
PubMed2006

Calculation of circular dichroism spectra from optical rotatory dispersion, and vice versa, as complementary tools for theoretical studies of optical activity using time-dependent density functional theory.

A comparison of two theoretical methods based on time-dependent density functional theory for the calculation of the linear dispersive and absorptive properties of chiral molecules has been made. For this purpose, a recently proposed computational method for the calculation of circular dichroism (CD) spectra from the imaginary part of the optical rotation parameter has been applied to six rigid organic molecules. The results have been compared to the CD spectra obtained from the rotatory strengths and from the Kramers-Kronig transformation of optical rotatory dispersion (ORD) curves. We have also investigated a criterion based on the Kramers-Kronig integration formula to determine a number of excitations in truncated CD spectra which may yield a reasonable low frequency resonant ORD. It has been tested by calculating the ORD from the sum-over-states formula both in the nonresonant and resonant regions. Finally, we have applied these methods to model the resonant optical activity of proline at low pH.

Circular Dichroism↗
PubMed2000

Methodology for examining polarized light interactions with tissues and tissuelike media in the exact backscattering direction.

The properties of polarized light emerging from turbid media in the exact backscattering direction are studied by modulating the incident light polarization state and isolating the synchronous signal with lock-in amplifier detection. The results are reported for polystyrene microsphere suspensions in distilled water, with and without glucose, and for both ex vivo and in vivo biological tissues. A new theoretical formulation based on Mueller calculus is developed to describe the observed behavior of the backscattered light in terms of two sample parameters: optical rotation and depolarization. This technique proved successful in modeling both phantom and tissue samples. Results showed the presence of a significant surviving polarization fraction in the backscattering direction even in extremely dense optical phantom media, an important finding that has not been observed at other detection angles. Substantial polarized light preservation in biological tissue samples is also demonstrated for this detection geometry. This illustrates the potential of using polarized light to investigate turbid biological materials in vivo in retroreflection geometry.

Female↗
PubMed2006

Theoretical analysis of the terahertz spectrum of the high explosive PETN.

The experimental solid-state terahertz (THz) spectrum (3 to 120 cm(-1)) of the high explosive pentaerythritol tetranitrate (PETN, C(5)H(6)N(4)O(12)) has been modeled using solid-state density functional theory (DFT) calculations. Solid-state DFT, employing the BP density functional, is in best qualitative agreement with the features in the previously reported THz spectrum. The crystal environment of PETN includes numerous intermolecular hydrogen-bonding interactions that contribute to large (up to 80 cm(-1)) calculated shifts in molecular normal-mode positions in the solid state. Comparison of the isolated-molecule and solid-state normal-mode calculations for a series of density functionals reveals the extent to which the inclusion of crystal-packing interactions and the relative motions between molecules are required for correctly reproducing the vibrational structure of solid-state THz spectra. The THz structure below 120 cm(-1) is a combination of both intermolecular (relative rotations and translations) and intramolecular (torsions, large amplitude motions) vibrational motions. Vibrational-mode analyses indicate that the first major feature (67.2 cm(-1)) in the PETN THz spectrum contains all of the optical rotational and translational cell modes and no internal (molecular) vibrational modes.

Journal Article↗
PubMed1994

Covariation of optic disc measurements and ocular parameters in the healthy eye.

To understand the variations in optic disc topography that may affect the local susceptibility of nerve fibers to glaucomatous damage, we evaluated the correlations between optic disc topography and selected ocular parameters in 210 normal eyes of healthy Japanese. In the total study group, eyes with a longer axial length had a longer distance between the disc and foveola, a larger index of ovalness and a larger disc (P < 0.01). A longer disc-foveola distance correlated with a larger index of ovalness (P < 0.01). The optic discs of severely myopic eyes had a considerably different structure from other eyes. Eyes with a tilted optic disc were unique in that the area of the optic disc was not large despite a positive correlation with long axial length (P < 0.01) a long disc-foveola distance (P < 0.01), and a large index of ovalness (P < 0.01). Eyes with a rotated optic disc were another special case. This eye type correlated in a contradictory fashion with two parameters: a large axial length (P < 0.01) and a short disc-foveola distance (P < 0.01). These findings suggest that changes in optic disc topography or susceptibility to glaucomatous damage correlate with selected ocular parameters but are not completely parallel.

