Direct Mechanocatalysis: Palladium as Milling Media and Catalyst in the Mechanochemical Suzuki Polymerization.

The milling ball is the catalyst. We introduce a palladium-catalyzed reaction inside a ball mill, which makes catalyst powders, ligands, and solvents obsolete. We present a facile and highly sustainable synthesis concept for palladium-catalyzed C-C coupling reactions, exemplarily showcased for the Suzuki polymerization of 4-bromo or 4-iodophenylboronic acid giving poly(para-phenylene). Surprisingly, we observe one of the highest degrees of polymerization (199) reported so far.

Closed-loop laser polishing using in-process surface finish metrology.

This paper lays out the trail onto a closed-loop polishing process of optical elements enabling the application of the optimum polishing time needed. To that aim, an in-process testing method for monitoring an inclusive microsurface quality (e.g., comprising surface roughness and scratch-and-dig) within the polishing spot is analyzed, and its applicability to closed-loop polishing for classical loose-abrasive full-aperture polishing as well as for computer-controlled laser polishing is experimentally tested and verified. This enables the determination of the optimum local dwell time resulting in stable and cost-optimized polishing.

Transfer of skills and comparison of performance between king vision® video laryngoscope and macintosh blade following an AHA airway management course.

BACKGROUND: To potentially optimize intubation skill teaching in an American Heart Association® Airway Management Course® for novices, we investigated the transfer of skills from video laryngoscopy to direct laryngoscopy and vice versa using King Vision® and Macintosh blade laryngoscopes respectively. METHODS: Ninety volunteers (medical students, residents and staff physicians) without prior intubation experience were randomized into three groups to receive intubation training with either King Vision® or Macintosh blade or both. Afterwards they attempted intubation on two human cadavers with both tools. The primary outcome was skill transfer from video laryngoscopy to direct laryngoscopy assessed by first attempt success rates within 60 s. Secondary outcomes were skill transfer in the opposite direction, the efficacy of teaching both tools, and the success rates and esophageal intubation rates of Macintosh blade versus King Vision®. RESULTS: Performance with the Macintosh blade was identical following training with either Macintosh blade or King Vision® (unadjusted odds ratio [OR] 1.09, 95% confidence interval [95% CI] 0.5-2.6). Performance with the King Vision® was significantly better in the group that was trained on it (OR 2.7, 95% CI 1.2-5.9). Success rate within 60 s with Macintosh blade was 48% compared to 52% with King Vision® (OR 0.85, 95% CI 0.4-2.0). Rate of esophageal intubations with Macintosh blade was significantly higher (17% versus 4%, OR 5.0, 95% CI 1.1-23). CONCLUSIONS: We found better skill transfer from King Vision® to Macintosh blade than vice versa and fewer esophageal intubations with video laryngoscopy. For global skill improvement in an airway management course for novices, teaching only video laryngoscopy may be sufficient. However, success rates were low for both devices.

Survey, Analysis and Comparison of Radar Technologies for Embedded Vital Sign Monitoring.

Contactless vital sign monitoring systems are becoming increasing in demand for a wide range of biomedical applications. Millimetre-wave radars and embedded signal processing are the most promising technologies to enable non-contact vital signs monitoring. In this work, the challenging task of heart rate estimation from radar data has been addressed. Three different radar systems from Infineon, Texas Instruments and Acconeer, and four algorithms, FFT, Median-FFT, STFT and Median-STFT, have been analysed and compared against a reference sensor. Accuracy, as well as power figures, have been reported for all the radar systems. A dataset of 16 volunteers has been acquired, yielding a total of 400 minutes of radar-recorded vital sign data. The accuracy of the four investigated algorithms has been reported on average and per subject for every radar. The algorithm exploiting the Short Time Fourier Transform (STFT) is able to achieve an error as low as 0.02% on a single person and of 6.4% in heart rate estimation on average across the whole dataset.

Chemotaxis to the quorum-sensing signal AI-2 requires the Tsr chemoreceptor and the periplasmic LsrB AI-2-binding protein.

