Furan–thiophene copolymers: Electrosynthesis and electrochemical behavior

The electrochemical copolymerization of furan and thiophene was performed at a constant electrode potential in a binary solvent system consisting of boron trifluoride/ethyl ether and an additional amount of ethyl ether (molar ratio = 1 : 2). The obtained homopolymers and copolymers were characterized with cyclic voltammetry and infrared spectroscopy. The influence of the applied electropolymerization potential and the monomer feed ratio of furan and thiophene on the copolymers was investigated. The furan–thiophene copolymers showed good stability of the redox activity in an acetonitrile‐based electrolyte solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Reprint of “Suppressing propylene carbonate decomposition by coating graphite electrode foil with silver”

A method has been developed to suppress the decomposition of propylene carbonate (PC) by coating graphite electrode foil with a layer of silver. Results from electrochemical impedance measurements show that the Ag-coated graphite electrode presents lower charge transfer resistance and faster diffusion of lithium ions in comparison with the virginal one. Cyclic voltammograms and discharge-charge measurements suggest that the decomposition of propylene carbonate and co-intercalation of solvated lithium ions are prevented, and lithium ions can reversibly intercalate into and deintercalate from the Ag-coated graphite electrode. These results indicate that Ag-coating is a good way to improve the electrochemical performance of graphitic carbon in PC-based electrolyte solutions.     

Preparation and characterisation of titanium dioxide films for catalytic applications generated by anodic spark deposition

The advanced plasma electrochemical process of anodic spark deposition (ASD) was used to generate photoactive titanium dioxide films on titanium metal substrates. A shift to easier-to-machine substrates was demonstrated by the deposition of a titanium film with physical vapour deposition onto different materials such as glass, silicon, and stainless steel prior to ASD. Obtained films were characterised by scanning electron microscopy, surface area measurement (Brunnauer-Emmett-Teller method, BET), X-ray diffraction, electron-probe microanalysis, and glow discharge spectroscopy. Additionally, film thickness was determined by eddy current measurements. Standard ASD conditions were defined as 180 V applied voltage over a 180 s hold time, a voltage ramp of 20 V/s, a duty cycle of 0.5 and a frequency of 1500 Hz. Most prominent characteristics of the titanium films produced under these standard conditions are a film thickness of ≤80 μm, a surface area of approximately 51 m²/g (BET) and an anatase content of approximately 30% and rutile content of approximately 70%. Furthermore, the film formation process is elucidated and the dependence of film thickness on deposition time and the dependence of the anatase and rutile content on the deposited mass are shown for varying ASD conditions.     

Landscape of Genomic Alterations and PD-L1 Expression in Early-Stage Non-Small-Cell Lung Cancer (NSCLC)—A Single Center,Retrospective Observational Study

Precision oncology and immunotherapy have revolutionized the treatment of advanced non-small-cell lung cancer (NSCLC). Emerging studies show that targeted therapies are also beneficial for patients with driver alterations such as epidermal growth factor receptor (EGFR) mutations in early-stage NSCLC (stages I–IIIA). Furthermore, patients with elevated programmed death-ligand 1 (PD-L1) expression appear to respond favorably to adjuvant immunotherapy. To determine the frequency of genomic alterations and PD-L1 status in early-stage NSCLC, we retrospectively analyzed data from 2066 unselected, single-center patients with NSCLC diagnosed using next-generation sequencing and immunohistochemistry. Nine-hundred and sixty-two patients (46.9%) presented with early-stage NSCLC. Of these, 37.0% had genomic alterations for which targeted therapies have already been approved for advanced NSCLC. The frequencies of driver mutations in the early stages were equivalent to those in advanced stages, i.e., the rates of EGFR mutations in adenocarcinomas were 12.7% (72/567) and 12.0% (78/650) in early and advanced NSCLC, respectively (p = 0778). In addition, 46.3% of early-stage NSCLC cases were PD-L1-positive, with a tumor proportion score (TPS) of ≥1%. With comparable frequencies of driver mutations in early and advanced NSCLC and PD-L1 overexpression in nearly half of patients with early-stage NSCLC, a broad spectrum of biomarkers for adjuvant and neoadjuvant therapies is available, and several are currently being investigated in clinical trials.     

