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Fragmentation and modification of iota-carrageenan and characterisation of the polysaccharide order-disorder transition in solution.

A procedure is described in detail by which the algal polysaccharide, iota-carrageenan, can be modified and fragmented to products of more regular structure and shorter chain length. Since most chains of this product can form uninterrupted helices they undergo the disorder-order transition without the gelation that is a feature of the behaviour of the natural polymer. The disorder-order transition becomes much sharper and occurs at higher temperatures with increasing chain length. The sign and magnitude of the accompanying shift in optical rotation can be estimated satisfactorily from the solid-state geometry of the helix using our semi-empirical method for correlating optical rotation with the conformations at glycosidic linkages. In solutions of the helical form, but not the coil form, cationic dyes such as methylene blue or acridine orange show induced optical activity and a changed visible spectrum which we attribute to binding and stacking on the helix. This also causes a shift in the temperature of the helix-coil transition. We discuss the possibility that the tendency of dyes to stack could drive polysaccharides into conformations that they would not otherwise adopt, with implications for their use as 'conformational probes'.

Carrageenan↗

Paired-angle-rotation scanning optical coherence tomography forward-imaging probe.

We report a novel forward-imaging optical coherence tomography (OCT), needle-probe paired-angle-rotation scanning OCT (PARS-OCT) probe. The probe uses two rotating angled gradient-index lenses to scan the output OCT probe beam over a wide angular arc (approximately 19 degrees half-angle) of the region forward of the probe. Among other advantages, this probe design is readily amenable to miniaturization and is capable of a variety of scan modes, including volumetric scans. To demonstrate the advantages of the probe design, we have constructed a prototype probe with an outer diameter of 1.65 mm and employed it to acquire four OCT images, with a 45 degrees angle between adjacent images, of the gill structure of a Xenopus laevis tadpole. The system sensitivity was measured to be 93 dB by using the prototype probe with an illumination power of 450 microW on the sample. Moreover, the axial and the lateral resolutions of the probe are 9.3 and 10.3-12.5 microm, respectively.

Computer-Aided Design↗

Isolation and characterization of a new bacterium capable of biotransforming cis -epoxysuccinic acid to D(-) -tartaric acid.

A bacterial strain 1-3 capable of enantioselectively hydrolyzing cis-epoxysuccinic acid to D(-)-tartaric acid was isolated from soil. Phenotypic characteristics, Biolog GN test and phylogenetic analysis of strain 1-3 indicated that it belongs to the genus Bordetella. cis-Epoxysuccinic acid could be used as a carbon source and inducer for production of cis-epoxysuccinic acid hydrolase. After the purification of the enzymatic biotransformed product, a colorless and scentless crystal was obtained, which was confirmed to be the tartaric acid with laevorotatory optical rotation by the (1)H nuclear magnetic resonance spectrum and optical rotation analysis.

Bacterial Proteins↗

Inverse scattering for rotationally scanned optical coherence tomography.

Optical coherence tomography of luminal structures, such as for intravascular or gastrointestinal imaging, is performed by using a fiber-optic catheter as a beam-delivery probe. The interrogating beam is scanned angularly by rotating the fiber around a fixed central axis. Because the beam is focused only at a fixed distance from the center of the fiber, only scatterers near this distance are resolved. We present a solution of the inverse scattering problem that provides an estimate of the susceptibility of the sample for an angularly scanned Gaussian beam focused at a fixed distance from the origin. This solution provides quantitatively meaningful reconstructions while also extending the volume of the sample that is resolvable by the instrument.

Algorithms↗

Time dependent density functional theory modeling of specific rotation and optical rotatory dispersion of the aromatic amino acids in solution.