AI-2 is an autoinducer made by many bacteria. LsrB binds AI-2 in the periplasm, and Tsr is the l-serine chemoreceptor. We show that AI-2 strongly attracts Escherichia coli. Both LsrB and Tsr are necessary for sensing AI-2, but AI-2 uptake is not, suggesting that LsrB and Tsr interact directly in the periplasm.

Clopidogrel improves endothelial function and NO bioavailability by sensitizing adenylyl cyclase in rats with congestive heart failure.

Clopidogrel treatment in patients with coronary artery disease not only inhibits platelet activation but also improves endothelial function and nitric oxide (NO) bioavailability. Congestive heart failure (CHF) is associated with endothelial dysfunction and increased platelet activation. In rats with CHF following myocardial infarction (MI), we investigated whether treatment with clopidogrel modifies endothelial function. Eight weeks after coronary artery ligation, rats with CHF were randomized to placebo or the P2Y(12) receptor antagonist clopidogrel (5 mg/kg twice daily, given by gavage) for another 2 weeks. Afterwards, endothelial function was assessed in isolated aortic rings in organ bath experiments. Acetylcholine-induced, endothelium-dependent, nitric oxide-mediated vasorelaxation was significantly attenuated in CHF rats compared to sham-operated animals, and was significantly improved by treatment with clopidogrel. Adenosine-induced vasorelaxation via adenylyl cyclase stimulation was attenuated in CHF and significantly improved by clopidogrel. Increased vasoconstriction to phenylephrine was observed in CHF, particularly evident under cyclooxygenase inhibition, but prevented by clopidogrel treatment. Vasoconstriction by the P2Y(12) activator 2MeS-ADP was increased in CHF. Clopidogrel-treated CHF animals displayed enhanced phosphorylation of AKT and eNOS. In conclusion, clopidogrel improved endothelial function and NO bioavailability in heart failure. During CHF, sensitivity to P2Y(12) signaling was increased leading to impaired adenylyl cyclase-mediated signaling. Chronic P2Y(12)-blockade with clopidogrel improved adenylyl cyclase-mediated signaling including increased AKT- and eNOS-phosphorylation contributing to improved NO-mediated vasorelaxation.

In situ cage experiments with Potamopyrgus antipodarum--a novel tool for real life exposure assessment in freshwater ecosystems.

In situ experiments are an important tool within ecotoxicological research but there is a lack of suitable methodologies especially for freshwater invertebrate species. Within this study, a novel in situ methodology with Potamopyrgus antipodarum was developed. Snails were inserted into cages, made of Plexiglas measuring 7 × 9 × 7 cm(3) and fixed with stainless steel pins into the sediment at the relevant sampling sites. During the experiment physico-chemical properties of the water and concentrations of metals, PAHs and PCBs were measured in the sediment. The growth and survival of the snails was not affected, but the reproduction increased significantly at one of the most polluted sites. The increase in reproduction was neither correlated with physico-chemical parameters, nor with the concentrations of the different compounds, but maybe related to certain groups of estrogenic compounds. The study demonstrates the excellent applicability of this novel in situ test.

Effects of cadmium on life-cycle parameters in a multi-generation study with Chironomus riparius following a pre-exposure of populations to two different tributyltin concentrations for several generations.

So far only a few studies have been performed to assess the effects of dynamic pollutant exposure on life-history parameters of invertebrates. In a previous multi-generation approach with the midge Chironomus riparius we tested if a chronic tributyltin pre-exposure alters the ability of a population to cope with subsequent cadmium stress. In the experiment two separate chironomid populations were exposed via sediments to different TBT-concentrations (4.46 and 8.93 µg Sn/kg dw) for several generations, followed by subsequent cadmium exposure (1.2 mg Cd/kg dw) for three generations. While the TBT-exposure to 4.46 µg Sn/kg dw had only small effects on the development and reproduction of C. riparius the higher TBT-concentration of 8.93 µg Sn/kg dw led to negative effects on life-history traits. Therefore, a higher adverse effect of the higher TBT-concentration and thus a higher susceptibility to other stressors could be assumed. Within, this paper only the results of the second stressor experiment were presented; clear effects of Cd on development and reproduction of C. riparius were determined independent of the pre-exposure scenario. While no differences in Cd-sensitivity were found between the population without pre-exposure to TBT and the population pre-exposed to the low TBT-concentration (4.46 µg Sn/kg dw), the pre-exposure of midges to the higher TBT-concentration (8.93 µg Sn/kg dw) resulted in a significantly higher susceptibility to subsequent Cd-stress. These results document that the exposure history may influence the reaction to altered chemical stress. Our findings are relevant to understand and predict the evolutionary fate of populations in rapidly changing, human-impacted environments. However, the fact that chemical-induced reduced genetic diversity, which is not necessarily linked to genetic adaptation, leads to a reduced fitness under altered stress conditions, is to our knowledge a novel finding.

