Highly Tin‐Selective Stille Coupling: Synthesis of a Polymer Containing a Stannole in the Main Chain

The incorporation of heavier Group 14 element heteroles into semiconducting polymers leads to unusual optoelectronic properties. However, polymers containing stannoles have not been accessible to date. We report a synthetic route to a well‐defined, stannole‐containing polymer, the first example of this class of π‐conjugated polymers. This route was made possible by developing difunctionalized stannole monomers and highly tin‐selective Stille coupling reactions that leave the tin in the stannole untouched. Compared to poly(3‐n‐hexylthiophene), the resulting polymer displays a remarkable bathochromic shift in its absorption.     

Cyclic antiautomorphisms of directed triple systems

A transitive triple, (a,b,c), is defined to be the set {(a,b), (b,c), (a,c)} of ordered pairs. A directed triple system of order v, DTS(v), is a pair (D,β), where D is a set of v points and β is a collection of transitive triples of pairwise distinct points of D such that any ordered pair of distinct points of D is contained in precisely one transitive triple of β. An antiautomorphism of a Directed triple system, (D,β), is a permutation of D that maps β to β⁻¹, where β ⁻¹ = {(c,b,a)|(a,b,c) E β}. In this article we give necessary and sufficient conditions for the existence of a Directed triple system of order v admitting an antiautomorphism consisting of a single cycle of length d and having v − d fixed points. Further, we give a more general result for partial Directed triple systems in which the missing ordered pairs are precisely those containing two fixed points. © 1996 John Wiley & Sons, Inc.     

Capillary zone electrophoresis with UV-scanning detection for the analysis of metal species and their organic binding partners in biological systems

A capillary zone electrophoretic method with UV-scanning detection for the separation and identification of both free ligands and metal species is presented. The electrophoretic behavior of naturally occurring binding partners such as organic acids and amino acids was studied and compared with their metal-complexes. Copper(II) complexes of citrate and amino acids showed decreased electrophoretic mobilities and altered UV spectra. The optimized method was validated on ultrafiltered cow's milk and human milk samples. In cow's milk six low molecular weight substances, including citrate, orotate, and hippurate, could be separated. Metal supplementation with Cu(II), Ni(II), or Zn(II) decreased not only the citrate peak but also the orotate signal and in the case of copper(II) supplementation a new signal for the copper(II)-citrate complex appeared. In human milk samples various amino acids such as glutamate, phenylalanine, tyrosine, and tryptophan could be identified besides citrate. The electrophoretic mobilites and peak areas of the amino acids were also influenced by the metal supplementation.     

Runge–Kutta Lawson schemes for stochastic differential equations

In this paper, we present a framework to construct general stochastic Runge–Kutta Lawson schemes. We prove that the schemes inherit the consistency and convergence properties of the underlying Runge–Kutta scheme, and confirm this in some numerical experiments. We also investigate the stability properties of the methods and show for some examples, that the new schemes have improved stability properties compared to the underlying schemes.

     

Numerical correction of optical vortex using a wrapped phase map analysis algorithm

We demonstrate experimentally a technique for the numerical correction of an optical vortex with a unitary topological charge. A developed algorithm based on the axial behavior of a reconstructed wavefront is used in the detection of the optical vortex. Optimizations of the number of axial phase maps and the window size used in the algorithm yield the precise coordinates of the vortex eye. The obtained coordinates and vortex handedness are used in designing a proper filter, facilitating numerical correction of the vortex phase map. The developed algorithm can be applied to absolute phase and phase difference maps obtained through any reconstruction method.     

Variable angle NMR spectroscopy and its application to the measurement of residual chemical shift anisotropy

The successful measurement of anisotropic NMR parameters like residual dipolar couplings (RDCs), residual quadrupolar couplings (RQCs), or residual chemical shift anisotropy (RCSA) involves the partial alignment of solute molecules in an alignment medium. To avoid any influence of the change of environment from the isotropic to the anisotropic sample, the measurement of both datasets with a single sample is highly desirable. Here, we introduce the scaling of alignment for mechanically stretched polymer gels by varying the angle of the director of alignment relative to the static magnetic field, which we call variable angle NMR spectroscopy (VA-NMR). The technique is closely related to variable angle sample spinning NMR spectroscopy (VASS-NMR) of liquid crystalline samples, but due to the mechanical fixation of the director of alignment no sample spinning is necessary. Also, in contrast to VASS-NMR, VA-NMR works for the full range of sample inclinations between 0° and 90°. Isotropic spectra are obtained at the magic angle. As a demonstration of the approach we measure 13C-RCSA values for strychnine in a stretched PDMS/CDCl? gel and show their usefulness for assignment purposes. In this context special care has been taken with respect to the exact calibration of chemical shift data, for which three approaches have been derived and tested.     

Perception of intrusive /r/ in English by native, cross-language and cross-dialect listeners

In sequences such as law and order, speakers of British English often insert /r/ between law and and. Acoustic analyses revealed such "intrusive" /r/ to be significantly shorter than canonical /r/. In a 2AFC experiment, native listeners heard British English sentences in which /r/ duration was manipulated across a word boundary [e.g., saw (r)ice], and orthographic and semantic factors were varied. These listeners responded categorically on the basis of acoustic evidence for /r/ alone, reporting ice after short /r/s, rice after long /r/s; orthographic and semantic factors had no effect. Dutch listeners proficient in English who heard the same materials relied less on durational cues than the native listeners, and were affected by both orthography and semantic bias. American English listeners produced intermediate responses to the same materials, being sensitive to duration (less so than native, more so than Dutch listeners), and to orthography (less so than the Dutch), but insensitive to the semantic manipulation. Listeners from language communities without common use of intrusive /r/ may thus interpret intrusive /r/ as canonical /r/, with a language difference increasing this propensity more than a dialect difference. Native listeners, however, efficiently distinguish intrusive from canonical /r/ by exploiting the relevant acoustic variation.     

Stable silencing of SNAP-25 in PC12 cells by RNA interference

Background  

SNAP-25 is a synaptic protein known to be involved in exocytosis of synaptic vesicles in neurons and of large dense-core vesicles in neuroendocrine cells. Its role in exocytosis has been studied in SNAP-25 knockout mice, in lysed synaptosomes lacking functional SNAP-25 and in cells after treatment with botulinum toxins A or E that specifically cleave SNAP-25. These studies have shown that SNAP-25 appears to be required for most but not all evoked secretion. In order to further study the role of SNAP-25 in catecholamine secretion from PC12 cells we have used the recently developed technique of RNA interference to generate PC12 cell lines with virtually undetectable levels of SNAP-25. RNA interference is the sequence-specific silencing or knockdown of gene expression triggered by the introduction of double-stranded RNA into a cell. RNA interference can be elicited in mammalian cells in a number of ways, one of which is by the expression of small hairpin RNAs from a transfected plasmid. Selection of stably transfected cell lines expressing a small hairpin RNA allows one-time characterization of the degree and specificity of gene silencing and affords a continuing source of well-characterized knockdown cells for experimentation.     

Influence of heat treatment temperature of carbon fiber felt substrate on polyaniline electrosynthesis and its properties

Journal of Solid State Electrochemistry - Polyaniline was electrosynthesized using three voltammetric cycles on carbon fiber felts annealed at 1400, 1600, 2000, and 2300 K. Felts and...     

Interpreting technical evidence from spectral imaging of paintings by Édouard Manet in the Courtauld Gallery

The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.