314 research outputs found
Strengthening of the C-F Bond in Fumaryl Fluoride with Superacids
The reaction of fumaryl fluoride with the superacidic solutions XF/MF5 (X=H, D;M=As, Sb) results in the formation of the monoprotonated and diprotonated species, dependent on the stoichiometric ratio of the Lewis acid to fumaryl fluoride. The salts [C4H3F2O2](+)[MF6](-) (M=As, Sb) and [C4H2X2F2O2](2+)([MF6](-))(2) (X=H, D;M=As, Sb) are the first examples with a protonated acyl fluoride moiety. They were characterized by low-temperature vibrational spectroscopy. Low-temperature NMR spectroscopy and single-crystal X-ray structure analyses were carried out for [C4H3F2O2](+)[SbF6](-) as well as for [C4H4F2O2](2+)([MF6](-))(2) (M=As, Sb). The experimental results are discussed together with quantum chemical calculations of the cations [C4H4F2O2 . 2 HF](2+) and [C4H3F2O2 . HF](+) at the B3LYP/aug-cc-pVTZ level of theory. In addition, electrostatic potential (ESP) maps combined with natural population analysis (NPA) charges were calculated in order to investigate the electron distribution and the charge-related properties of the diprotonated species. The C-F bond lengths in the protonated dication are considerably reduced on account of the +R effect
Towards understanding the variability in biospheric CO2 fluxes:Using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2
Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world
Different metabolic responses during incremental exercise assessed by localized 31P MRS in sprint and endurance athletes and untrained individuals
Until recently, assessment of muscle metabolism was only possible by invasive sampling. 31P magnetic resonance spectroscopy ( 31P MRS) offers a way to study muscle metabolism non-invasively. The aim of the present study was to use spatially-resolved 31P MRS to assess the metabolism of the quadriceps muscle in sprint-trained, endurance-trained and untrained individuals during exercise and recovery. 5 sprint-trained (STA), 5 endurance-trained (ETA) and 7 untrained individuals (UTI) completed one unlocalized 31P MRS session to measure phosphocreatine (PCr) recovery, and a second session in which spatially-resolved 31P MR spectra were obtained. PCr recovery time constant (τ) was significantly longer in STA (50±17 s) and UTI (41±9 s) than in ETA (30±4 s), (P\u3c0.05). PCr changes during exercise differed between the groups, but were uniform across the different components of the quadriceps within each group. pH during recovery was higher for the ETA than for the UTI (P\u3c0.05) and also higher than for the STA (P\u3c0.01). Muscle volume was greater in STA than in UTI (P\u3c0.05) but not different from ETA. Dynamic 31P MRS revealed considerable differences among endurance and sprint athletes and untrained people. This non-invasive method offers a way to quantify differences between individual muscles and muscle components in athletes compared to untrained individuals. 2013 Georg Thieme Verlag KG Stuttgart.New York
Cardiac Imaging Using Clinical 1.5 T MRI Scanners in a Murine Ischemia/Reperfusion Model
To perform cardiac imaging in mice without having to invest in expensive dedicated equipment, we adapted a clinical 1.5 Tesla (T) magnetic resonance imaging (MRI) scanner for use in a murine ischemia/reperfusion model. Phase-sensitive inversion recovery (PSIR) sequence facilitated the determination of infarct sizes in vivo by late gadolinium enhancement. Results were compared to histological infarct areas in mice after ischemia/reperfusion procedure with a good correlation (r = 0.807, P < .001). In addition, fractional area change (FAC) was assessed with single slice cine MRI and was matched to infarct size (r = −0.837) and fractional shortening (FS) measured with echocardiography (r = 0.860); both P < .001. Here, we demonstrate the use of clinical 1.5 MRI scanners as a feasible method for basic phenotyping in mice. These widely available scanners are capable of investigating in vivo infarct dimensions as well as assessment of cardiac functional parameters in mice with reasonable throughput
Discrete interactions between a few interlayer excitons trapped at a MoSe<sub>2</sub>–WSe<sub>2</sub> heterointerface
Interlayer excitons (IXs) in hetero-bilayers of transition metal
