Crystalline polymers in real space

Recent work has resolved uncertainties as to how polymers develop their melt-crystallized textures and brought a unified context to the subject. Spherulites form because of the long molecular length not because of its polydispersity. When a molecule is only partly attached to a growing lamella the unattached portions will occupy adjacent space and exert a short-range repulsive pressure on any neighbouring lamella at a branch point. This is confirmed by monodisperse long n-alkanes forming spherulites only with chainfolded lamellae not when crystallizing as extended chains. An additional textural element, cellulation, is superposed on regular spherulitic growth beyond a certain radius (in linear-low-density polyethylenes) when there is sufficient fractional crystallization of segregated species which lower the local equilibrium melting temperature and thence the isothermal supercooling and growth rate, the last declining continuously to an asymptotic limit. First results show that both the radius to cellulation and the cell width are effectively independent of growth velocity; neither scales with the diffusion length. A possible explanation is proposed for this novel situation which has no precedent in either polymeric or non-polymeric systems.     

Analysis of large screening data sets via adaptively grown phylogenetic-like trees

As the use of high-throughput screening systems becomes more routine in the drug discovery process, there is an increasing need for fast and reliable analysis of the massive amounts of the resulting data. At the forefront of the methods used is data reduction, often assisted by cluster analysis. Activity thresholds reduce the data set under investigation to manageable sizes while clustering enables the detection of natural groups in that reduced subset, thereby revealing families of compounds that exhibit increased activity toward a specific biological target. The above process, designed to handle primarily data sets of sizes much smaller than the ones currently produced by high-throughput screening systems, has become one of the main bottlenecks of the modern drug discovery process. In addition to being fragmented and heavily dependent on human experts, it also ignores all screening information related to compounds with activity less than the threshold chosen and thus, in the best case, can only hope to discover a subset of the knowledge available in the screening data sets. To address the deficiencies of the current screening data analysis process the authors have developed a new method that analyzes thoroughly large screening data sets. In this report we describe in detail this new approach and present its main differences with the methods currently in use. Further, we analyze a well-known, publicly available data set using the proposed method. Our experimental results show that the proposed method can improve significantly both the ease of extraction and amount of knowledge discovered from screening data sets.     

Fully fluorinated imidodiphosphinate shells for visible- and NIR-emitting lanthanides: hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C--F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di(pentafluorophinoyl)}-P,P-dipentafluorophenylphosphinimidic acid (HF20tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X--H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F20tpip)3], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF20tpip and [Gd(F20tpip)3] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F20tpip)3] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F20tpip)3], [Er(F20tpip)3] and [Yb(F20tpip)3] in deuteurated acetonitrile are 44, 741 and 1111 micros. The highest value observed for the [Yb(F20tpip)3] complex is more than half the value of the Yb ion radiative lifetime.     

Electron microscopy and quantitative polymer morphology

The lamellar nature of semi-crystalline polymers can now be studied systematically using transmission electron microscopy, especially following permanganic etching. In combination with thermal analysis and selective extraction followed by molecular characterisation, this approach allows the distribution of lamellae, thermal stability and molecular constitution to be mapped in real space. Extension of this methodology has allowed the extraction of individual melt-crystallized lamellae from bulk polymer. Their study is adding to understanding of fundamental processes of crystal growth.     

Neuropeptide delivery to the brain: a von Willebrand factor signal peptide to direct neuropeptide secretion

Background  

Multiple neuropeptides, sometimes with opposing functions, can be produced from one precursor gene. To study the roles of the different neuropeptides encoded by one large precursor we developed a method to overexpress minigenes and establish local secretion.     

Quantitative Spektralanalyse

Ohne Zusammenfassung     

Neutral transverse momentum spectra in 60 and 200A·GeV16O+nucleus and proton+nucleus reactions

Transverse momentum (p _T) distributions fo inclusive photons and neutral pions at midrapidity are measured with a lead glass calorimeter in 60 and are measured with a lead glass calorimeter in 60 and 200A·Gev¹⁶O+nucleus and and proton+nucleus reactions. Inclusive photon distributions are compared for central and peripheral reactions. The degree of centrality is determined either from the charged particle multiplicity or from the remaining projectile energy in the forward direction. Deviations from a nucleus+nucleus interaction model based upon linear extrapolation from p+p reactions are observed in central¹⁶O+Au data. The variation of theaverage transverse momentum is investigated as function of centrality. The target-mass and energy dependence of π⁰ p _T distributions are presented. For¹⁶O+Au a change of slope in these distributions is observed atp _t ≈0.8 GeV/c compatible with hydrodynamic expansion models.     

A Diselenide Turn-On Fluorescent Probe for the Detection of Thioredoxin Reductase

We report the first diselenide-based probe for the selective detection of thioredoxin reductase (TrxR), an enzyme commonly overexpressed in melanomas. The probe design involves conjugation of a seminaphthorhodafluor dye with a diselenide moiety. TrxR reduces the diselenide bond, triggering a fluorescence turn-on response of the probe. Kinetic studies reveal favorable binding of the probe with TrxR with a Michaelis–Menten constant (K_m) of 15.89 μm . Computational docking simulations predict a greater binding affinity to the TrxR active site in comparison to its disulfide analogue. In vitro imaging studies further confirmed the diselenide probe exhibited improved signaling of TrxR activity compared to the disulfide analogue.     

Changes in the melting behavior with the radial distance in isotactic polypropylene spherulites

The melting of highly tactic i‐polypropylene occurs in two stages even for crystallization at 145 °C, a temperature at which reorganization during scanning is negligible. A comparison of two such polypropylenes, one nucleated and the other not nucleated, together with fractions from the latter, has been made with electron microscopy following permanganic etching, in addition to differential scanning calorimetry. This has allowed the two melting stages to be assigned to two components of the lamellar morphology, with progressive changes in both occurring with increasing radial distance within a spherulite. The highest melting temperature is for dominant radial lamellae far from a spherulite center. The lowest melting regions are the evenly crosshatched spherulite centers and a narrow peripheral band. Lower melting is attributed to the suppression of isothermal lamellar thickening paralleling recent direct demonstrations in polyethylene. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2342–2354, 2003