High- and low-temperature modifications of Sc3RuC4 and Sc3OsC4--relativistic effects, structure, and chemical bonding.

Sc(3)RuC(4) and Sc(3)OsC(4) were synthesized by arc-melting and subsequent annealing. At room temperature, they crystallize with the Sc(3)CoC(4) structure, space group Immm. At 223 and 255 K, Sc(3)RuC(4) and Sc(3)OsC(4), respectively, show a monoclinic distortion caused by a pair-wise displacement of the one-dimensional [Ru(C(2))(2)](delta-) and [Os(C(2))(2)](delta-) polyanions, which are embedded in a scandium matrix. Superstructure formation leads to shorter Ru-Ru and Os-Os distances of 316 pm between adjacent [Ru(C(2))(2)](delta-) and [Os(C(2))(2)](delta-) polyanions. Each ruthenium (osmium) atom is covalently bonded to four C(2) pairs with Ru-C (Os-C) distances of 220-222 pm. A comparison of the C-C bond distances at room temperature in Sc(3)TC(4) with T representing a group 8 transition metal (Fe, Ru, Os) reveals a minimum in the case of the 4d metal Ru: 144.98(11) pm (Fe), 142.8(7) pm (Ru), and 144.6(4) pm (Os). Analysis of the local electronic structure of the [T(C(2))(2)] moieties hints at a complex interplay between chemical bonding and relativistic effects, which is responsible for the V-shaped pattern of the C-C bond distances (long, short, and long for T = Fe, Ru, and Os, respectively). Relativistic effects lead to a strengthening of covalent T-C bonding. This is shown on the basis of periodic DFT calculations by a significant increase of the charge density at the T-C bond critical points (0.55 < 0.57 < 0.64 eA(-3)) down the row of group 8 elements. These structural characteristics and topological features do not change in the corresponding low-temperature phases of Sc(3)RuC(4) and Sc(3)OsC(4). However, topological analyses of theoretical charge density distributions reveal distinct changes of the valence shell charge concentrations at the transition metal centers due to the monoclinic distortions. Presumably, the local electronic situation at the transition metals reflects the origin and extent of these monoclinic distortions.

On the Bending and Stretching of Liquid Metal Receive Coils for Magnetic Resonance Imaging.

The eGaIn coil on neoprene demonstrated in this paper presents a stretchable radio frequency receive coil for magnetic resonance imaging (MRI). The coil with dimensions [Formula: see text] is tuned to resonate at 128 MHz for 3 T MRI. We investigate the effect of stretching (up to 40% strain) and bending (50 mm radius of curvature) of the coil on the coil's resistance and resonance frequency. Measurements and simulations show a decrease in resonance frequency of 2.5 MHz per 10% strain. The higher resistivity of liquid metal compared to copper reduces the SNR of MRI scans by 34%; therefore, a tradeoff between flexibility and performance remains. Nevertheless, we have successfully performed MRI scans with the liquid metal coil.

Automatic Resonance Frequency Retuning of Stretchable Liquid Metal Receive Coil for Magnetic Resonance Imaging.

