Conformational analysis of dipeptide‐derived polyisocyanides

The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003     

Analysis of tunable diode-laser spectra of Q(J,0) lines in CH3F near 1475 cm using a multispectrum fitting technique

We have analyzed the methyl fluoride ^RQ(J,0)Q branch lines located near 1475 cm⁻¹ using a simultaneous multi-spectrum fitting technique. In this analysis we have used previously recorded diode-laser data in which we collected many data points covering only one or two Q branch lines in a particular run. The analysis consists of simultaneously fitting 57 spectra collected with numerous pressure and path length conditions for all absorption lines. The data are concatenated to create one continuous spectrum of the Q branch. We have determined the intensity and self-broadened widths at 296 K for 23 ^RQ(J,0) lines.     

Ein Verfahren zur Trennung des Zinks von allen Metallen seiner Gruppe

Ohne Zusammenfassung     

Vascular morphology by three-dimensional magnetic resonance imaging

A three-dimensional examination of blood vessels is provided using MR data from seven cases. The vascular surfaces are constructed with an algorithm that automatically follows the selected artery or vein and generates a projected three-dimensional gradient shaded image. Fast 3DFT pulse sequences were optimized to enhance the time-of-flight contrast of the intravascular region. By increasing the surface threshold value in a three-dimensional head study, the flesh of a patient's face was peeled away to demonstrate the superfacial temporal artery. Gated cardiac images show the great vessels and cardiac chambers. A three-dimensional view of the aorta shows an irregular surface in the vicinity of an adrenal tumor. 3D MR exams provide a non-invasive technique for assessing vascular morphology in a clinical setting.     

Activity of microemulsion-based nanoparticles at the human bio-nano interface: concentration-dependent effects on thrombosis and hemolysis in whole blood

Background: Although microemulsion-based nanoparticles (MEs) may be useful for drug delivery or scavenging, these benefits must be balanced against potential nanotoxicological effects in biological tissue (bio-nano interface). We investigated the actions of assembled MEs and their individual components at the bio-nano interface of thrombosis and hemolysis in human blood. Methods: Oil-in-water MEs were synthesized using ethylbutyrate, sodium caprylate, and pluronic F-68 (ME4) or F-127 (ME6) in 0.9% NaCl_w/v. The effects of MEs or components on thrombosis were determined using thrombo-elastography, platelet contractile force, clot elastic modulus, and platelet counting. For hemolysis, ME or components were incubated with erythrocytes, centrifuged, and washed for measurement of free hemoglobin by spectroscopy. Results and conclusions: The mean particle diameters (polydispersity index) for ME6 and ME4 were 23.6 ± 2.5 nm (0.362) and 14.0 ± 1.0 nm (0.008), respectively. MEs (0, 0.03, 0.3, 3 mM) markedly reduced the thromboelastograph maximal amplitude in a concentration-dependent manner (49.0 ± 4.2, 39.0 ± 5.6, 15.0 ± 8.7, 3.8 ± 1.3 mm, respectively), an effect highly correlated (r2 = 0.94) with similar changes caused by pluronic surfactants (48.7 ± 10.9, 30.7 ± 15.8, 20.0 ± 11.3, 2.0 ± 0.5) alone. Neither oil nor sodium caprylate alone affected the thromboelastograph. The clot contractile force was reduced by ME (27.3 ± 11.1–6.7 ± 3.4 kdynes/cm², P = 0.02, n = 5) whereas the platelet population not affected (175 ± 28–182 ± 23 10⁶/ml, P = 0.12, n = 6). This data suggests that MEs reduced platelet activity due to associated pluronic surfactants, but caused minimal changes in protein function necessary for coagulation. Although pharmacological concentrations of sodium caprylate caused hemolysis (EC₅₀ = 213 mM), MEs and pluronic surfactants did not disrupt erythrocytes. Knowledge of nanoparticle activity and potential associated nanotoxicity at this bio-nano interface enables rational ME design for in vivo applications.     

Synthesis and properties of the nanocomposite of zink oxide and poly(amic acid)

The composite comprised of zinc oxide quantum dots and poly(amic acid) (PAAc) was prepared and studied by X-rays diffraction, X-ray photoelectron spectroscopy, light scattering, UV absorbance and UV fluorescence. The UV absorbance of the ZnO/PAAc composite was found to be much larger than that of its components taken separately. The fluorescence of the ZnO/PAAc composite was found to be shifted to longer wavelengthes in comparison with pure ZnO. The presence of the dopant dodecylbenzenesulfonic acid was found to affect the observed fluorescence.     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

Modelling and design of a travelling-wave electro-optic modulator on InP

Based on a rigorous vectorial analysis, a fast travelling-wave Mach–Zehnder modulator is modelled and designed. The cross-section of the semiconductor layer stack and the lossy electrodes are carefully modelled using the method of lines in order to investigate propagation characteristics, velocity and losses. This yields an accurate microwave and optical field distribution to explain the behaviour of the component. In order to enhance the modulation efficiency, design curves are derived and the cross-sectional dimensions for minimum microwave loss are determined. The loss of the optimized modulator agrees very well with small-signal measurements up to 40 GHz and HFSS simulations. The layerstack of the fabricated device is suitable for integration with InP multi-wavelength lasers.     

A fast method to measure the thickness of removed layer from etching of SSNTD based on EDXRF

Solid state nuclear track detectors are commonly used for measurements of concentrations of radon gas and/or radon progeny. All these measurements depend critically on the thickness of the removed layer during etching. However, the thickness of removed layer calculated using the etching period does not necessarily provide a sufficiently accurate measure of the thickness. For example, the bulk etch rate depends on the strength of stirring during etching for the LR 115 detector. We propose here to measure the thickness of the removed layer by using energy-dispersive X-ray fluorescence spectrometry. In the present work, a reference silver nitrate pellet is placed beneath the LR 115 detector, and the fluorescence X-ray intensity for silver is then measured. We have found a linear relationship between the X-ray intensity and the thickness of the removed layer for LR 115 detector. This provides a fast method to measure the thickness of removed layer from etching of LR 115 detector. However, this method was found to be inapplicable for the CR-39 detector. Therefore, alternative methods have yet to be explored for the CR-39 detector.     

NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies

In this work, the melting-point depression and molecular dynamics of hexamethyldisilane confined within five controlled pore glasses, with mean diameters ranging from 7.9 to 23.9 nm, are studied by high-field (9.4 T) nuclear magnetic resonance (NMR), and the results are discussed with reference to the bulk substance. The melting-point depression in pores with radiusR follows the simplified Gibbs-Thompson equation ΔT=k _p/(R−s) with ak _p value of 74 K · nm and ans value of 1 nm. To our knowledge, this is the first time thek _p value of hexamethyldisilane is reported. Proton spin-lattice relaxation times (T ₁), spin-spin relaxation times (T ₂), and diffusivities (D) are reported as a function of temperature. The confinement in the pores gives rise to substantial changes in the molecular dynamics and the phase behavior. The line-shape measurements reveal a two-phase system assigned to a relatively mobile component at the pore walls and a crystalline solid at the center of the pores. However, theT ₂ measurements show that the mobile phase also embraces a minor component attributed to nonfrozen liquid in pockets or micropores. The diffusivity of the major narrow-line component is approximately three orders of magnitude larger than that in the plastic bulk phase, reflecting fast diffusion of mobile molecules. Below the melting region,T ₁ of the narrow line is significantly shorter thanT ₁ of the broad line, suggesting that the molecular reorientation is more hindered close to the surface than at the center of the pore.