Time Dependent Density Functional Theory (TDDFT) along with the COnductor-like Screening MOdel (COSMO) has been applied to model the specific rotation at 589.3 nm and the optical rotatory dispersion (ORD) of the aromatic amino acids phenylalanine, tyrosine, histidine, and tryptophan. Solution structures at low, neutral, and high pH were determined. Both the anomalous dispersion absorbing (resonance) region and the lower energy (transparent) region of the ORD of the compounds were modeled. Linear response calculation of the specific rotation and ORD as well as Kramers-Kronig transformations of calculated circular dichroism spectra to model resonant ORD were compared with experimental data from the literature.

Amino Acids, Aromatic↗

Tryptophanyl-tRNA synthetase from beef pancreas. Spectroscopic analysis of the stoichiometry of formation of the enzyme-tryptophanyl-adenylate complex.

The dimeric enzyme tryptophanyl-tRNA synthetase from beef pancreas catalyses the stoichiometric formation of one mole of tryptophanyl-adenylate per subunit. This formation is associated with optical changes (absorbance, fluorescence, optical rotation) and is confirmed by analytical ultracentrifugation. An equal amplitude of the change is observed for each adenylation site at pH 8.0, 25 degrees C, regardless of the optical method used. The formation of two tryptophanyl adenylates per dimer corresponds to a molar absorbance change delta epsilon 291 = 12000 +/- 500 cm-1 M-1, to a fluorescence quenching of 24 per cent at 340 nm and to a variation in optical rotation of 6 per cent at 313 nm. The circular dichroic band of the adenosine moiety of ATP is strongly increased. The addition of sodium pyrophosphate to the tryptophanyl-adenylate-enzyme complex restores the absorbance and fluorescence amplitude observed prior to the addition of ATP to the enzyme. Magnesium ions are necessary to the reaction. A pertubation of the environment of both the protein and the substrates (tryptophan and ATP) have to be taken into account to explain the magnitude of the observed changes.

Adenosine Triphosphate↗

Structural studies of the carbohydrate moieties of lectins from potato (Solanum tuberosum) tubers and thorn-apple (Datura stramonium) seeds.

1. Methylation analysis of potato (Solanum tuberosum) lectin and thorn-apple (Datura stramonium) lectin confirmed previous conclusions that both glycoproteins contained high proportions of l-arabinofuranosides and lesser amounts of d-galactopyranosides. The arabinofuranosides are present in both lectins as short unbranched chains containing 1-->2- and 1-->3-linkages, which are known to be linked to hydroxyproline. Galactopyranosides are present as monosaccharides, which are known to be attached to serine, in potato lectin and as both the monosaccharide and the 1-->3-linked disaccharide in Datura lectin. 2. Alkaline digestion of potato lectin and subsequent separation of the components by gel filtration led to the isolation of four fractions corresponding to the mono-, di-, tri- and tetra-arabinosides of hydroxyproline. The latter two fractions accounted for over 70% of the total hydroxyproline. 3. Methylation analysis was used to show that the triarabinoside contained only 1-->2-linkages between sugars, but that the tetra-arabinoside contained both 1-->2- and 1-->3-linkages. Direct-insertion mass spectrometry of these compounds using electron impact and chemical ionization, in a comparison with other known structural patterns, was used to determine the sequences of the sugars, which were Araf1-->2Araf1-->2Araf1-->Hyp and Araf1-->3Araf1-->2Araf1-->2Araf 1-->Hyp. 4. On the basis of optical rotation it had previously been suggested [Allen, Desai, Neuberger & Creeth (1978) Biochem. J.171, 665-674] that all the arabinose of potato lectin was present as the beta-l-furanoside. However, measurement of the optical rotations of the hydroxyprolyl arabinosides showed that whereas the diarabinoside had a molar rotation ([m]) value close to that predicted, the triarabinoside was more dextrorotatory and the tetra-arabinoside was less dextrorotatory than expected. Possible explanations for these findings are that, although the di- and tri-arabinosides contain exclusively beta-arabinofuranosides, in the tri-arabinoside, interactions between pentose units lead to an enhanced positive rotation. The tetra-arabinoside, however, is proposed to contain a single alpha-arabinofuranoside residue, which is responsible for the lower than expected positive rotation. The observed rotation of the tetra-arabinoside was found to be close to the theoretical value predicted on that basis. Furthermore, the action of a specific alpha-arabinofuranosidase on the tetrasaccharide was to remove a single arabinose residue, presumably the terminal non-reducing sugar, and to produce a product that was indistinguishable on electrophoresis from the triarabinoside. Changes in rotation were compatible with this assumption. 5. It is concluded that the structures of the hydroxyprolyl tri- and tetra-arabinosides of potato lectin are: betaAraf1-->2betaAraf1-->2betaAraf1-->Hyp and alphaAraf1-->3betaAraf1-->2betaAraf 1-->2betaAraf1-->Hyp. These are identical with compounds that have been isolated from the insoluble hydroxyproline-rich glycoproteins of plant cell walls.

