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1
Content available remote Dual-wavelength laser polarimeter and its performance capabilities
EN
A dual-wavelength optical polarimetric approach has been proposed as a means of elimination of the systematic errors and estimation of the optical anisotropy parameters for a single DKDP crystal. Our HAUP-related polarimeter uses two semiconductor lasers with the neighbouring wavelengths of 635 nm and 650 nm. Based on the temperature dependence analysis of small characteristic azimuths of light polarization with respect to the axis of the sample, we found the parameters of imperfections of polarization system. We acquired eigen waves ellipticities in a DKDP crystal and found perpendicular to the optic axis value of the optical rotatory power. Our results correlate positively with previously measured data for KDP crystals.
EN
The results of measurements of Kerr constant in castor oil, obtained by dynamic-polarimetric method are presented. Variable optical path length and four measurement setup configurations were used. They differed by the orientation of polarizer and of quarterwave plate and therefore they were non-equivalent when other, unwanted effects occurred. It was shown that the Kerr constant measurement performed with use of only one system configuration and one length of optical path may be strongly affected by other effects, however taking the arithmetic mean of two results obtained from appropriate system configurations significantly reduces this error. Theoretical dependences were fitted to the experimental results, which allowed for approximation of other constants, like dichroism, linear birefringence and optical activity induced by external electric field (electrogyration).
PL
Przedstawiono wyniki pomiarów stałej Kerra w oleju rycynowym metodą polaryzacyjno-optyczną dla różnych długości drogi światła w próbce przy czterech konfiguracjach pomiarowych, nierównoważnych pod względem wpływu innych niepożądanych efektów, które różnią się orientacjami polaryzatora i płytki ćwierćfalowej. Pokazano, że pomiar stałej Kerra przeprowadzony dla tylko jednej konfiguracji pomiarowej przy jednej długości drogi światła w próbce może być obciążony znacznym wkładem kilku innych niepożądanych efektów, jednakże obliczenie średniej arytmetycznej z pomiarów w dwóch odpowiednio dobranych konfiguracjach pomiarowych pozwala na znaczne zredukowanie błędów pomiarowych. Do wyników doświadczalnych dopasowano zależności teoretyczne, co oprócz pomiaru stałej Kerra pozwoliło także na zgrubne oszacowanie innych wielkości takich jak dichroizm, liniowa dwójłomność i aktywność optyczna indukowana polem elektrycznym (elektrożyracja).
EN
This works presents an extended theoretical analysis of the response of experimental setup to an applied electric field during measurements of electro-optic coefficients in optically active liquids using an optical polarimetric technique. The analysis includes liquids belonging to ∞ ∞, ∞ 2 and ∞ Curie symmetry groups and the following phenomena were taken into account: natural optical activity, natural linear birefringence, dichroism, and the effects induced by an applied electric field – linear and quadratic electro-optic effects and linear and quadratic electrogyration. The presented example concerns numerical error analysis for measurement of the quadratic electro-optic effect in castor oil, which exhibits the symmetry ∞ 2 between a pair of plane-parallel electrodes.
PL
Przedstawiono rozszerzoną teoretyczną analizę odpowiedzi układu pomiarowego na przyłożone pole elektryczne podczas pomiarów współczynników efektu elektrooptycznego w cieczy aktywnej optycznie metodą polaryzacyjno-optyczną. Analiza obejmuje ciecze o symetriach wewnętrznych opisanych grupami Curie ∞ ∞, ∞ 2 oraz ∞ i uwzględnia następujące zjawiska: naturalna aktywność optyczna, naturalna dwójłomność liniowa, dichroizm oraz efekty indukowane przez przyłożone pole elektryczne – liniowy i kwadratowy efekt elektrooptyczny oraz liniowa i kwadratowa elektrożyracja. Przedstawiony przykład dotyczy numerycznej analizy błędu pomiaru kwadratowego efektu elektrooptycznego w oleju rycynowym, który wykazuje symetrię ∞ 2 po umieszczeniu go pomiędzy płasko-równoległymi elektrodami.
