Second harmonic generation and polar order in thin films of polyesters

A series of optically active main chain polyesters were synthesized by high temperature polycondensation from biphenolic azo chromophores with azobenzene-4,4'-dicarbonylchloride and 1,4:3,6-dianhydro-D-sorbitol ([!]_D²⁵=+42.5°). The second harmonic generation of the polyesters is studied in thin films. The polar order in films is determined from the UV-visible absorption spectra. The variation in SHG intensity with chiral monomer concentration is explained as a function of polar order. The polymers with chiral units showed good second harmonic efficiency. The intensity of second harmonic light (532 nm) increased with angle of incidence and indicated the polar order in the plane of the film. The SH signal also showed good temporal stability.     

Diastereoselective formation of 2-aryl-3-arenesulfonyl 4-ethyl-1,3-oxazolidines: An X-ray crystallographic and H NMR study

N-Arylsulfonamides of (R)- and (S)-2-amino-1-butanol, on condensation with aromatic aldehydes produced diastereomerically pure 2-aryl-3-arenesulfonyl 4-ethyl-1,3-oxazolidines. The absolute configurations of one enantiomeric pair have been determined from two fully refined X-ray structures, supplemented by nmr data.     

Back Reaction in Static Einstein Spaces—Change of Entropy

Using the thermodynamical approach and the method of York, the back-reaction of anti-de Sitter Schwarzschild black hole in thermal equilibrium with conformal spin-2 field is studied. It is found that both approaches give identical results.     

Second‐harmonic response of a series of chiral polyesters: A joint experimental and theoretical study

A series of polyesters with π‐conjugated donor–acceptor segments was synthesized by the condensation of azobenzene‐4,4′‐dicarbonylchloride with 1,4:3,6‐dianhydro‐D‐sorbitol ([α] = + 42.5°) and biphenolic chromophores, bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylmethane and bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylsulfone. The polymers were characterized by spectral methods (IR, ultraviolet–visible, and NMR), thermal methods (thermogravimetry and differential scanning calorimetry), wide‐angle X‐ray scattering, and polarimetry. The polymers containing isosorbide units were optically active and crystalline. They exhibited glass‐transition temperature values between 100 and 160 °C and were stable up to 400 °C. The second‐harmonic generation (SHG) efficiency of the polymers was experimentally verified by a powder‐reflection technique with 2‐methyl‐4‐nitroaniline as a reference. The SHG efficiencies of the polymers were compared to those of the chromophores and explained as a function of the percentage of chiral composition. The hyperpolarizability β values were also determined by a two‐level model solvatochromic method and computational methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2868–2877, 2002     

Subsecond luminescence intensity fluctuations of single CdSe quantum dots

Photoluminescence (PL) intermittency characteristics are examined for single quantum dots (QDs) in a CdSe QD sample synthesized at a slow rate at 75 degrees C. Although the PL quantum efficiency was relatively low ( approximately 0.25), we noticed that the PL intensity of single CdSe QDs fluctuated on a subsecond time scale with short-lived "on" and "off" states. The subsecond PL intensity fluctuations of CdSe QDs are different from "on" and "off" PL blinking generally observed for QDs fluctuating on a millisecond to minute time scale. We characterized single QDs by identifying polarized excitations, topographic imaging using atomic force microscopy (AFM), and transmission electron microscopy (TEM). From analysis of the PL intensity trajectories from >100 single CdSe QDs, the average intermittency time was 213 ms. From the PL quantum efficiency, slow growth of QDs, intensity trajectory analyses, and previous reports relating surface trap states and PL properties of QDs, we attribute the subsecond PL intensity fluctuations of single CdSe QDs and short-lived "on" and "off" states to a high-density distribution of homogeneous surface trap states.     