Growth and exopolysaccharide yield of Lactobacillus delbrueckii ssp. bulgaricus DSM 20081 in batch and continuous bioreactor experiments at constant pH

Some Lactobacillus delbrueckii ssp. bulgaricus strains are able to synthesize exopolysaccharides (EPS) and are therefore highly important for the dairy industry as starter cultures. The aim of this study was to investigate the nutritional requirements for growth and EPS production of Lactobacillus delbrueckii ssp. bulgaricus DSM 20081. A medium was developed from a semi-defined medium (SDM) in which glucose was replaced by lactose and different combinations of supplements (nucleobases, vitamins, salts, sodium formate and orotic acid) were added. Constant pH batch fermentation with the modified medium resulted in an EPS yield of approximately 210 mg glucose equivalents per liter medium. This was a 10-fold increase over flask cultivation of this strain in SDM. Although not affecting cell growth, the mixture of salts enhanced the EPS synthesis. Whereas EPS production was approximately 12 mg/g dry biomass without salt supplementation, a significantly higher yield (approximately 20 mg/g dry biomass) was observed after adding the salt mixture. In continuous fermentation, a maximal EPS concentration was obtained at a dilution rate of 0.31/h (80 mg EPS/L), which corresponded to a specific EPS production of 49 mg/g dry biomass.     

Stimulation of Bone Healing by Sustained Bone Morphogenetic Protein 2 (BMP-2) Delivery

The aim of the study was to investigate the effect of a sustained release of bone morphogenetic protein2 (BMP-2) incorporated in a polymeric implant coating on bone healing. In vitro analysis revealed a sustained, but incomplete BMP-2 release until Day 42. For the in vivo study, the rat tibia osteotomy was stabilized either with control or BMP-2 coated wires, and the healing progress was followed by micro computed tomography (μCT), biomechanical testing and histology at Days 10, 28, 42 and 84. MicroCT showed an accelerated formation of mineralized callus, as well as remodeling and an increase of mineralized/total callus volume (p = 0.021) at Day 42 in the BMP-2 group compared to the control. Histology revealed an increased callus mineralization at Days 42 and 84 (p = 0.006) with reduced cartilage at Day 84 (p = 0.004) in the BMP-2 group. Biomechanical stiffness was significantly higher in the BMP-2 group (p = 0.045) at Day 42. In summary, bone healing was enhanced after sustained BMP-2 application compared to the control. Using the same drug delivery system, but a burst release of BMP-2, a previous published study showed a similar positive effect on bone healing. Distinct differences in the healing outcome might be explained due to the different BMP release kinetics and dosages. However, further studies are necessary to adapt the optimal release profiles to physiological mechanisms.     

Bifunctional electrodes for an integrated water-electrolysis and hydrogen-oxygen fuel cell with a solid polymer electrolyte

An alternative concept of an integrated water electrolysis/hydrogen-hydrogen fuel cell using metal electrocatalysts and a solid polymer electrolyte is described. Instead of operating both electrodes as hydrogen and oxygen electrodes respectively the electrodes are used as oxidation and reduction electrodes in both modes of operation. A more suitable selection of electrocatalysts and an improved cell design are possible; both can increase the efficiency of the cell considerably. New results on the electrocatalytic activity of various noble-metal containing catalysts with respect to both oxygen evolution and hydrogen oxidation in a proton exchange membrane-cell at 80°C are reported. Kinetic data derived from Tafel plots of the oxygen evolution polarization curves agree closely with those of experiments with aqueous sulphuric acid electrodes. This agreement allows the determination of kinetic parameters for electrocatalysts difficult to prepare in solid smooth electrodes but easy to be made into porous deposits. Polarization curves of the hydrogen oxidation reaction clearly indicate a relative activity rating of the studied catalysts. In cycling tests the lifetime stability of the new bifunctional oxidation electrode was determined. Polarization data obtained under these conditions agree with those obtained in earlier experiments where electrodes were exposed to only one type of oxidation reaction. During a test of 10 cycles (30 min of electrolyser and 30 min of fuel cell mode each) no changes in the electrode potential were observed. With the conventional cell design employing a hydrogen and an oxygen electrode both catalyzed with platinum and a current density of 100 mA cm^–2 a storage efficiency of 50% was calculated; with the alternative concept of oxidation and reduction electrodes and selected oxidation catalysts this was improved to 57%. With further improvements these efficiencies seem possible even at current densities of 500 mA cm^–2.     

Electrochemical and DFT-studies of substituted thiophenes

UV-vis absorption spectra and cyclic voltammograms of a selection of substituted thiophenes and their oligomers carrying trifluoracetyl acetone functional groups have been obtained. A comparison with calculated values of HOMO-LUMO energies (the former corresponding to the ionization potentials E_i) shows strong correlations between calculated and experimentally obtained data; they are in close agreement with estimates in terms of electron-donating and -withdrawing effects from an empirical point of view.