Anthropometry↗
PubMed2006

Nonlinear, binocular interactions underlying flow field selectivity of a motion-sensitive neuron.

Neurons in many species have large receptive fields that are selective for specific optic flow fields. Here, we studied the neural mechanisms underlying flow field selectivity in lobula plate tangential cells (LPTCs) of the blowfly. Among these cells, the H2 cell responds preferentially to visual stimuli approximating rotational optic flow. Through double recordings from H2 and many other LPTCs, we characterized a bidirectional commissural pathway that allows visual information to be shared between the hemispheres. This pathway is mediated by axo-axonal electrical coupling of H2 and the horizontal system equatorial (HSE) cell located in the opposite hemisphere. Using single-cell ablations, we found that this pathway is sufficient to allow H2 to amplify and attenuate dendritic input during binocular visual stimuli. This is accomplished through a modulation of H2's membrane potential by input from the contralateral HSE cell, which scales the firing rate of H2 during visual stimulation but is not sufficient to induce action potentials.

Action Potentials↗
PubMed2005

Discrete flexoelectric polarizations and biaxial subphases with periodicities other than three and four layers in chiral smectic liquid crystals frustrated between ferroelectricity and antiferroelectricity.

The subphase for the temperature range that lies in between Sm-C(A)* and the three-layer Sm-C(A)* (1/3)subphase has been confirmed to exist using the measurements of electric-field-induced birefringence, optical rotation, and the characteristic reflection bands in the antiferroelectric liquid-crystalline compound, 1-trifluoromethylundecyl-4-(4'-dodecyloxybiphenyl-4-yl-carbonyloxy)-3-fluorobenzoate (12BIMF10). The measurements of electric-field-induced birefringence and optical rotatory power are made on -thick homeotropic cells, and the characteristic reflection bands are observed in free-standing films of thicknesses ranging from 30 to 50 microm. Several binary mixtures have been prepared by mixing (S)-12BIMF10 with (S)-4-(1-methylheptyloxycarbonyl)-phenyl-4'-octylbiphenyl-4-carboxylate (MHPBC), and the effect of racemization of the compound on the character of the biaxial subphase (other than three and four layers) is also discussed. The results are interpreted in terms of the Emelyanenko-Osipov model [Phys. Rev. E 68, 051703 (2003)]; the effective long-range couplings between the director orientations in separated smectic layers emerge after the minimization of free energy with respect to the total (ordinary spontaneous and discrete flexoelectric) polarizations, lifting the degeneracy and producing the nonplanar structures of the subphases.

Journal Article↗
PubMed1985

Laser scanning phase modulation microscope.

We describe the concept and first implementation of an innovative new instrument for quantitative light microscopy. Currently, it provides selective imaging of optical path differences due to birefringence; with further development, it is also possible to selectively image several optical properties, including refractive path differences, optical rotation, and linear and circular dichroism, all with diffraction-limited resolution. An image consists of a 512 X 512 element array, with each pixel displaying one of 256 grey levels, linearly proportional to the specific optical property being observed. Additionally, conventional brightfield and polarized light microscopy are available, with the accompanying advantages of laser scanning and digital image processing. The microscope consists of three subsystems, representing three distinct technologies. The laser scanning subsystem moves a focused microspot across the specimen; the output of a photodetector is an electric signal corresponding to a scanned image. The image display subsystem digitizes this signal and displays it as an image on a video monitor. When used in conjunction with a phase modulation feedback loop, the image formed is of the specimen's birefringent retardation or other selected optical property. The digitized images are also available for computer enhancement.

Animals↗
PubMed1977

Physicochemical properties of a lipase from Pseudomonas fluorescens.

The molecular weight of traicylglycerol lipase (EC 3.1.1.3) from Pseudomonas fluorescens is estimated to be approx. 33 000 by sodium dodecyl sulfate electrophoresis and Sephadex G-75 gel filtration. The lipase appears to be a single-chain protein and contains neither sugar nor lipid. The enzyme has a sedimentation coefficient (S20,w) of 3.06, an intrinsic viscosity of 3.0 g/ml and a partial specific volume of 0.730 g/ml, with an isoelectric point of pH 4.46. Amino acid analysis showed that the enzyme contained few sulfur-containing amino acid residues with no disulfide links. The N-terminal residue of the enzyme was found to be alanine and optical rotation dispersion analysis showed that about 20% of the enzyme structure was in a helicla configuration.