Stretchable magnetic resonance (MR) receive coils show shifts in their resonance frequency when stretched. An in-field receiver measures the frequency response of a stretchable coil. The receiver and coil are designed to operate at 128 MHz for a 3T MR scanner. Based on the measured frequency response, we are able to detect the changes of the resonance frequency of the coil. We show a proportional-integral-derivative controller that tracks the changes in resonance frequency and retunes the stretchable coil. The settling time of the control loop is less than 3.8ms. The retuning system reduces the loss in signal-to-noise ratio of phantom images from 1.6 dB to 0.3 dB, when the coil is stretched by 40% and the coil is retuned to 128 MHz.

Variation in sensitivity to cadmium among genetically characterized laboratory strains of the midge Chironomus riparius.

Estimating the extent of intraspecific variation in sensitivity to contaminant exposure is important in order to explain variation in the outcome of toxicity tests and to predict the effects of chemical stress on natural populations of plants and animals. However, only few studies provide evident data concerning intraspecific variation in life-history traits caused by a differential response to chemical stress. In this study, we compared the life-history response of six laboratory strains of the midge Chironomus riparius to cadmium exposure in a full life-cycle assay. In addition, the level of genetic variation in all strains was measured at five variable microsatellite loci. Several significant differences in life-history traits among the strains were observed in controls and cadmium treatments. The extent of variation among strains was largest at moderate cadmium concentration (0.42 mg Cd/kg dw). At increased Cd concentrations all strains showed similar levels of high mortality and reduced reproductive success. All strains exhibited considerable levels of genetic impoverishment compared to field populations. Strains with low genetic variation showed reduced fitness in the controls and were more susceptible to Cd exposure. For instance, no reproductive success in the lowest Cd treatment was observed for the strain with the lowest level of genetic diversity. In contrast, this Cd concentration had no negative effects on life-history traits of more variable strains. These results confirm recent findings, that inbreeding and reduced genetic variation influence the reaction of populations towards environmental stress. In addition, we show that the level of genetic variation and inbreeding directly influences the outcome of toxicity tests and contributes to the lack of reproducibility of test results among laboratories.

Speed of sound in bubble-free ice.

The speed of sound in a large volume of bubble-free ice was measured with high accuracy using a linear array of six piezoceramic lead zirconium titanate (PZT) receivers. This array was deployed in an approximately 3 m(3) water tank, which was cooled down to -20 degrees C. The freezing process was performed inside a cooling container. Bubble-free ice was obtained using a freeze control unit, which filters and degases the water during the freezing process. A dedicated geometry was used to position PZT receivers and an emitter such that systematic errors were minimized. With this setup the longitudinal and the transverse components of the speed of sound were measured at temperatures between 17 and 0 degrees C in water and between 0 and -20 degrees C in ice with an uncertainty of approximately 0.3%.

Metal-Halide Perovskites for Gate Dielectrics in Field-Effect Transistors and Photodetectors Enabled by PMMA Lift-Off Process.

Metal-halide perovskites have emerged as promising materials for optoelectronics applications, such as photovoltaics, light-emitting diodes, and photodetectors due to their excellent photoconversion efficiencies. However, their instability in aqueous solutions and most organic solvents has complicated their micropatterning procedures, which are needed for dense device integration, for example, in displays or cameras. In this work, a lift-off process based on poly(methyl methacrylate) and deep ultraviolet lithography on flexible plastic foils is presented. This technique comprises simultaneous patterning of the metal-halide perovskite with a top electrode, which results in microscale vertical device architectures with high spatial resolution and alignment properties. Hence, thin-film transistors (TFTs) with methyl-ammonium lead iodide (MAPbI3 ) gate dielectrics are demonstrated for the first time. The giant dielectric constant of MAPbI3 (>1000) leads to excellent low-voltage TFT switching capabilities with subthreshold swings ≈80 mV decade-1 over ≈5 orders of drain current magnitude. Furthermore, vertically stacked low-power Au-MAPbI3 -Au photodetectors with close-to-ideal linear response (R2 = 0.9997) are created. The mechanical stability down to a tensile radius of 6 mm is demonstrated for the TFTs and photodetectors, simultaneously realized on the same flexible plastic substrate. These results open the way for flexible low-power integrated (opto-)electronic systems based on metal-halide perovskites.