Amino Acids↗

Multi-beam polarized photometric detector for high-performance liquid chromatography.

A novel multi-beam polarized photometric detector (PPD) for high-performance liquid chromatography (HPLC) is described. By pairing a polarizing prism with a thin quartz plate as a retarder, many linear polarized beams are produced at every 1/2 wavelength of the plate, and the polarizing axes of the adjacent beams intersect each other. The addition of another prism inclining its polarizing axis by pi/4 against the first one enables the simultaneous measurement of optical rotations based on the PPD at many wavelengths. The combination of these optics with a photo-diode array detector can be used to construct a modulated type polarimeter. This detector is designed to measure the optical rotation of an analyte at its absorption band. The spline function connecting the points at 1/4 wavelengths of the plate was used as a baseline to extract the PPD waves. The use of the similarity factor as a noise filter gave high sensitivity. Application of the proposed technique to an analyte carrying the Cotton absorption band provided good results.

Chromatography, High Pressure Liquid↗

Some aspects about the structure of the optically isotropic phase in a bent-core liquid crystal: chiral, polar, or steric origin.

We have studied a bent-core liquid crystal where two different optically isotropic phases can be induced by a strong electric field. Depending on the field treatment the phases can present optical rotation or be optically inactive. The switching dynamics of the phases is studied by means of electrooptic and optical second-harmonic generation measurements. It is found that the ground state of the phases is locally antiferroelectric. The structure of the phases is consistent with a disordered version of the kind of structures recently proposed for the smectic blue phase: layered systems with high Gaussian curvature. The origin of the smectic layer distortion is discussed. It is concluded that the direct reason for the curvature of planes is of steric nature.

Journal Article↗

Optical properties of an isotrophic optically active medium at oblique incidence.

The optical properties of an isotropic optically active medium at oblique incidence have been investigated. It was found that the amount of transmitted light converted from p polarization to s polarization and vice versa, through an isotropic optically active medium, is independent of the state of incident polarization. Though the optical rotation through the optically active medium is same for p and s polarization at normal incidence, it becomes different at oblique incidences.

Journal Article↗

[Isoelectric spectra of blood serum albumin in patients with disturbed thyroid gland function and nephrotic syndrome].

In patients suffering from diffuse toxic goiter, hypothyrosis and nephrotic syndrome changes in dynamics of treatment are found in the albumin molecule by means of the isoelectric focusing in the borate-polyol system and spectropolarimetry. The changes consist in an increased content of the albumin fractions in the range of pH 4.3-4.5 and 5.5-5.7. In patients suffering from toxic goiter conservative therapy rises the content of the fractions in the range of pH 4.3-4.5, whereas under hypothyrosis and nephrotic syndrome the content of the fraction decreases in the range of pH 5.5-5.7. Parallel studies of the dispersion of albumin optic rotation support despiralization of its molecule under all the dispersion of albumin optic rotation support despiralization of its molecule under all types of the pathology. The results obtained may be of diagnostic and prognostic significance.

Goiter↗

Determination of enantiomeric purity of ephedrine and pseudoephedrine by high-performance liquid chromatography with dual optical rotation/UV absorbance detection.

