Liquid–Vapor Interface of Formic Acid Solutions in Salt Water: A Comparison of Macroscopic Surface Tension and Microscopic in Situ X-ray Photoelectron Spectroscopy Measurements

The liquid–vapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquid–vapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquid–vapor interface. XPS measurements over an experimental probe depth of 51 Å gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental −0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.

Nanoscale switching characteristics of nearly tetragonal BiFeO3 thin films

We have investigated the nanoscale switching properties of strain-engineered BiFeO(3) thin films deposited on LaAlO(3) substrates using a combination of scanning probe techniques. Polarized Raman spectral analysis indicates that the nearly tetragonal films have monoclinic (Cc) rather than P4mm tetragonal symmetry. Through local switching-spectroscopy measurements and piezoresponse force microscopy, we provide clear evidence of ferroelectric switching of the tetragonal phase, but the polarization direction, and therefore its switching, deviates strongly from the expected (001) tetragonal axis. We also demonstrate a large and reversible, electrically driven structural phase transition from the tetragonal to the rhombohedral polymorph in this material, which is promising for a plethora of applications.

A 950 yr temperature reconstruction from Duckhole Lake, southern Tasmania, Australia

A lack of quantitative high resolution paleoclimate data from the Southern Hemisphere limits the ability to examine current trends within the context of long-term natural climate variability. This study presents a temperature reconstruction for southern Tasmania based on analyses of a sediment core from Duckhole Lake (43.365°S, 146.875°E). The relationship between non-destructive whole core scanning reflectance spectroscopy measurements in the visible spectrum (380–730 nm) and the instrumental temperature record (ad 1911–2000) was used to develop a calibration-in-time reflectance spectroscopy-based temperature model. Results showed that a trough in reflectance from 650 to 700 nm, which represents chlorophyll and its derivatives, was significantly correlated to annual mean temperature. A calibration model was developed (R = 0.56, p auto < 0.05, root mean squared error of prediction (RMSEP) = 0.21°C, five-year filtered data, calibration period 1911–2000) and applied down-core to reconstruct annual mean temperatures in southern Tasmania over the last c. 950 years. This indicated that temperatures were initially cool c. ad 1050, but steadily increased until the late ad 1100s. After a brief cool period in the ad 1200s, temperatures again increased. Temperatures steadily decreased during the ad 1600s and remained relatively stable until the start of the 20th century when they rapidly decreased, before increasing from ad 1960s onwards. Comparisons with high resolution temperature records from western Tasmania, New Zealand and South America revealed some similarities, but also highlighted differences in temperature variability across the mid-latitudes of the Southern Hemisphere. These are likely due to a combination of factors including the spatial variability in climate between and within regions, and differences between records that document seasonal (i.e. warm season/late summer) versus annual temperature variability. This highlights the need for further records from the mid-latitudes of the Southern Hemisphere in order to constrain past natural spatial and seasonal/annual temperature variability in the region, and to accurately identify and attribute changes to natural variability and/or anthropogenic activities.

The AEgIS experiment

The AEgIS experiment is presently almost completely installed at CERN. It is currently taking data with antiprotons, electrons and positrons. The apparatus is designed to form a cold, pulsed beam of antihydrogen to measure the Earth’s gravitational acceleration g on antimatter and to perform spectroscopy measurements. This paper describes the main features of the apparatus and shows a selected review of some achieved results.

CH4, CO, and H2O spectroscopy for the Sentinel-5 Precursor mission: an assessment with the Total Carbon Column Observing Network measurements

The TROPOspheric Monitoring Instrument (TROPOMI) will be part of ESA's Sentinel-5 Precursor (S5P) satellite platform scheduled for launch in 2015. TROPOMI will monitor methane and carbon monoxide concentrations in the Earth's atmosphere by measuring spectra of back-scattered sunlight in the short-wave infrared (SWIR). S5P will be the first satellite mission to rely uniquely on the spectral window at 4190–4340 cm−1 (2.3 μm) to retrieve CH4 and CO. In this study, we investigated if the absorption features of the three relevant molecules CH4, CO, and H2O are adequately known. To this end, we retrieved total columns of CH4, CO, and H2O from absorption spectra measured by two ground-based Fourier transform spectrometers that are part of the Total Carbon Column Observing Network (TCCON). The retrieval results from the 4190–4340 cm−1 range at the TROPOMI resolution (0.45 cm−1) were then compared to the CH4 results obtained from the 6000 cm−1 region, and the CO results obtained from the 4190–4340 cm−1 region at the higher TCCON resolution (0.02 cm−1). For TROPOMI-like settings, we were able to reproduce the CH4 columns to an accuracy of 0.3% apart from a constant bias of 1%. The CO retrieval accuracy was, through interference, systematically influenced by the shortcomings of the CH4 and H2O spectroscopy. In contrast to CH4, the CO column error also varied significantly with atmospheric H2O content. Unaddressed, this would introduce seasonal and latitudinal biases to the CO columns retrieved from TROPOMI measurements. We therefore recommend further effort from the spectroscopic community to be directed at the H2O and CH4 spectroscopy in the 4190–4340 cm−1 region.

