Oxidative coupling as a biomimetic approach to the synthesis of scytonemin

The first total synthesis of the dimeric alkaloid pigment scytonemin is described. The key transformations in its synthesis from 3-indole acetic acid are a Heck carbocyclization and a Suzuki-Miyaura cross-coupling, orchestrated in a stereospecific tandem fashion, followed by a biosynthetically inspired oxidative dimerization. The tandem sequence generates a tetracyclic (E)-3-(arylidene)-3,4-dihydrocyclopenta[b]indol-2(1H)-one that is subsequently dimerized into the unique homodimeric core structure of scytonemin.     

Carbon stripper foils for high current heavy ion operation

For the proposed new heavy ion linac@GSI the installation of a carbon foil stripper section is under discussion. High duty factor as well as high current (but low duty factor) heavy ion beams were used for machine experiments. Long term tests were performed to check the carbon foil durability. Relevant beam parameters have been measured in three measurement campaigns. After beam testing stripper foils were analyzed with different offline methods. Additionally promising results of high current beam irradiation of rotating target wheels will be presented. In the transfer line to the SIS 18 the heavy ion beam is stripped to higher charge states in a thick carbon foil. The stripper foil is loaded with 3 % of the beam power. To avoid evaporation in a single beam pulse, the beam is rapidly swept over its width. Experiences collected during the last decade of foil stripper operation at GSI will be presented.     

A tandem MS precursor-ion scan approach to identify variable covalent modification of albumin Cys34: a new tool for studying vascular carbonylation

We developed a liquid chromatography electrospray ionisation multi-stage mass spectrometry (LC-ESI-MS/MS) approach based on precursor-ion scanning and evaluated it to characterize the covalent modifications of Cys34 human serum albumin (HSA) caused by oxidative stress and reactive carbonyl species (RCS) adduction. HSA was isolated and digested enzymatically to generate a suitable-length peptide (LQQCPF) containing the modified tag residue. The resulting LQQCPF peptides were identified by LC-ESI-MS/MS in precursor-ion scan mode and further characterized in product-ion scan mode. The product ions for precursor-ion scanning were selected by studying the MS/MS fragmentation of a series of LQQCPF derivatives containing Cys34 modified with different alpha,beta-unsaturated aldehydes and di and ketoaldehydes. We used a Boolean logic to enhance the specificity of the method: this reconstitutes a virtual current trace (vCT) showing the peaks in the three precursor-ion scans, marked by the same parent ion. The method was first evaluated to identify and characterize the Cys34 covalent adducts of HSA incubated with 4-hydroxy-hexenal, 4-hydroxy-trans-2-nonenal (HNE) and acrolein (ACR). Then we studied the Cys34 modification of human plasma incubated with mildly oxidized low-density lipoproteins (LDL), and the method easily identified the LQQCPF adducts with HNE and ACR. In other experiments, plasma was oxidized by 2,2'-azobis(2-amidinopropane) HCl (AAPH) or by Fe2+/H2O2. In both conditions, the sulfinic derivative of LQQCPF was identified and characterized, indicating that the method is suitable not only for studying RCS-modified albumin, but also to check the oxidative state of Cys34 as a marker of oxidative damage.     

Carbonated ferric green rust as a new material for efficient phosphate removal

Novel TiO(2)/carbon nanocomposites were prepared through the pyrolysis of TiO(2)/poly(furfuryl alcohol) hybrid materials, which were obtained by the sol-gel method, starting from titanium tetraisopropoxide (TTIP) and furfuryl alcohol (FA) precursors. Six different TiO(2)/C samples were prepared based on different TiO(2) nanoparticle sizes and TiO(2)/FA ratios. All of the samples were characterized using X-ray diffraction, infrared, and Raman spectroscopy. The results indicated effective FA polymerization onto the TiO(2) (anatase) nanoparticles, polymer conversion to disordered carbon following the pyrolysis, and a simultaneous TiO(2) anatase-rutile phase transition. The resulting TiO(2)/carbon composites were used as photocatalysts in the advanced oxidative process (AOP) for the degradation of reactive organic dyes in aqueous solution. The results indicate excellent photocatalytic performance (degradation of 99% of the dye after 60 min) with several advantages over traditional TiO(2)-based photocatalysts.     

Combination of DQ and ZQ Coherences for Sensitive Through‐Bond NMR Correlation Experiments in Biosolids under Ultra‐Fast MAS

A double‐zero quantum (DZQ)‐refocused INADEQUATE experiment is introduced for J‐based NMR correlations under ultra‐fast (60 kHz) magic angle spinning (MAS). The experiment records two spectra in the same dataset, a double quantum–single quantum (DQ‐SQ) and zero quantum–single quantum (ZQ‐SQ) spectrum, whereby the corresponding signals appear at different chemical shifts in ω₁. Furthermore, the spin‐state selective excitation (S³E) J‐decoupling block is incorporated in place of the second refocusing echo of the INADEQUATE scheme, providing an additional gain in sensitivity and resolution. The two sub‐spectra acquired in this way can be treated separately by a shearing transformation, producing two diagonal‐free single quantum (SQ‐SQ)‐type spectra, which are subsequently recombined to give an additional sensitivity enhancement, thus offering an improvement greater than a factor of two as compared to the original refocused INADEQUATE experiment. The combined DZQ scheme retains transverse magnetization on the initially polarized (I) spin, which typically exhibits a longer transverse dephasing time (T₂′) than its through‐bond neighbour (S). By doing so, less magnetization is lost during the refocusing periods in the sequence to give even further gains in sensitivity for the J correlations. The experiment is demonstrated for the correlation between the carbonyl (CO) and alpha (CA) carbons in a microcrystalline sample of fully protonated, [¹⁵N,¹³C]‐labelled Cu^II, Zn^II superoxide dismutase, and its efficiency is discussed with respect to other J‐based schemes.     

Validation of the antifactor Xa and antifactor IIa assays for the potency assessment of nadroparin in pharmaceutical formulations

The low-molecular weight heparin nadroparin calcium is used clinically for the prevention and treatment of venous and arterial thrombosis. The antifactor Xa and antifactor IIa assays were validated by investigating the parameters of range, linearity (r2 = 0.9905 and r2 = 0.9914, respectively) precision, accuracy, and robustness. The 2 methods incorporated a chromogenic endpoint and detection at 405 nm, yielding good results with detection limits of 0.004 and 0.01 IU/mL and quantitation limits of 0.01 and 0.03 IU/mL, respectively, for the antifactor Xa and antifactor IIa assays. Nadroparin calcium pharmaceutical products were evaluated by the antifactor Xa assay and the antifactor IIa assay, giving potencies between 93.86 and 109.88%, with an antifactor Xa/antifactor IIa ratio between 3.2 and 3.7. The results demonstrated the validity of the assays that are useful methodologies for the routine quality control of nadroparin in pharmaceutical formulations.     

Seebeck coefficients of half-metallic ferromagnets

In this article the Co₂ based Heusler compounds are discussed as potential materials for spin voltage generation. The compounds were synthesized by arc melting and consequent annealing. Band structure calculations were performed which revealed the compounds to be half-metallic ferromagnets. Magnetometry was performed on the samples and the Curie temperatures and the magnetic moments were determined. The Seebeck coefficients were measured from low to ambient temperatures for all compounds. For selected compounds high temperature measurements up to 900 K were performed.