Greenish‐yellow‐, yellow‐, and orange‐light‐emitting iridium(III) polypyridyl complexes with poly(ε‐caprolactone)–bipyridine macroligands

A set of novel greenish‐yellow‐, yellow‐, and orange‐light‐emitting polymeric iridium(III) complexes were synthesized with the bridge‐splitting method. The respective dimeric precursor complexes, [Ir(ppy)₂‐μ‐Cl]₂ (ppy = 2‐phenylpyridine) and [Ir(ppy? CHO)₂‐μ‐Cl]₂ [ppy? CHO = 4‐(2‐pyridyl)benzaldehyde], were coordinated to 2,2′‐bipyridine carrying poly(ε‐caprolactone) tails. The resulting emissive polymers were characterized with one‐dimensional (¹H) and two‐dimensional (¹H? ¹H correlation spectroscopy) nuclear magnetic resonance and infrared spectroscopy, gel permeation chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and the successful coordination of the iridium(III) centers to the 2,2′‐bipyridine macroligand was revealed. The thermal behavior was studied with differential scanning calorimetry and correlated with atomic force microscopy. Furthermore, the quantitative coordination was verified by both the photophysical and electrochemical properties of the mononuclear iridium(III) compounds. The photoluminescence spectra showed strong emissions at 535 and 570 nm. The color shifts depended on the substituents of the cyclometallating ligands. Cyclic voltammetry gave oxidation potentials of 1.23 V and 1.46 V. Upon the excitation of the films at 365 nm, yellow light was observed, and this could allow potential applications in light‐emitting devices. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2765–2776, 2005     

Eine vereinfachte Methode zur Bestimmung der Alkali-Labilit?t von St?rkeprodukten

Ohne Zusammenfassung     

Surface and bulk morphology of cold-crystallized poly(ethylene terephthalate)

The morphology/habit of crystals of cold-crystallized poly(ethylene terephthalate) (PET) has been evaluated using scanning and transmission electron microscopy and using atomic force microscopy. The combination of different preparation and analysis techniques allowed assessing the structure at the nanometer scale of films of PET at both the surface and the bulk. It is found that crystals formed on heating the amorphous glass to a temperature higher than the glass transition temperature are of lamellar shape in the bulk and almost isometric habit at the surface. This finding is explained by different rates of nucleation/crystallization in the bulk and at the surface, being supported by the observation of nanometer-scale surface heterogeneities after quenching PET to ambient temperature before crystallization was initiated by heating.     

Structure elucidation of the unprecedented asymmetric bis-chelate complex [Pd(1,3-bis(di(o-methoxy-m-methylphenyl)phosphino)propane)2]2+ in the solid state and in solution

Complexes of the type [Pd(ligand)(2)](anion)(2) were prepared with a series of bidentate di(o-methoxyphenyl)phosphine ligands with increasing steric bulk on the meta position of the phenyl groups: m-H (L1); m-MeO (L2); and m-Me (L3). The solid-state structure of [Pd(L2)(2)](OTs)(2) revealed that the two ligands are symmetrically coordinated to Pd(2+). In the solid state structure of [Pd(L3)(2)](OTs)(2) however, the two ligands are unsymmetrically coordinated to Pd(2+), yielding an unprecedented conformation of this bis-chelate P(4)Pd(2+) complex. (1)H-(1)H-COSY and NOESY analysis and a (31)P-NMR simulation showed that the asymmetric structure of [Pd(L3)(2)](OTs)(2) is retained in solution.     

Automated mass spectrometric analysis of urinary and plasma serotonin

Serotonin emerges as crucial neurotransmitter and hormone in a growing number of different physiologic processes. Besides extensive serotonin production previously noted in patients with metastatic carcinoid tumors, serotonin now is implicated in liver cell regeneration and bone formation. The aim was to develop a rapid, sensitive, and highly selective automated on-line solid-phase extraction method coupled to high-performance liquid chromatography–tandem mass spectrometry (XLC-MS/MS) to quantify low serotonin concentrations in matrices such as platelet-poor plasma and urine. Fifty microliters plasma or 2.5 μL urine equivalent were pre-purified by automated on-line solid-phase extraction, using weak cation exchange. Chromatography of serotonin and its deuterated internal standard was performed with hydrophilic interaction chromatography. Mass spectrometric detection was operated in multiple reaction monitoring mode using a quadrupole tandem mass spectrometer with positive electrospray ionization. Serotonin concentrations were determined in platelet-poor plasma of metastatic carcinoid patients (n = 23) and healthy controls (n = 22). Urinary reference intervals were set by analyzing 24-h urine collections of 120 healthy subjects. Total run-time was 6 min. Intra- and inter-assay analytical variation were <10%. Linearity in the 0–7300 μmol/L calibration range was excellent (R² > 0.99). Quantification limits were 30 and 0.9 nmol/L in urine and plasma, respectively. Platelet-poor serotonin concentrations in metastatic carcinoid patients were significantly higher than in controls. The urinary reference interval was 10–78 μmol/mol creatinine. Serotonin analysis with sensitive and specific XLC-MS/MS overcomes limitations of conventional HPLC. This enables accurate quantification of serotonin for both routine diagnostic procedures and research in serotonin-related disorders.     

Subpicosecond pulse generation from a 1.56 μm mode-locked VECSEL

Near-transform-limited subpicosecond pulses at 1.56 μm were generated from an optically pumped InP-based vertical-external-cavity surface-emitting laser (VECSEL) passively mode-locked at 2 GHz repetition rate with a fast InGaAsNSb/GaAs semiconductor saturable absorber mirror (SESAM). The SESAM microcavity resonance was adjusted via a selective etching of phase layers specifically designed to control the magnitude of both the modulation depth and the intracavity group delay dispersion of the SESAM. Using the same VECSEL chip, we observed that the mode-locked pulse duration could be reduced from several picoseconds to less than 1 ps with a detuned resonant SESAM.