The Escherichia coli MotAB proton channel unplugged.

The MotA and MotB proteins of Escherichia coli serve two functions. The MotA4MotB2 complex attaches to the cell wall via MotB to form the stator of the flagellar motor. The complex also couples the flow of hydrogen ions across the cell membrane to movement of the rotor. The TM3 and TM4 transmembrane helices of MotA and the single TM of MotB comprise the proton channel, which is inactive until the complex assembles into a motor. Here, we identify a segment of the MotB protein that acts as a plug to prevent premature proton flow. The plug is in the periplasm just C-terminal to the MotB TM. It consists of an amphipathic alpha helix flanked by Pro52 and Pro65. When MotA is over-expressed with MotB deleted for residues 51-70, a massive influx of protons acidifies the cytoplasm without significantly depleting the proton motive force. Either that acidification or some sequela thereof, such as potassium or water efflux from the cells, inhibits growth. The Pro residues and Ile58, Tyr61, and Phe62 are essential for plug function. Cys-substituted MotB proteins form a disulfide bond between the two plugs that hold the channels open, and the plugs function intrans within the MotA4MotB2 complex. We present a model in which the MotA4MotB2 complex forms in the bulk membrane. Before association with a motor, we propose the plugs insert into the cell membrane parallel with its periplasmic face and interfere with channel formation. When a complex incorporates into a motor, the plugs leave the membrane and associate with each other via their hydrophobic faces to hold the proton channel open.

Improved endothelial function and reduced platelet activation by chronic HMG-CoA-reductase inhibition with rosuvastatin in rats with streptozotocin-induced diabetes mellitus.

Diabetes is associated with endothelial dysfunction and platelet activation, both of which may contribute to increased cardiovascular risk. We investigated whether the hydroxy-3-methyl-glutaryl CoA reductase inhibitor rosuvastatin improves endothelial function and reduces platelet activation in diabetic rats. Therefore, male Wistar rats were injected with streptozotocin (STZ, 50mg/kg i.v.) to induce insulin-deficient diabetes. Treatment with rosuvastatin (20mg/[kg day]) or vehicle was initiated 2 weeks after injection of STZ and continued for 2 weeks. Thereafter, platelet activation was assessed in fresh whole blood and vascular function was characterized in isolated aortic segments in organ bath chambers. Endothelium-dependent relaxation induced by acetylcholine was significantly attenuated in diabetic rats and improved by treatment with rosuvastatin (maximum relaxation, % of precontraction-control: 99.8+/-0.2, STZ-vehicle: 80.7+/-2.9, STZ-rosuvastatin: 98.9+/-0.7; p<0.01). Similarly, treatment with rosuvastatin significantly reduced fibrinogen-binding to activated GPIIb/IIIa (mean fluorescence-control: 161.0+/-6.9, STZ-vehicle: 207.8+/-15.9, rosuvastatin: 173.6+/-5.3; p<0.05) and P-Selectin surface expression on platelets (mean fluorescence-control: 76.5+/-7.3, STZ-vehicle: 92.1+/-5.5, rosuvastatin: 75.2+/-6.5; p<0.05), while both markers of platelet activation were increased in diabetic rats. Therefore, rosuvastatin treatment normalizes endothelial function and reduces platelet activation in diabetic rats. These effects may contribute to the reduction of cardiovascular events by statins in diabetic patients.

Consequences of inbreeding and reduced genetic variation on tolerance to cadmium stress in the midge Chironomus riparius.

