Low power upconversion using MLCT sensitizers

Selective low energy excitation of the metal-to-ligand charge transfer (MLCT) transition in [Ru(dmb)(3)](2+)(dmb = 4,4'-dimethyl-2,2'-bipyridine) in the presence of anthracene or 9,10-diphenylanthracene yields easily visualized upconverted singlet fluorescence resulting from triplet-triplet annihilation at low excitation power.     

A New Synthesis of Charge‐Neutral Tris‐Pyrazolyl and ‐Methimazolyl Borate Ligands

The dimethylamine in the adducts [(HNMe₂)B(azolyl)₃] (azolyl=methimazolyl, pyrazolyl), obtained by reaction of the azole with B(NMe₂)₃, can readily be substituted with a range of nitrogen donors to provide new charge‐neutral, tripodal ligands in high yield. This observation has led to a revision of an earlier interpretation of the mechanism of the formation of these species. The donor properties of the ligands [(nmi)B(azolyl)₃] (nmi=N‐methylimidazole) have been compared with their anionic analogues [HB(azolyl)₃]^? by synthesis of their manganese(I)–tricarbonyl complexes and comparison of their infrared ν_CO energies. This comparison indicates that the new neutral ligands are only marginally weaker donors than the corresponding anionic hydrotris(azolyl)borate ligands. This may be explained by the ability of the attached nmi ring to stabilize a positive charge remotely from the coordinated metal, which may also account for the fact that the [(nmi)B(pyrazolyl)₃] ligand is a substantially stronger donor than the similarly neutral tris(pyrazolyl)methane ligand.     

Regioregular poly(3‐alkanoylthiophene): Synthesis and electrochemical,photophysical, charge transport,and photovoltaic properties

Head‐to‐tail regioregular poly(3‐heptanoylthiophene) (PHOT) was synthesized by Ni‐catalyzed polycondensation of the 2,2‐dimethyl‐1,3‐propanediol‐protected Grignard monomer followed by deprotection. Cyclic voltammetric (CV) study demonstrates that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of PHOT are 0.5 eV lower in energy than those of the head‐to‐tail poly(3‐hexylthiophene) (HT‐P3HT). Their optical band gaps are essentially the same. Incomplete photoluminescence (PL) quenching was observed in thin films of the 1:1 blend of PHOT and HT‐P3HT. PHOT displayed a glass transition at ～269 °C and decomposed at ～300 °C according to differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Wide‐angle X‐ray diffraction (WAXD) study showed that PHOT exists in a not highly ordered state in solid films especially in the π‐stacking direction. Only p‐channel activity was observed in field‐effect transistors (FETs) for PHOT. The hole mobility was on the order of 10^?4 cm² V^?1 s^?1. Photovoltaic devices with an active layer of 1:1 blend of PHOT and PC₇₁BM had a power conversion efficiency (PCE) of ～0.5%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Hot or not—the influence of elevated temperature and microwave irradiation on the solid phase synthesis of an affibody

Despite the advances of solid phase peptide synthesis (SPPS) the synthesis of long peptides is still challenging. Microwave irradiation and conventional heating are considered to improve the efficiency of SPPS. It has been shown that conventional heating and heating by microwave irradiation improves the efficiency of solid phase synthesis of peptides that are prone to aggregation as compared to the synthesis at room temperature. In this Letter, the influence of elevated temperature and microwave irradiation on the homogeneity of the synthesis product of a 58-mer peptide affibody has been compared. A detailed analysis by high resolution HPLC and LC-MS mass spectrometry using a high-mass resolution Orbitrap Exactive mass spectrometer was performed. This study revealed that neither thermal heating nor microwave heating improves the yield and purity of the crude product as compared to the synthesis at room temperature. In contrast, the formation of undesirable side products rather increased by microwave irradiation. These results indicate that neither heating nor microwave enhancement of solid phase synthesis does allow a significant improvement of peptide sequences with a low aggregation potential.     

Processive replication of single DNA molecules in a nanopore catalyzed by phi29 DNA polymerase

Coupling nucleic acid processing enzymes to nanoscale pores allows controlled movement of individual DNA or RNA strands that is reported as an ionic current/time series. Hundreds of individual enzyme complexes can be examined in single-file order at high bandwidth and spatial resolution. The bacteriophage phi29 DNA polymerase (phi29 DNAP) is an attractive candidate for this technology, due to its remarkable processivity and high affinity for DNA substrates. Here we show that phi29 DNAP-DNA complexes are stable when captured in an electric field across the α-hemolysin nanopore. DNA substrates were activated for replication at the nanopore orifice by exploiting the 3'-5' exonuclease activity of wild-type phi29 DNAP to excise a 3'-H terminal residue, yielding a primer strand 3'-OH. In the presence of deoxynucleoside triphosphates, DNA synthesis was initiated, allowing real-time detection of numerous sequential nucleotide additions that was limited only by DNA template length. Translocation of phi29 DNAP along DNA substrates was observed in real time at ?ngstrom-scale precision as the template strand was drawn through the nanopore lumen during replication.     

Influence on elemental status by hip-endoprostheses

For many clinical purposes various artificial devices are applied, which contact human tissue and can thus cause adverse reactions between prosthetic surfaces and body components. Of the many materials applied for orthopaedic joint replacements the most common are cobalt-chromium-molybdenum alloys. In these cases considerable amounts of cobalt-chromium-molybdenum wear particles are released from the prostheses which have to be regarded as a cause of long-time problems for the patient.Since these particles are dissolved in body fluids of the surrounding area they are distributed in the whole body via blood. Elevated metal concentrations have been found in blood and urine of persons with endoprostheses. Partly the metals are excreted via urine, but to some extend they accumulate in different organs.Therefore this study dealt with the development of an analytical method for the determination of seven relevant trace elements, namely Al, Co, Cr, Mo, Nb, Ni, and Ti in nine kinds of human tissue (brain, heart, kidney, liver, lung, muscle, lymphatic nodes, spleen, body fat) starting with drawing of the sample, sample work up and finally analysis by means of atomic spectrometry. The optimized method was then applied to determine the metal contents in organs of persons (post mortem) with total hip replacements with metal on metal bearing surfaces. Comparison of the data obtained with those of persons without hip-endoprostheses shows that brain and lung are the main targets for elemental accumulation in persons with hip-endoprostheses. Mo and Nb represent the elements with the highest tendency to be accumulated.