Amino Acids↗
PubMed1970

Changes in axon birefringence during the action potential.

1. Observations have been made on the changes in optical retardation accompanying the passage of impulses along crab leg nerves and squid giant axons.2. The nerves were mounted on the stage of a polarizing microscope, at 45 degrees to the planes of polarization and analysis, brightly illuminated with white light. During the nerve impulse the intensity of the light passing the analyser decreased temporarily by 1 part in 10(3)-10(6). Signal-averaging techniques were used to obtain an acceptable ratio of signal to noise.3. The changes in light intensity recorded under these conditions were shown to arise almost entirely from alterations in retardation, with little or no interference from scattering, absorption, linear dichroism or optical rotation effects; the occurrence of stimulus and coupling artifacts was also ruled out.4. In the squid giant axon, the retardation change was shown to be located in a thin cylinder immediately surrounding the axoplasm, and to have a radially oriented optic axis.5. The time course of the decrease in optical retardation was very similar to that of the action potential recorded with an intracellular electrode, suggesting that the retardation closely followed the electrical potential across the membrane.

Action Potentials↗
PubMed2006

Representation of behaviourally relevant information by blowfly motion-sensitive visual interneurons requires precise compensatory head movements.

Flying blowflies shift their gaze by saccadic turns of body and head, keeping their gaze basically fixed between saccades. For the head, this results in almost pure translational optic flow between saccades, enabling visual interneurons in the fly motion pathway to extract information about translation of the animal and thereby about the spatial layout of the environment. There are noticeable differences between head and body movements during flight. Head saccades are faster and shorter than body saccades, and the head orientation is more stable between saccades than the body orientation. Here, we analyse the functional importance of these differences by probing visual interneurons of the blowfly motion pathway with optic flow based on either head movements or body movements, as recorded accurately with a magnetic search coil technique. We find that the precise head-body coordination is essential for the visual system to separate the translational from the rotational optic flow. If the head were tightly coupled to the body, the resulting optic flow would not contain the behaviourally important information on translation. Since it is difficult to resolve head orientation in many experimental paradigms, even when employing state-of-the-art digital video techniques, we introduce a 'headifying algorithm', which transforms the time-dependent body orientation in free flight into an estimate of head orientation. We show that application of this algorithm leads to an estimated head orientation between saccades that is sufficiently stable to enable recovering information on translation. The algorithm may therefore be of practical use when head orientation is needed but cannot be measured.

Algorithms↗
PubMed2003

Perception of self-motion from peripheral optokinetic stimulation suppresses visual evoked responses to central stimuli.

In a previous functional neuroimaging study we found that early visual areas deactivated when a rotating optical flow stimulus elicited the illusion of self-motion (vection) compared with when it was perceived as a moving object. Here, we investigated whether electrical cortical responses to an independent central visual probe stimulus change as a function of whether optical flow stimulation in the periphery induces the illusion of self-motion or not. Visual-evoked potentials (VEPs) were obtained in response to pattern-reversals in the central visual field in the presence of a constant peripheral large-field optokinetic stimulus that rotated around the naso-occipital axis and induced intermittent sensations of vection. As control, VEPs were also recorded during a stationary peripheral stimulus and showed no difference than those obtained during optokinetic stimulation. The VEPs during constant peripheral stimulation were then divided into two groups according to the time spans where the subjects reported object- or self-motion, respectively. The N70 VEP component showed a significant amplitude reduction when, due to the peripheral stimulus, subjects experienced self-motion compared to when the peripheral stimulus was perceived as object-motion. This finding supplements and corroborates our recent evidence from functional neuroimaging that early visual cortex deactivates when a visual flow stimulus elicits the illusion of self-motion compared with when the same sensory input is interpreted as object-motion. This dampened responsiveness might reflect a redistribution of sensorial and attentional resources when the monitoring of self-motion relies on a sustained and veridical processing of optic flow and may be compromised by other sources of visual input.

Adult↗
PubMed1977

[Physico-chemical characteristics of the new antitumor antibiotic virenomycin].