Improved water vapour spectroscopy in the 4174-4300 cm-1 region and its impact on SCIAMACHY HDO/H2O measurements

The relative abundance of the heavy water isotopologue HDO provides a deeper insight into the atmospheric hydrological cycle. The SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY) allows for global retrievals of the ratio HDO/H2O in the 2.3 micron wavelength range. However, the spectroscopy of water lines in this region remains a large source of uncertainty for these retrievals. We therefore evaluate and improve the water spectroscopy in the range 4174–4300 cm−1 and test if this reduces systematic uncertainties in the SCIAMACHY retrievals of HDO/H2O. We use a laboratory spectrum of water vapour to fit line intensity, air broadening and wavelength shift parameters. The improved spectroscopy is tested on a series of ground-based high resolution FTS spectra as well as on SCIAMACHY retrievals of H2O and the ratio HDO/H2O. We find that the improved spectroscopy leads to lower residuals in the FTS spectra compared to HITRAN 2008 and Jenouvrier et al. (2007) spectroscopy, and the retrievals become more robust against changes in the retrieval window. For both the FTS and SCIAMACHY measurements, the retrieved total H2O columns decrease by 2–4% and we find a negative shift of the HDO/H2O ratio, which for SCIAMACHY is partly compensated by changes in the retrieval setup and calibration software. The updated SCIAMACHY HDO/H2O product shows somewhat steeper latitudinal and temporal gradients and a steeper Rayleigh distillation curve, strengthening previous conclusions that current isotope-enabled general circulation models underestimate the variability in the near-surface HDO/H2O ratio.

Effects of exposure to physical factors on homeopathic preparations as determined by ultraviolet light spectroscopy

Clinical trials have reported statistically significant and clinically relevant effects of homeopathic preparations. We applied ultraviolet (UV) spectroscopy to investigate the physical properties of homeopathic preparations and to contribute to an understanding of the not-yet-identified mode of action. In previous investigations, homeopathic preparations had significantly lower UV light transmissions than controls. The aim of this study was to explore the possible effects of external factors (UV light and temperature) on the homeopathic preparations. Homeopathic centesimal (c) dilutions, 1c to 30c, of copper sulfate (CuSO(4)), decimal dilutions of sulfur (S(8)), 1x to 30x, and controls (succussed potentization medium) were prepared, randomized, and blinded. UV transmission was measured at six different time points after preparation (from 4 to 256 days). In addition, one series of samples was exposed to UV light of a sterilization lamp for 12 h, one was incubated at 37 degrees Celsius for 24 h, and one was heated to 90 degrees Celsius for 15 min. UV light transmission values from 190 or 220 nm to 340 nm were measured several times and averaged. After each exposure, UV transmission of the homeopathic preparations of CuSO(4) was significantly reduced compared to the controls, particularly after heating to 37 degrees Celsius. Overall, the nonexposed CuSO(4) preparations did not show significantly lower UV transmission compared to controls; however, the pooled subgroup of measurements at days 26, 33, and 110 yielded significant differences. UV light transmission for S(8) preparations did not show any differences compared to controls. Our conclusion is that exposure to external factors, incubation at 37 degrees Celsius in particular, increases the difference in light transmission of homeopathic CuSO(4) preparations compared to controls.

The effect of arts speech therapy on cerebral oxygenation and low frequency hemodynamic oscillations measured using functional near-infrared spectroscopy