Inbreeding and loss of genetic variation are considered to be major threats to small and endangered populations. The reduction of fitness due to inbreeding is believed to be more severe under stressful environmental conditions. We generated nine strains of the ecotoxicological model organism Chironomus riparius of different inbreeding levels in order to test the hypothesis that the inbreeding level and thus the degree of genome-wide homozygosity influences the life-history under cadmium exposure. Therefore, midge populations were exposed to a gradient of sediment-bound cadmium. The level of genetic variation in the used strains was assessed using microsatellite markers. In the life-cycle tests, inbreeding reduced fitness within C. riparius populations both under control and stressed conditions. However, differences between genetically diverse and impoverished strains were greatest at high cadmium exposure. Overall, inbreeding effects were not only dependent on cadmium concentrations in the sediment, but also on the life-history trait investigated. While some parameters where only affected by inbreeding, others were altered by both, inbreeding and cadmium. For the larval developmental time, a significant interaction was found between inbreeding and cadmium stress. While all strains showed a similar developmental time under control conditions, high rates of inbreeding led to a significantly delayed emergence time under high cadmium concentrations, resulting in longer generation periods and reduced population growth rates as population-relevant effects. The results show, that bioassays with C. riparius are affected by the level of inbreeding within Chironomus test strains. Pollution stress is therefore likely to affect the survival of rare and endangered populations more severe than that of large and genetically diverse ones.

Multi-generation studies with Chironomus riparius--effects of low tributyltin concentrations on life history parameters and genetic diversity.

While toxicological data are available for numerous chemicals from standard tests, little is known on effects of pollutants over several generations or regarding chronic effects of chemicals on genetic diversity. Within the experiments, effects of the model pollutant tributyltin (TBT) were investigated over eleven generations at a sublethal TBT concentration of 4.46 microg as Sn kg-1 sediment dw on life-cycle parameters and genetic variability of Chironomus riparius. Moreover, the adaptation potential towards TBT was determined. This experimental design enables the identification of TBT effects on life-cycle parameters and the determination of a potential extinction risk caused by chronic exposure. Furthermore, effects on the genetic structure can be determined, which are not predictable based solely on knowledge of the toxic mode of action of the chemical. Genetic variety was determined via microsatellite analysis, measuring individual length differences of highly variable satellite DNA fragments. For the identification of changes in tolerances towards the stressor, acute and chronic toxicity experiments were conducted. During the multi-generation study, significant effects on development and reproduction were determined. For some generations, the emergence was significantly (p<0.05) delayed under TBT exposure. Reproduction seems to be a sensitive parameter as well, whereby females laid significantly larger egg masses (p<0.05) in the latter generations. TBT did not affect the population growth rate nor the genetic variability, while clear deviations from the Hardy-Weinberg equilibrium appeared. The study also provides strong evidence for the acquirement of a higher tolerance towards the stressor in the TBT-exposed group.

Genetic impoverishment in laboratory cultures of the test organism Chironomus riparius.

Genetic diversity among laboratory and field populations of Chironomus riparius was investigated using microsatellite DNA analysis. Individuals of midge cultures reared in 10 different laboratories showed a clear reduction in the number of alleles per locus and in the level of heterozygosity compared to two natural populations sampled in southern Germany. To reconstruct the rate of genetic impoverishment under laboratory conditions, genetic diversity was monitored in a C. riparius laboratory population for 23 generations. Additionally, 11 populations originating from different laboratories were crossed, and genetic diversity was compared among pure, crossed, and natural populations. The results demonstrate that C. riparius strains used in standard toxicity tests exhibit low levels of genetic variability. In addition, our experiments show that refreshment of stocks with individuals from other laboratories is not sufficient to restore genetic variation. Potential consequences of genetic impoverishment and improvements for toxicological bioassays are discussed.

Adsorbed Eutectic GaIn Structures on a Neoprene Foam for Stretchable MRI Coils.

Stretchable conductors based on eutectic gallium-indium (eGaIn) alloy are patterned on a polychloroprene substrate (neoprene foam) using stencil printing. By tuning the amount of eGaIn on the neoprene substrate, different strain-sensitivity of electrical resistance is achieved. Conductors with a layer of eGaIn, which adsorbs to the walls of 60-100 µm wide neoprene cells, change their electrical resistance for 5% at 100% strain. When the amount of eGaIn is increased, the cells are filled with eGaIn and the strain-sensitivity of the electrical resistance rises to 300% at 100% strain. The developed conductors are patterned as stretchable on-body coils for receiving magnetic signals in a clinical magnetic resonance imaging setup. First images with a stretchable coil are acquired on an orange and compared to the images that are recorded using a rigid copper coil of the same size.