A reversed-phase high-performance liquid chromatography (HPLC) method with dual optical rotation/UV absorbance detection has been developed for the determination of enantiomeric purity of ephedrine hydrochloride and pseudoephedrine hydrochloride using an achiral column. The method gave a correlation coefficient of 0.9997 for the plot of log(optical rotation response) versus log (concentration) over the range of 0.06-10 mg ml(-1) of (+)-ephedrine hydrochloride (20 microliters injection). The limit of detection was 1.0 micrograms. Enantiomeric purity is shown to be most readily determined by measuring optical rotation, alpha, and absorbance, A, responses for standard and unknown samples, and using the equation (alpha/A)u/(alpha/A)s = (2xu - 1)/(2xs - 1), where x is the mole fraction of one of the enantiomers and subscripts s and u refer to standard and unknown, respectively. In blind trials using unknown mixtures of (+)- and (+/-)-ephedrine hydrochloride and a (+)-ephedrine hydrochloride standard, enantiomeric purities were determined to +/- 0.4% (95% confidence level) with five or six replicate 50 micrograms injections. The method has also been applied to the determination of the enantiomer mole fraction of (+)-pseudoephedrine hydrochloride in a cough linctus, giving xu = 0.99 +/- 0.01 with seven replicate injections of 20-fold diluted linctus samples containing 7.5 micrograms of the chiral compound being assayed. Unlike conventional polarimetry, the method does not require chemically-pure samples and can be orders of magnitude more economical in material.

Antitussive Agents↗

Stereoselective Synthesis of (+)-Avarol, (+)-Avarone, and Some Nonracemic Analogues.

Synthesis of the rearranged drimane sesquiterpenoids (+)-avarol and (+)-avarone from Wieland-Miescher ketone is described. This synthetic sequence provides convenient access to the natural enantiomers and, based on comparison of the optical rotation of synthetic avarol dimethyl ether with literature data, affords material of significantly higher optical rotation than a natural source. Similar synthetic strategies have been used to obtain several related compounds, including a decalin bearing an exocyclic olefin and a highly substituted cyclohexane, that can be viewed as hybrids of the trans-fused avarol and cis-fused arenarol skeletons.

Journal Article↗

Stereospecific inversion of l-alpha-methylfluorene-2-acetic acid to its d-enantiomer in the dog.

1. After administration of dl-alpha-methylfluorene-2-acetic acid to dogs, the optical rotation of the drug in blood increased with time. Of the total drug in blood, the d-enantiomer increased from 61 to 80% between 3 and 24 h after administration; by 384 h it was 100%. 2. Both l- and d-enantiomers had plasma half-lives and excretion characteristics similar to those of the dl-racemic mixture, indicating that the increase in the proportion of the d-enantiomer was not due to more rapid excretion of the l-enantiomer. 3. Studies of optical rotation and circular dichroism demonstrated that the l-enantiomer was converted to the d-enantiomer in the blood of the dog, but the d-enantiomer remained unchanged. After administration of the l-enantiomer, the d-enantiomer increased from 26 to 71% of the total drug in blood between 0-3 and 2 days after administration; 14 days after dosing, almost all of the drug was present as the d-enantiomer. 4. Isomerization of l-alpha-methylfluorene-2-acetic acid to its d-enantiomer also occurs in rat, monkey and man.

Acetates↗

General approach for the synthesis of sarpagine indole alkaloids. Enantiospecific total synthesis of (+)-vellosimine, (+)-normacusine B, (-)-alkaloid Q3, (-)-panarine, (+)-Na-methylvellosimine, and (+)-Na-methyl-16-epipericyclivine.