Introduction: As a previous study revealed, arts speech therapy (AST) affects cardiorespiratory interaction [1]. The aim of the present study was to investigate whether AST also has effects on brain oxygenation and hemodynamics measured non-invasively using near-infrared spectroscopy (NIRS). Material and methods: NIRS measurements were performed on 17 subjects (8 men and 9 women, mean age: 35.6 ± 12.7 y) during AST. Each measurement lasted 35 min, comprising 8 min pre-baseline, 10 min recitation and 20 min post-baseline. For each subject, measurements were performed for three different AST recitation tasks (recitation of alliterative, hexameter and prose verse). Relative concentration changes of oxyhemoglobin (Δ[O2Hb]) and deoxyhemoglobin (Δ[HHb]) as well as the tissue oxygenation index (TOI) were measured using a Hamamatsu NIRO300 NIRS device and a sensor placed on the subjects forehead. Movement artifacts were removed using a novel method [2]. Statistical analysis (Wilcoxon test) was applied to the data to investigate (i) if the recitation causes changes in the median values and/or in the Mayer wave power spectral density (MW-PSD, range: 0.07–0.13 Hz) of Δ[O2Hb], Δ[HHb] or TOI, and (ii) if these changes vary between the 3 recitation forms. Results: For all three recitation styles a significant (p < 0.05) decrease in Δ[O2Hb] and TOI was found, indicating a decrease in blood flow. These decreases did not vary significantly between the three styles. MW-PSD increased significantly for Δ[O2Hb] when reciting the hexameter and prose verse, and for Δ[HHb] and TOI when reciting alliterations and hexameter, representing an increase in Mayer waves. The MW-PSD increase for Δ[O2Hb] was significantly larger for the hexameter verse compared to alliterative and prose verse Conclusion: The study showed that AST affects brain hemodynamics (oxygenation, blood flow and Mayer waves). Recitation caused a significant decrease in cerebral blood flow for all recitation styles as well as an increase in Mayer waves, particularly for the hexameter, which may indicate a sympathetic activation. References 1. D. Cysarz, D. von Bonin, H. Lackner, P. Heusser, M. Moser, H. Bettermann. Am J Physiol Heart Circ Physiol, 287 (2) (2004), pp. H579–H587 2. F. Scholkmann, S. Spichtig, T. Muehlemann, M. Wolf. Physiol Meas, 31 (5) (2010), pp. 649–662

Restricted or severely hindered diffusion of intramyocellular lipids in human skeletal muscle shown by in vivo proton MR spectroscopy

Although magnetic resonance spectroscopy can be used as a unique tool to study molecular diffusion, it is rarely used to measure the diffusion properties of intramyocellular and extramyocellular lipids. Lipids have very low apparent diffusion coefficients (ADCs), which make these measurements difficult and necessitate strong diffusion gradients and long diffusion times. Consequence is that these measurements have inherently low signal-to-noise ratio and are prone to artifacts. The addition of physiological triggering and individual storage and processing of the spectra is seen to be a possible approach to maximize signal intensity and achieve high reproducibility of the experiments. Thus, the optimized measurement protocol was used to investigate the diffusion properties of lipids in human skeletal muscle in vivo. At a diffusion time of about 110 ms, intramyocellular lipids show a significantly lower ADC (2.0 × 10(-6) mm(2)/s, 95% confidence interval 1.10 × 10(-6) to 2.94 × 10(-6) mm(2)/s) than extramyocellular lipids (1.58 × 10(-5) mm(2)/s, 95% confidence interval 1.41 × 10(-5) to 1.75 × 10(-5) mm(2)/s). Because the chemical properties of both lipid pools can be assumed to be similar, the difference can only be attributed to restricted or severely hindered diffusion in the intramyocellular droplets.

Femtosecond Rotational Raman Coherence Spectroscopy of Cyclohexane in a Pulsed Supersonic Jet

We combine the technique of femtosecond degenerate four-wave mixing (fs-DFWM) with a high repetition-rate pulsed supersonic jet source to obtain the rotational coherence spectrum (RCS) of cold cyclohexane (C(6)H(12)) with high signal/noise ratio. In the jet expansion, the near-parallel flow pattern combined with rapid translational cooling effectively eliminate dephasing collisions, giving near-constant RCS signal intensities over time delays up to 5 ns. The vibrational cooling in the jet eliminates the thermally populated vibrations that complicate the RCS coherences of cyclohexane at room temperature [Bragger, G.; et al. J. Phys. Chem. A 2011, 115, 9567]. The rotational cooling reduces the high-J rotational-state population, yielding the most accurate ground-state rotational constant to date, B(0) = 4305.859(9) MHz. Based on this B(0), a reanalysis of previous room-temperature gas-cell RCS measurements of cydohexane gives improved vibration rotation interaction constants for the v(32), v(6), v(16), and v(24) vibrational states. Combining the experimental B(0)(C(6)H(12)) with CCSD(T) calculations yields a very accurate semiexperimental equilibrium structure of the chair isomer of cyclohexane

Quantitative (1)H magnetic resonance spectroscopy of myoglobin de- and reoxygenation in skeletal muscle: reproducibility and effects of location and disease

1H-magnetic resonance spectroscopy ((1)H-MRS) of deoxymyoglobin (DMb) provides a means to noninvasively monitor the oxygenation state of human skeletal muscle in work and disease. As shown in this work, it also offers the opportunity to measure the absolute tissue content of DMb, the basic oxygen consumption of resting muscle, and the reperfusion characteristics after release of a pressure cuff. The methodology to determine these tissue properties simultaneously at two positions along the calf is presented. The obtained values are in agreement with invasive determinations. The reproducibility of the (1)H-MRS measurements is established for healthy controls and patients with peripheral arterial disease (PAD). A location dependence in axial direction, as well as differences between controls and patients are demonstrated for all parameters. The reoxygenation time in particular is expected to provide a means to quantitatively monitor therapies aimed at improving muscular perfusion in these patients.