EN
Using a highly accurate polarimetric method, we determine the gyration tensor component g11 for Ca3Ga2Ge4O14 (CGG) crystals. For this aim we employ a single-wavelength high-accuracy polarimeter and eliminate the main systematic errors of our polarimetric measurements. A calculation technique based on the polarizability theory for optical activity (OA) is applied to derive optical rotatory power (ORP) for the CGG. A comparison of the observed and calculated OA parameters confirms the validity of our theoretical calculations. Dispersions of both the ordinary and extraordinary refractive indices and the ORP are calculated.
EN
Five new optically active poly(amide-imide)s(PAIs) 5a - e were prepared by direct polycondensation reaction of N,N0 - (pyromellitoyl) bis-L-tyrosine 3 as chiral dicarboxylic acid with various aromatic diamines 4a - e. Triphenylphosphite(TPP)/pyridine(py) in the presence of calcium chloride (CaCl2) and N-methyl-2-pyrrolidone (NMP) were successfully applied to direct polycondensation reaction. The resulting new polymers were obtained in good yields with inherent viscosities ranging between 0.48 dL/g and 0.6 dL/g. They were analyzed with a C.H.N. elemental analyzer, FTIR, 1H-NMR, UV-VIS spectroscopy and polarimeter (speci?c rotation measurement, [a] 25 D ). Thermogravimetric analysis (TGA) indicated that the residual weight percentage of polymers at 600 °C were between 48.66 % and 64.21 %, which showed their thermal stability. These polymers are attractive to be used as packing materials in chromatography columns for separation of enantiomers.
EN
In this part selenuranes (10-Se-4 and 10-Se-5) and perselenuranes 12-Se-6 as well as telluranes 10-Te-4 and pertelluranes 12-Te-6 will be presented. The main goal is to describe recent reports on the synthesis, chemical, physical, spectral and conformational behavior, stereochemistry, stability and biological activity of these compounds. Their occurrence as reaction intermediates will also be shown.
EN
In this part of the review one of the most famous 10-S-4 sulfurane called Martin sulfurane together with sulfuranes 10-S-5 and persulfuranes 12-S-6 will be presented. Martin sulfurane has been well known for a relatively long time but it is still useful in organic synthesis as a dehydrating, coupling and oxidizing agent. Its use in selected substitution reactions will be also described. Next, synthesis and selected properties of sulfuranes 10-S-5, mainly sulfurane oxides, and persulfuranes 12-S-6, will be shown. Besides synthetic methods, the review is focused on the investigations of the stability and isomerization of these types of compounds, which is particularly interesting for persulfuranes, because of the presence of three 3c-4e bonds.
EN
The compounds presented herein are sulfuranes 10-S-3 and 10-S-4 containing hypervalent sulfur atom. They have been known for a relatively long time. Nevertheless, they, and especially 10-S-4 species, are still of great interest due to their unique properties. The review presents recent approaches to the synthesis of these compounds, their selected structural, physical, chemical, stereochemical and electronic properties and their use as reagents and catalysts in several reaction types. The presence of structures of these types as intermediates, which explains selected reaction mechanisms, will also be shown.
EN
The goal of this four-part review is a presentation of the results of recent studies on the properties and chemistry of hypervalent sulfur, selenium and tellurium compounds. The term “hypervalency” has been known since 1969 when Musher used it to describe molecules bearing heteroatoms which formally did not fulfill the octet rule. This violation was explained by the postulate concerning the existence of a 3-center 4-electron bond between a hypervalent heteroatom and two axial electronegative ligands. The bond is the a combination of two ligand orbitals and a pz orbital of a central heteroatom which results in the formation of three molecular orbitals. The distances between the central atom and these two ligands are longer than the length of the typical sp2 bonds, such as equatorial ones. Moreover, the effective electron density is shifted from the central atom towards the axial ligands what results in the fulfillment of the octet rule of this atom. The geometry of this system is trigonal bipyramid (Fig. 2), except from compounds having three 3-center 4-electron (3c-4e) bonds which have tetragonal bipyramid geometry (Fig. 3). The term “geometry” includes positions of ligands and lone electron pairs. The stability of hypervalent compounds is affected by a few factors: electronegativity of ligands, formation of five-membered cyclic structures involving the central atom and the number of electron shells of the central atom. Martin proposed three-symbol notation N-X-L for these structures, which was further modified (Tab. 1). Hypervalent compounds can isomerize according to various mechanisms: Berry pseudorotation (Scheme 1), turnstile rotation (Scheme 2), cuneal inversion (Scheme 3), lever mechanism (Scheme 4), or Bailar twist (Scheme 5). Furthermore, hypervalent structures of 10-X-4 and 10-X-5 type with trigonal bipyramid geometry, C1 or C2 symmetry and at least three different ligands can exist as optically active species (Tab. 2, Fig. 5–7, Scheme 6), especially the "spiro" ones, which are resistant to isomerization. In 1977 Martin and Balthazor proposed extended Cahn-Ingold-Prelog convention for description of the absolute configuration of chiral hypervalent compounds (Fig. 5).