dichalcogenides (TMDs) represent an exciting emergent class of long-lived
dipolar composite bosons in an atomically thin, near-ideal two-dimensional (2D)
system. The long-range interactions that arise from the spatial separation of
electrons and holes can give rise to novel quantum, as well as classical
multi-particle correlation effects. In order to acquire a detailed
understanding of the possible many-body effects, the fundamental interactions
between individual IXs have to be studied. Here, we trap a tunable number of
dipolar within a nanoscale confinement potential induced by placing a
MoSe-WSe hetero-bilayer (HBL) onto an array of SiO nanopillars. We
control the mean occupation of the IX trap via the optical excitation level and
observe discrete sharp-line emission from different configurations of
interacting IXs. We identify these features as different multiparticle states
with via their power dependencies and directly measure the
hierarchy of dipolar and exchange interactions as increases. The
interlayer biexciton () is found to be an emission doublet that is
blue-shifted from the single exciton by meV and split by
meV. The blueshift is even more pronounced for triexcitons
( meV), quadexcitons ( meV) and quintexcitons
( meV). These values are shown to be mutually consistent with
numerical modelling of dipolar excitons confined to a harmonic trapping
potential having a confinement lengthscale in the range nm. Our
results contribute to the understanding of interactions between IXs in TMD HBLs
at the discrete limit of only a few excitations and represent a key step
towards exploring quantum correlations between them.Comment: 15 pages, 3 figures plus Supplementary Information (19 pages, 11
pages
In-vivo visualisation of the anatomical structures related to the acupuncture points Dai mai and Shen mai by MRI: A single-case pilot study
BACKGROUND: The concept of acupuncture point localisation in Traditional Chinese Medicine (TCM) is based on millenary practical experience. Modern imaging methods such as PET, MRI and SPECT have been used primary for the investigation of the mechanisms of action of acupuncture. In this pilot single-case study we have evaluated the technical possibilities for in-vivo imaging of the anatomical relations of acupuncture points using state of the art MRI. METHODS: Preliminary experiments relating to the quality of acupuncture needles under the setting of MRI were done both with stainless steel and gold needles. In a second step, in-vivo imaging was carried out. A licensed acupuncture practitioner (RM) chose two points belonging to the so-called extraordinary vessels. In 2 sequential, separate procedures, he inserted himself gold acupuncture needles using a neutral technique (known as Ping Bu Ping Xie) into the Dai mai and Shen mai points, i.e. gall bladder 26 and bladder 62. Imaging was done on a Siemens Magnetom Avanto MR scanner using a head array and body coil. Mainly T1-weighted imaging sequences, as routinely used for patient exams, were used to obtain multi-slice images. RESULTS: In the preliminary experiments only acupuncture needles made of gold showed enough stability in order to be used for further imaging procedures. Using an onion and a banana as an object, further studies showed that the gold needles produced a void defect that corresponds to the tip of the inserted needle, while at the same time an artefactually increased diameter was observed. The in-vivo experiments showed that the Dai mai point was in relation to the abdominal internal oblique muscle. The Shen mai point artefact showed up close to the longus and brevis peroneal tendons at the fibular malleolus. Side effects related to heating or burning were not observed. Improved anatomical recognition was obtained using 3D-volume rendering techniques. CONCLUSION: Through an adequate choice of acupuncture material (gold needles) as well as of ideal MRI imaging sequences it has been possible to visualize the anatomical characteristics at the acupuncture points Dai mai and Shen mai in-vivo. At the selected sites the needles showed a relation to tendino-fascial and muscular structures. These anatomical structures fit well into the recently described WOMED concept of lateral tension in which these acupuncture points play a regulatory role
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