Virenomycin, a new crystalline antitumor antibiotic was isolated from the mycelium of Streptomyces virens. The antibiotic contained: C 64.87 per cent, H 5.66 per cent, methoxylic groups 9.5 per cent. The melting temperature was 255-260 degrees (dec.), [alpha]20D=-17 (c 0.142, chloroform). Virenomycin had a complex UV spectrum with lambdamax. 245 (677), 265 (453), 275 (542), 287 (507), 395 (222) nm. A chromofor fragment and carbohydrate (C7H14O5) were found in the methanolysis products. Virenomycin was close to antibiotic c B-21085 BY THe physico-chemical properties and differed from it in the character of the UV spectrum and the values of the specific absorption, as well as by the optic rotation in dimethyl sulphoxide and acetic acid.

Antibiotics, Antineoplastic↗
PubMedDate not supplied

Ternary complexes of palladium (II) with levamisole and L-amino acids.

The complexes of general formula [(LMS)2Pd(amino acid)]Cl with LMS = levamisole, and amino acid = L-alanine, L-phenylglycine, L-phenylalanine, L-valine, L-methionine, and L-proline, were synthesized by the interaction of [(LMS)2PdCl2] with the sodium salts of L-amino acids. The newly synthesized complexes are characterized by elemental analysis, conductivity, magnetic susceptibility, optical rotation measurements, and UV-Vis, IR and 13C NMR spectral data. Levamisole is coordinated to palladium via the N-7 nitrogen and the amino acids through the amino nitrogen and carboxylate oxygen, except for L-methionine which binds the metal via nitrogen and sulfur atoms. Optically active [(LMS)2Pd(amino acid)]Cl complexes are obtained when L-amino acids or D,L-amino acids are used for the synthesis of these complexes. L-Methionine and L-proline complexes induce new cell forms in Baker's yeast (Saccharomyces cerevisiae) cells.

Adjuvants, Immunologic↗
PubMed1999

Stereo-specific cytotoxic effects of gossypol enantiomers and gossypolone in tumour cell lines.

The naturally occurring compound, gossypol, has been previously used as a male oral contraceptive, for the treatment of benign gynaecological conditions and cancer patients. Long-term daily dosing with gossypol is associated with minimal side effects and no myelosuppression. Since gossypol exhibits atropisomerism due to the restricted rotation about the 2,2' carbon bond, we have isolated the l- and d-isomers by Schiff's base formation using a chiral amine and regenerated the enantiomers by acid hydrolysis. The enantiomers and the proposed oxidative metabolite, gossypolone, were characterized by HPLC, 1H-NMR and optical rotation. The cytotoxicity was assessed in cell cultures derived from melanoma, lung, breast, cervix, and leukaemia using the MTT viability assay. The cytotoxicity of gossypolone was similar to racemic gossypol in five out of the six cell lines studied. The l-enantiomer of gossypol induced a dose-dependent cell kill in all cell lines with a mean IC50 of 20 microM and was significantly more potent than racemic gossypol, the d-enantiomer of gossypol and gossypolone. In addition, when the leukaemia line was exposed to l-gossypol (0.5-10 microM) over a 4-day period, a schedule-dependent decrease in cell viability was observed. l-Gossypol was also compared with respective drugs used to treat patients with melanoma, lung cancer and leukaemia. The data indicate that l-gossypol was significantly more active than cisplatin, melphalan and dacarbazine in the two melanoma lines, cisplatin and daunorubicin in the lung line and hydroxyurea and busulphan in the leukaemia line. Preliminary studies using one melanoma line showed that the l-isomer induced cell shrinkage, membrane blebbing and DNA fragmentation, characteristics suggestive of apoptotic cell death.

Antineoplastic Agents↗
PubMedDate not supplied

Imaging polarimetry for high throughput chiral screening.

Imaging polarimetry was demonstrated as a highly parallel method of determining optical rotation of biochemical samples. The imaging polarimeter utilized a bright, uniform light source wavelength-filtered to near the sodium D line, a sample array flanked by inlet and analyzing polarizers, and a CCD camera fitted with an equal-perspective telecentric lens. The prototype apparatus was demonstrated to have an optical resolution better than 0.08 degrees. The potential for high throughput screening was demonstrated by imaging chiral solutions in 1536-well microtiter plates and by real-time monitoring of 30 simultaneous chiral enzymatic reactions. Improvements in polarizer and CCD technology may broadly expand the technique's applicability to fields such as directed evolution and combinatorial chemistry, where screening throughput is currently limiting for chiral applications.

Algorithms↗