Strongly Phosphorescent Iridium(III)-Porphyrins - New Oxygen Indicators with Tuneable Photophysical Properties and Functionalities

Synthesis and characterization of four iridium(III)-octaethylporphyrins and a π-extended iridium(III)-benzoporphyrin are presented. Strong room-temperature phosphorescence was observed for all of the complexes with quantum yields of up to 30 %. Axial ligands were introduced to tune the photophysical properties and the solubility. Complexes bearing lipophilic ligands such as pyridine or N-(n-butyl)imidazole were incorporated into polystyrene to obtain optical oxygen sensors. Covalent coupling of the dye is possible by introduction of ligands with binding domains (1-imidazoleacetic acid). This enabled preparation of a water-soluble oxygen probe (by staining bovine serum albumin) and a trace oxygen sensor (by coupling to amino-modified silica gel).     

Synthesis and structure‐activity relationship of several aromatic ketone‐based two‐photon initiators

Several novel aromatic ketone‐based two‐photon initiators containing triple bonds and dialkylamino groups were synthesized and the structure‐activity relationships were evaluated. Branched alkyl chains were used at the terminal donor groups to improve the solubility in the multifunctional monomers. Because of the long conjugation length and good coplanarity, the evaluated initiators showed large two‐photon cross section values, while their fluorescence lifetimes and quantum yields strongly depend on the solvent polarity. All novel initiators exhibited high activity in terms of two‐photon‐induced microfabrication. This is especially true for fluorenone‐based derivatives, which displayed much broader processing windows than well‐known highly active initiators from the literature and commercially available initiators. While the new photoinitiators gave high reactivity in two‐photon‐induced photopolymerization at concentration as low as 0.1% wt, these compounds are surprisingly stable under one photon condition and nearly no photo initiation activity was found in classical photo DSC experiment. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Surface‐Plasmon‐Coupled Emission of Rhodamine 110 in a Silica Nanolayer

The first observation of strong directional surface‐plasmon‐coupled emission (SPCE) of Rhodamine 110 in silica nanofilms deposited on silver nanolayers is reported. The preparation of the material is described in detail. The intensity of SPCE exceeds 10 times that of free space fluorescence and total linear light polarization in the SPCE ring is observed. A new experimental setup and an original data collection method is presented. Our material completely preserves its fluorescence properties for at least eight months.     

Adsorption and structure formation of the weak polyelectrolytic diblock copolymer,PVP-<Emphasis Type="Italic">b</Emphasis>-PDMAEMA

This paper reports on the pH-dependent adsorption of weak the polyelectrolytic diblock copolymer poly(2-vinylpyridine)-block-poly(dimethylaminoethyl methacrylate), (PVP-b-PDMAEMA). Aqueous PVP-b-PDMAEMA solutions have been adsorbed on alkaline pretreated silicon substrates. Altogether two copolymers differing in block ratio and molecular weight were used for the investigations. While the electrical charge of both samples in solution was investigated by electrophoretic measurements, the adsorbed polymer layers were studied with ellipsometry and atomic force microscopy (AFM). Depending on pH the electrical charge of both blocks of the diblock copolymer varied. Three different regimes have been identified. Under acidic conditions at pH<5, both blocks are mainly positively charged. At medium pH between 5 and 8, only the PDMAEMA block is positively charged. At pH>8, both blocks are nearly uncharged and a polymer precipitation occurred in solution. Each of these pH regimes was characterized by a specific adsorption behaviour leading to two adsorption maxima at acidic and alkaline pH values, while at medium pH a plateau in the adsorbed amount was observed. Moreover, the structures of the polyelectrolytes formed on the substrate after adsorption were specific to each of the three pH regimes.     

