FLAVIN-PHOTOREDUCTION BY CYANIDE: NUCLEOPHILIC ADDITION IN THE EXCITED TRIPLET STATE

Abstract— Flavin photochemistry as well as biochemistry consists of competitive 1e⁻ - and 2e⁻ -reduction pathways, depending on the nature of the substrate. We show that cyanide ion is a photosubstrate which suppresses 1e⁻-oxidoreduction and leads to exclusive formation of 6- and 9-cyano-1,5-dihydroflavin. The photoreduction mechanism is thus revealed as a nucleophilic addition of cyanide ion at the excited flavin triplet. Preparative photochemistry and isolation and characterization of cyanoflavins have been done, as well as thorough mechanistic studies by conventional flash photolysis. In contrast, nitrite ion is shown to be a normal photosubstrate for flavins leading to exclusive 1e⁻ -transfer followed by back donation.     

Solutions for biomedical grid computing—Case studies from the D-Grid project Services@MediGRID

The project Services@MediGRID consortium established a tool set of grid-based biomedical services since 2008. The services are related to genetic analysis, genome data visualization, and pharmacokinetic modeling. Furthermore, business concepts for these services have been examined which are supported by an accounting and billing service. While the tools cover a whole service chain for biomedicine, the business concepts are rather heterogeneous. However, the overall addressed target market areas show promising potential. In addition, a structured coaching process reduces friction in the technology transfer from grid computing to biomedicine. This should be considered for similar future endeavors.     

Phosphonylation Controls the Protein Corona of Multifunctional Polyglycerol‐Modified Nanocarriers

Nanocarriers are a platform for modern drug delivery. In contact with blood, proteins adsorb to nanocarriers, altering their behavior in vivo. To reduce unspecific protein adsorption and unspecific cellular uptake, nanocarriers are modified with hydrophilic polymers like poly(ethylene glycol) (PEG). However, with PEG the attachment of further functional structures such as targeting units is limited. A method to introduce multifunctionality via polyglycerol (PG) while maintaining the hydrophilicity of PEG is introduced. Different amounts of negatively charged phosphonate groups (up to 29 mol%) are attached to the multifunctional PGs (M_n 2–4 kg mol^?1, Ð < 1.36) by post‐modification. PGs are used in the miniemulsion/solvent evaporation procedure to prepare model nanocarriers. Their behavior in human blood plasma is investigated to determine the influence of the negative charges on the protein adsorption. The protein corona of PGylated nanocarriers is similar to PEGylated analogs (on same nanocarriers), but the protein pattern could be gradually altered by the integration of phosphonates. This is the first report on the gradual increase of negative charges on nanocarriers and intriguingly up to a certain amount of phosphonate groups per nanocarrier the protein pattern remains relatively unchanged, which is important for the future design of nanocarriers.     

Die isotherme Kompressibilität einiger amorpher und teilkristalliner Hochpolymerer im Temperaturbereich von 20–250 °C und bei Drucken bis zu 2000 kp/cm2

Ohne Zusammenfassung Mit 12 Abbildungen and 6 Tabellen Vorgetragen in der Sitzung des Fachausschusses Hochpolymere auf der Jahrestagung des Verbandes Deutscher Physikalischer Gesellschaften in Wien am 20. Oktober 1961.     

Unveiling Luminescent IrI and RhI N-Heterocyclic Carbene Complexes: Structure,Photophysical Specifics,and Cellular Localization in the Endoplasmic Reticulum

Complexes of Rh^I and Ir^I of the [M(COD)(NHC)X] type (where M=Rh or Ir, COD=1,5-cyclooctadiene, NHC=N-heterocyclic carbene, and X=halide) have recently shown promising cytotoxic activities against several cancer cell lines. Initial mechanism of action studies provided some knowledge about their interaction with DNA and proteins. However, information about their cellular localization remains scarce owing to luminescence quenching within this complex type. Herein, the synthesis of two rare examples of luminescent Rh^I and Ir^I [M(COD)(NHC)I] complexes with 1,8-naphthalimide-based emitting ligands is reported. All new complexes are comprehensively characterized, including with single-crystal X-ray structures. Steric crowding in one derivative leads to two distinct rotamers in solution, which apparently can be distinguished both by pronounced NMR shifts and by their respective spectral and temporal emission signatures. When the photophysical properties of these new complexes are exploited for cellular imaging in HT-29 and PT-45 cancer cell lines, it is demonstrated that the complexes accumulate predominantly in the endoplasmic reticulum, which is an entirely new finding and provides the first insight into the cellular localization of such Ir^I(NHC) complexes.     

Spin‐Crossover Complex on Au(111): Structural and Electronic Differences Between Mono‐ and Multilayers

Submono‐, mono‐ and multilayers of the Fe(II) spin‐crossover (SCO) complex [Fe(bpz)₂(phen)] (bpz=dihydrobis(pyrazolyl)borate, phen=1,10‐phenanthroline) have beenprepared by vacuum deposition on Au(111) substrates and investigated with near edge X‐ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM). As evidenced by NEXAFS, molecules of the second layer exhibit a thermal spin crossover transition, although with a more gradual characteristics than in the bulk. For mono‐ and submonolayers of [Fe(bpz)₂(phen)] deposited on Au(111) substrates at room temperature both NEXAFS and STM indicate a dissociation of [Fe(bpz)₂(phen)] on Au(111) into four‐coordinate complexes, [Fe(bpz)₂], and phen molecules. Keeping the gold substrate at elevated temperatures ordered monolayers of intact molecules of [Fe(bpz)₂(phen)] are formed which can be spin‐switched by electron‐induced excited spin‐state trapping (ELIESST).     

Using linear programming to analyze and optimize stochastic flow lines

This paper presents a linear programming approach to analyze and optimize flow lines with limited buffer capacities and stochastic processing times. The basic idea is to solve a huge but simple linear program that models an entire simulation run of a multi-stage production process in discrete time, to determine a production rate estimate. As our methodology is purely numerical, it offers the full modeling flexibility of stochastic simulation with respect to the probability distribution of processing times. However, unlike discrete-event simulation models, it also offers the optimization power of linear programming and hence allows us to solve buffer allocation problems. We show under which conditions our method works well by comparing its results to exact values for two-machine models and approximate simulation results for longer lines.