On-chip non-invasive and label-free cell discrimination by impedance spectroscopy

OBJECTIVES: Many flow-cytometric cell characterization methods require costly markers and colour reagents. We present here a novel device for cell discrimination based on impedance measurement of electrical cell properties in a microfluidic chip, without the need of extensive sample preparation steps and the requirement of labelling dyes. MATERIALS AND METHODS, RESULTS: We demonstrate that in-flow single cell measurements in our microchip allow for discrimination of various cell line types, such as undifferentiated mouse fibroblasts 3T3-L1 and adipocytes on the one hand, or human monocytes and in vitro differentiated dendritic cells and macrophages on the other hand. In addition, viability and apoptosis analyses were carried out successfully for Jurkat cell models. Studies on several species, including bacteria or fungi, demonstrate not only the capability to enumerate these cells, but also show that even other microbiological life cycle phases can be visualized. CONCLUSIONS: These results underline the potential of impedance spectroscopy flow cytometry as a valuable complement to other known cytometers and cell detection systems.

Leg ischemia: assessment with MR angiography and spectroscopy

PURPOSE: To prospectively determine reproducibility of magnetic resonance (MR) angiography and MR spectroscopy of deoxymyoglobin in assessment of collateral vessels and tissue perfusion in patients with critical limb ischemia (CLI) and to follow changes in patients undergoing intramuscular vascular endothelial growth factor (pVEGF)-C gene therapy, percutaneous transluminal angioplasty, supervised exercise training, or no therapy. MATERIALS AND METHODS: Study and gene therapy protocols were approved, and all patients gave written informed consent. To determine repeatability and reproducibility, seven patients underwent MR angiography and five underwent MR spectroscopy. The techniques were used to judge disease progress in 12 other patients with or without therapy: MR angiography to help determine change in visualization of collateral vessels and MR spectroscopy to help assess change in perfusion at proximal and distal calf levels. MR angiographic results were subjectively analyzed by three blinded readers. Intraobserver variability was expressed as 95% confidence interval (CI) (n=7); interobserver variability, as kappa statistic (n=15). Reexamination variability of MR spectroscopy was given as 95% CI for subsequent recovery times, and correlation with disease extent was calculated with Kendall taub rank correlation. Fisher-Yates test was used to correlate changes with pressure measurements and clinical course. RESULTS: Intraobserver and interobserver concordance was sensitive for detection of collateral vessels. Intraobserver agreement was 85.7% (95% CI: 42.1%, 99.6%). Interobserver agreement was high for small collateral vessels (kappa=0.74, P <.001) and fair for large collateral vessels (kappa=0.36, P=.002). MR spectroscopy was reproducible (95% CI: +/-26 seconds for proximal, +/-21 seconds for distal) and showed a correlation with disease extent (proximal calf, taub=0.84, P <.001; distal calf, taub=0.68, P=.04). Small collateral vessels increased over time (P=.04) but did not correlate with pressure measurements and clinical course. Recovery time correlated with clinical course (proximal calf, P=.03; distal calf, P=.005). CONCLUSION: MR angiography and MR spectroscopy of deoxymyoglobin can help document changes in visualization of collateral vessels and tissue perfusion in patients with CLI.

Physiological effects of mechanical pain stimulation at the lower back measured by functional near-infrared spectroscopy and capnography

The aim was to investigate the effect of mechanical pain stimulation at the lower back on hemodynamic and oxygenation changes in the prefrontal cortex (PFC) assessed by functional near-infrared spectroscopy (fNIRS) and on the partial pressure of end-tidal carbon dioxide ( PetCO 2) measured by capnography. 13 healthy subjects underwent three measurements (M) during pain stimulation using pressure pain threshold (PPT) at three locations, i.e., the processus spinosus at the level of L4 (M1) and the lumbar paravertebral muscles at the level of L1 on the left (M2) and the right (M3) side. Results showed that only in the M2 condition the pain stimulation elicited characteristic patterns consisting of (1) a fNIRS-derived decrease in oxy- and total hemoglobin concentration and tissue oxygen saturation, an increase in deoxy-hemoglobin concentration, (2) a decrease in the PetCO 2 response and (3) a decrease in coherence between fNIRS parameters and PetCO 2 responses in the respiratory frequency band (0.2-0.5 Hz). We discuss the comparison between M2 vs. M1 and M3, suggesting that the non-significant findings in the two latter measurements were most likely subject to effects of the different stimulated tissues, the stimulated locations and the stimulation order. We highlight that PetCO 2 is a crucial parameter for proper interpretation of fNIRS data in experimental protocols involving pain stimulation. Together, our data suggest that the combined fNIRS-capnography approach has potential for further development as pain monitoring method, such as for evaluating clinical pain treatment.