Isometric graphing and multidimensional scaling for reaction-diffusion modeling on regular and fractal surfaces with spatiotemporal pattern recognition

Heterogeneous surface reactions exhibiting complex spatiotemporal dynamics and patterns can be studied as processes involving reaction-diffusion mechanisms. In many realistic situations, the surface has fractal characteristics. This situation is studied by isometric graphing and multidimensional scaling (IGMDS) of fractal surfaces for extracting geodesic distances (i.e., shortest scaled distances that obtain edges of neighboring surface nodes and their interconnections) and the results obtained used to model effects of surface diffusion with nonlinear reactions. Further analysis of evolved spatiotemporal patterns may be carried out by IGMDS because high-dimensional snapshot data can be efficiently projected to a transformed subspace with reduced dimensions. Validation of the IGMDS methodology is carried out by comparing results with reduction capabilities of conventional principal component analysis for simple situations of reaction and diffusion on surfaces. The usefulness of the IGMDS methodology is shown for analysis of complex patterns formed on both regular and fractal surfaces, and using generic nonlinear reaction-diffusion systems following FitzHugh Nagumo and cubic reaction kinetics. The studies of these systems with nonlinear kinetics and noise show that effects of surface disorder due to fractality can become very relevant. The relevance is shown by studying properties of dynamical invariants in IGMDS component space, viz., the Lyapunov exponents and the KS entropy for interesting situations of spiral formation and turbulent patterns.     

Complexometric determination of thallium(III) in pure solution,alloys, and complexes using semicarbazide hydrochloride as a releasing agent

A simple and accurate complexometric method is proposed for the determination of Tl(III) using semicarbazide hydrochloride as a releasing agent. In the presence of diverse metal ions, thallium is complexed first with a known excess of EDTA, and the surplus EDTA is then titrated with standard zinc sulfate at pH 5.0–6.0 (hexamine) using xylenol orange indicator. An excess of 5% aqueous neutral solution of semicarbazide hydrochloride is then added and the released EDTA is titrated against standard zinc sulfate solution. The method works well in the range 2–50 mg of Tl(III) with relative errors < 0.5%, standard deviations 0.05mg and coefficient of variation 0.4%. The method is applied for the determination of thallium content in complexes and alloy compositions     

Simple method for the determination of rosiglitazone in human plasma using a commercially available internal standard

To the best of our knowledge, bioanalytical methods to determine rosiglitazone in human plasma reported in literature use internal standards that are not commercially available. Our purpose was to develop a simple method for the determination of rosiglitazone in plasma employing a commercially available internal standard (IS). After the addition of celecoxib (IS), plasma (0.25 mL) samples were extracted into ethyl acetate. The residue after evaporation of the organic layer was dissolved in 750 microL of mobile phase and 50 microL was injected on to HPLC. The separation was achieved using a Hichrom KR 100, 250 x 4.6 mm C(18) with a mobile phase composition potassium dihydrogen phosphate buffer (0.01 m, pH 6.5):acetonitrile:methanol (40:50:10, v/v/v). The flow-rate of the mobile phase was set at 1 mL/min. The column eluate was monitored by fluorescence detector set at an excitation wavelength of 247 nm and emission wavelength of 367 nm. Linear relationships (r(2) > 0.99) were observed between the peak area ratio rosiglitazone to IS vs rosiglitazone concentrations across the concentration range 5-1000 ng/mL. The intra-run precision (%RSD) and accuracy (%Dev) in the measurement of rosiglitazone were <+/-10.69 and <-12.35%, respectively across the QC levels (50-1000 ng/mL). The extraction efficiency was >80% for both rosiglitazone and IS from human plasma. The lower limit of quantitation of the assay was 5 ng/mL. In summary, the methodology for rosiglitazone measurement in plasma was simple, sensitive and employed a commercially available IS.     

Magnetic field rectifiers using semicircular Josephson junctions

A novel method for rectifying alternating magnetic fields is demonstrated using fluxons in semicircular Josephson junctions. An external magnetic field applied parallel to the dielectric barrier of the semicircular junction has opposite polarities at the ends of the junction and supports penetration of opposite polarity fluxons into the junction in the presence of a constant dc bias. When the direction of the field is reversed, flux penetration is not possible and a flux-free state exists in the junction. Thus, effective rectification of an alternating magnetic field can be achieved in semicircular Josephson junctions. This unique phenomenon is specific to this geometry and can be employed in rf SQUID magnetometers.