EN
Presented experimental data show that castor oil between metal flat electrodes can not be satisfactorily described as an isotropic liquid of ∞ ∞ symmetry, even in the absence of an electric field between the electrodes. Correct description of optical properties requires the assumption of 2 ∞ symmetry and consideration of circular birefringence, linear birefringence and dichroism occurring at the same time. Disappearance of linear birefringence and dichroism in castor oil has been observed several days after filling cuvette witch metal electrodes, which suggests the usefulness of such measurements to study the aging processes. The results presented are also important for correct interpretation of future measurements of electro-optic and electrogyration effects in liquids.
PL
Przedstawiono wyniki pomiarów wskazujące, że olej rycynowy umieszczony pomiędzy metalowymi płaskimi elektrodami nie może być zadowalająco opisany jako ciecz izotropowa o symetrii ∞ ∞ nawet przy braku pola elektrycznego pomiędzy elektrodami. Poprawny opis właściwości optycznych wymaga założenia symetrii 2 ∞ oraz uwzględnienia jednocześnie dwójłomności kołowej, dwójłomności liniowej i dichroizmu. Zaobserwowano zanikanie dwójłomności liniowej i dichroizmu w oleju rycynowym po kilkunastu dniach od napełnienia kuwety z metalowymi elektrodami, co wskazuje na przydatność pomiarów tych wielkości do badań procesów starzenia. Przedstawione rezultaty mają także znaczenie dla poprawnej interpretacji przyszłych pomiarów efektów elektro-optycznych i elektrożyracji w cieczach.
EN
Chirality is of paramount importance in chemistry and life sciences. Electronic circular dichroism (ECD) as well as optical rotation (OR) are fundamental properties of chiral molecules. These chiroptical properties provide rich information about conformation and configuration of the molecules. Although empirical correlations between chiroptical phenomena, mostly ECD, and molecular stereochemistry have existed for some time, the development of new accurate theoretical methods opened new opportunities for correlation of chiroptical properties with structure. Computational chemistry has made an amazing progress during the past two decades, moving this highly specialized discipline into the mainstream, and making a renaissance in chiroptical methods. This short review is meant as an introduction to the modern approach to optical activity of chiral molecules. Some illustrative applications will put the emphasis on practical applications of the theoretical/experimental analysis of complex molecules including highly flexible bistramide C and noncovalently bonded donor-acceptor dyad. The importance of the solvent effect is briefly discussed and a typical methodology is described and its strengths and weak points are commented.
12
Content available remote Acoustogyration diffraction of optical waves : case of SiO₂ and TeO₂ crystals
EN
Interaction of acoustic and light waves with accounting for elastooptic and elastogyration effects is theoretically described. Collinear acoustogyration diffraction in quartz and paratellurite crystals is experimentally investigated and thoroughly analyzed. Piezogyration effect is experimentally studied for TeO₂ crystals. The acoustogyration efficiency and the acoustogyration figure of merit calculated for a number of crystals (GaAs, TeO₂ and SiO₂) are shown to be too small for experimental detection. On the other hand, we demonstrate that the light diffraction at periodical distribution of the imaginary part of dielectric permittivity related to the piezogyration effect should, in principle, be observed for the case of interaction of optical waves with enantiomorphous ferroelastic domain structure and in cholesteric liquid crystals.
13
Content available remote Light-controlled helical pitch and dynamic gratings
EN
A chiral nematic liquid crystal (LC) with a photo-sensitive chiral agent is employed for a light-controlled modulation of optical activity and used as a model substance for a dynamic diffraction grating recording. The described liquid crystalline system has shown a strong nonlinear response with effective parameter of cubic nonlinearity being much greater of that characteristic of the orientational nonlinearity of LC. A simple mathematical model of light diffraction on the grating of modulated optical activity was developed. Calculated values of intensities and polarisation states of diffracting beams have shown very good agreement with the experimental data. LC systems with light-controlled chirality could be promising media for nonlinear optical applications or all-optical switching devices.