The first total synthesis of (+)-Na-methyl-16-epipericyclivine (9) was completed [from d-(+)-tryptophan methyl ester] in an overall yield of 42% (eight reaction vessels). The optical rotation [[alpha]D +22.8 (c 0.50, CHCl3)] obtained on this material confirmed that the reported optical rotation [[alpha]D 0 (c 0.50, CHCl3)]47 was biogenetically unreasonable. The total syntheses of (+)-vellosimine, (+)-normacusine B, (-)-alkaloid Q3, (-)-panarine, and (+)-Na-methylvellosimine are also described. Moreover, a mixed sample (1:1) of synthetic (-)-panarine and natural (-)-panarine yielded only one set of signals in the 13C NMR; this indicated that the two compounds are identical and further confirmed the correct configuration of (+)-vellosimine, (+)-normacusine B, and (-)-alkaloid Q3. In this approach, the key templates, (-)-Na-H,Nb-benzyltetracyclic ketone 15a and (-)-Na-methyl,Nb-benzyltetracyclic ketone 43 were synthesized on multihundred gram scale by the asymmetric Pictet-Spengler reaction and a stereocontrolled Dieckmann cyclization via improved sequences. An intramolecular palladium (enolate-mediated) coupling reaction was employed to introduce the C(19)-C(20) E-ethylidene function in the sarpagine alkaloids for the first time in stereospecific fashion.

Alkaloids↗

Poincaré sphere representation of the fixed-polarizer rotating-retarder optical system.

The trajectory of the polarization state of a monochromatic light beam after it passes through a fixed linear polarizer and a rotating linear retarder of arbitrary retardance delta is determined on the Poincaré sphere. The three-dimensional figure-8 contour is shown to be the line of intersection of a right-circular cylinder with the sphere. The cylinder is parallel to the polar (S3) axis, touches the sphere at the equator (at the point that represents the linear polarization transmitted by the fixed polarizer), and has a radius r = sin2(delta/2). Projections of the trajectory in the coordinate planes of the normalized Stokes parameter space (s1, s2, S3) are also determined.

Journal Article↗

The identification of Combretum gums which are not permitted food additives, II.

Combretum gums, readily available at low prices in East and West Africa, may be offered for sale as 'gum arabic'. Vigilance is necessary to detect such misrepresentations because Combretum gums differ greatly from gum arabic (Acacia senegal (L.) Willd.) in terms of quality, solution properties and value. Moreover, because there is no toxicological evidence for their safety in use, Combretum gums are not included in any of the international lists of permitted food additives. Food manufacturers and regulatory authorities therefore require data that characterize Combretum gums so that their use in foodstuffs can be prevented. This paper presents such data for the gums from a further six Combretum species. All of these have negative optical rotations similar to that of food grade gum arabic. It is no longer sufficient, therefore, to rely solely on an optical rotation measurement to confirm the identity of gum arabic. The additional analyses necessary to differentiate between Combretum gums and gum arabic are discussed.

Amino Acids↗

Labdanes and isopimaranes from Platycladus orientalis and their effects on erythrocyte membrane and on Plasmodium falciparum growth in the erythrocyte host cells.

Six labdanes (1-6) and four isopimaranes (7-10), including three new natural products (7, 9, and 10), were isolated from Platycladus orientalis, and their structures determined using 1D and 2D NMR methods, ion-cyclotron resonance HRMS, and optical rotation data. Relative configurations of all chiral centers in the isopimaranes were determined using NOESY experiments at 600 and 800 MHz. Specific optical rotation data were used to correlate absolute configurations. Compounds 1-9 and aframodial (11) were tested for their in vitro antiplasmodial activity and for their ability to induce changes of erythrocyte shape in order to obtain data about possible correlation between the two effects. All compounds tested exhibited weak (IC(50) > 25 microM) in vitro antiplasmodial effects against Plasmodium falciparum strain 3D7. At the same time, the compounds caused echinocytic or stomatocytic changes of the erythrocyte membrane curvature, indicative of their incorporation into the lipid bilayer, in the concentration region where the antiplasmodial activity was observed. The antiplasmodial effect of these compounds thus appears to be an indirect effect on the erythrocyte host cell. Weak or moderate antiplasmodial activity observed with many other apolar natural products, in particular those with amphiphilic structures, is also likely to be an indirect effect.

Animals↗