Effect of processing conditions on the properties of high molecular weight conductive polyaniline fiber

Polyaniline–emeraldine base (EB) fiber with excellent mechanical and electrical properties have been spun from highly concentrated (20% w/w), EB/N‐methyl‐2‐pyrrolidinone (NMP)/2‐methylaziridine (2 MA) solution. These solutions had gelation times, which varied from hours to days depending on the molar ratio of 2 MA to EB tetramer repeating unit in the N‐methyl‐2‐pyrrolidinone (NMP) solvent. To better compare the mechanical and electrical properties, dense films were also prepared by thermal evaporation of less concentrated solution (1% w/w). Both fibers and films were amenable to thermal stretching with maximum draw ratios of 4 : 1 and these stretched samples exhibited the greatest tensile strength overall. Wide‐angle X‐ray diffraction (WAXD) of as‐spun and 4‐times stretched fiber showed a completely amorphous structure. Fiber subjected to heat treatment at 250 °C under N₂ flux for 2 h displayed further improvements in mechanical properties because of crosslinking between the polymer chains. Fibers and films were later doped by immersion in a variety of aqueous acid solutions. Room temperature DC conductivities for the doped samples ranged from 6 × 10⁻⁴ to 45 S/cm depending on the specific choice of acid. Scanning electron microscopy of fiber samples shows the presence of macrovoid formation during fiber spinning. Continued refinement of the processing parameters and fiber post‐treatment, to enhance chain alignment and increase fiber density, will likely lead to additional improvements in the fiber mechanical and electrical properties. Characterization of emeraldine base (EB) powder, solution, films, and fibers by UV‐Vis, DSC, TGA, and WAXD were also performed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 194–204, 2000     

Olefin polymerization with Me4Cp–Amido complexes with electron‐withdrawing groups

A series of Me₄Cp–amido complexes {[η⁵:η¹‐(Me₄C₅)SiMe₂NR]TiCl₂; R = t‐Bu, 1 ; C₆H₅, 2 ; C₆F₅, 3 ; SO₂Ph, 4 ; or SO₂Me, 5 } were prepared and investigated for olefin polymerization in the presence of methylaluminoxane (MAO). X‐ray crystallography of complexes 3 and 4 revealed very long Ti N bonds relative to the bonds of 1 . These complexes were employed for ethylene–styrene copolymerizations, styrene homopolymerizations, and propylene homopolymerizations in the presence of MAO. The productivities of the catalysts derived from 3 – 5 were much lower than the productivity of the catalyst derived from 1 for the propylene polymerizations and ethylene–styrene copolymerizations, whereas the styrene polymerization activities were much higher for the catalysts derived from 3 – 5 than for the catalyst derived from 1 . The polymerization behavior of the catalysts derived from the metallocenes 3 – 5 were more reminiscent of monocyclopentadienyl titanocene Cp′TiX₃/MAO catalysts than of CpATiX₂/MAO catalysts such as 1 containing alkylamido ligands. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4649–4660, 2000     

Surface structure analysis of thin dewetted polymer blend films

The surface structure of thin polymer blend films of deuterated polystyrene (dPS) and polyparamethylstyrene (PpMS) after annealing above the glass transition temperature was investigated. With scanning force microscopy (SFM) the surface topography originated by a dewetting process is detected. The sample surface is covered with small droplets consisting of several polymer molecules. Utilizing grazing incidence small angle neutron scattering (GISANS) the topographical information as well as the in‐plane composition is probed. For thin confined blend films a substructure of the droplets resulting from an additional phase separation process at different length scales is detected.     

Organometallic alkane CH activation

The title topic is reviewed with emphasis on catalysis and on recent advances. Alkane σ complexes, Shilov chemistry and oxidative addition routes are covered. Attention is also given to σ bond metathesis, surface-bound organometallics and CH activation involving carbene complexes. Closely related reactions of non-alkane substrates such as the Murai reaction are also discussed.     

Observation of an unprecedented Cu Bis-His site: crystal structure of the H129V mutant of nitrite reductase

Copper nitrite reductases contain both an electron-transfer type 1 Cu site and a catalytic type 2 Cu site. We have mutated one of the type 2 copper ligating histidines to observe the effect on catalytic turnover. This mutation has created a unique site where Cu is ligated by 2 His Nepsilon2 atoms alone.