PL
Szkła, obok półprzewodników i metali, są podstawowym materiałem do budowy elementów w optoelektronice i mikroelektronice. Praktyczna wiedza o szkłach rozszerza się wraz z rozwojem ich zastosowań w telekomunikacji i budowie mikrosystemów. Wiele elementów funkcjonalnych fotoniki budowanych jest ze szkieł nieliniowych. Optyczne zjawiska nieliniowe indukowane w szkle pozwalają na budowę nowych mikroelementów fotonicznych zastępujących złożone rozwiązania klasycznej optyki objętościowej. W artykule, który jest pierwszą częścią cyklu prac o szkłach nieliniowych, dokonano definicji szkła nieliniowego przez porównanie ze szkłem liniowym. Określono obszary nieliniowości szkieł, bazując na wzajemnym oddziaływaniu ośrodka, fali optycznej i innych pól fizycznych. Zebrano tutaj te nieliniowe cechy elektryczne szkieł, które decydują o ich nieliniowych właściwościach optycznych.
EN
Glasses, together with semiconductors and metals, are fundamental materials for building of components for optoelectronics and micro-electronics. Practical knowledge about glasses extends considerably with strong development of their applications in telecommunications and the construction of microsystems. Many functional components of the photonics is manufactured of nonlinear glasses. Nonlinear optical phenomena induced in glasses allow for building of new microcom-ponents, replacing complex solutions of classical volume optics. The paper, which is the first part of a cycle on nonlinear glasses, defines the nonlinear glass by its comparison with a linear one. The areas of glass nonlinearities were defined basing on mutual interaction of medium, optical wave and interacting external physical fields. There were gathered these nonlinear electrical properties of glasses which decide of their nonlinear optical properties.
PL
Otrzymano szereg dikwasów zawierających ugrupowania imidowe (dikarboksyimidów) w reakcji bezwodnika kwasu trimelitowego bądź dibezwodników różnych kwasów tetrakarboksylowych z optycznie czynnymi a-aminokwasami. W nielicznych tylko przypadkach uzyskano pożądane, o odpowiednim stopniu czystości produkty (zgodność temperatury topnienia z danymi literaturowymi, budowa chemiczna potwierdzona badaniami IR i 1H NMR). W większości reakcji powstawały produkty zanieczyszczone, trudne do wydzielenia i identyfikacji. Z wybranych dikwasów otrzymano odpowiednie chlorki w standardowej reakcji z chlorkiem tionylu.
EN
Several diacids, containing imide groups (dicarboxyimides), have been prepared in the reaction of trimellitic anhydride or dianhydrides: pyromellitic, bicyclo[2,2,2]-oct-7-en-2,3,5,6-tetracarboxylic, benzophenone-3,3',4,4'-tetracarboxylic, perylene-3,4,9,10-tetracarboxylic or biphthalic one with optically active a-amino acids such as L-alanine, D-alanine, D/L-alanine, L-leucine, L-isoleucine, L-phenylalanine, L-valine or L-2-aminobutyric acid (Table 1, Scheme A). The products of desired purity were obtained in only few cases (agreement of melting point with literature data, chemical structure confirmed by IR and 1H NMR methods, Fig. 1-4). In majority of reactions the impured products, difficult to separation and identification, were obtained. From the chosen diacids the proper chlorides were obtained via standard reaction with thionyl chloride (Table 2).
16
EN
Commonly available hydrolytic enyzymes are capuble of recognizing heteroatom stereogenic centres. A review of the application of these enzymes in the preparation of optically active sulfur and phosphorus compounds, based on the results from the authors' Laboratory, is presented.
PL
Powszechnie dostępne enzymy hydrolityczne są w stanie rozpoznać stereogenne centra heteroatmowe. Niniejszy przegląd przedstawia zastosowanie tego typu enzymów w syntezie optycznie czynnych połączeń siarki i fosforu ze szczególnym uwzględnieniem wyników badań pochodzących z Laboratorium autorów.
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