Vibration-rotation spectra of CH3F

Rotational structure has been resolved and analyzed in the 1049-cm−1 parallel fundamental and the 1182 cm−1 perpendicular fundamental bands in the infrared spectrum of the CH3F molecule. Combination bands at 2223 cm−1 and around 2650 cm−1 have also been studied. The effective resolving power of the spectrometer was 0.25 cm−1 for all these bands. The two long-wavelength fundamentals have been analyzed in much greater detail than in previous work, and a complete analysis of the perpendicular band has been made, including the J-structure in the P and R branches of the sub-bands. Rotational constants of CH3F determined in this work and elsewhere are summarized in Table XIII of the text. Some anomalous intensity perturbations in the rotation lines of the 1182-cm−1 fundamental have been observed, and are discussed.

Vibration-rotation bands of diazomethane

Some absorption bands of diazomethane vapour between 1950-3500 cm-1 have been measured with very high resolving power. The rotational structure of two parallel bands and of one perpendicular band has been resolved, and approximate values have been determined for the rotational constants. The results are consistent with the geometrical structure usually accepted for this molecule. A peculiarity in the results for the band near 2100 cm-1, together with other facts, leads to the suggestion that a tautomeric form of this molecule exists, HCN=NH, being an isoelectronic analogue of hydrazoic acid.

The fundamental vibration-rotation band of hydrogen chloride

The fundamental vibration-rotational absorption band of hydrogen chloride near 3 45,t has been remeasured using higher resolving power than previously. The wave-lengths of the absorption lines have been determined more precisely, and the isotopic splitting of lines has been completely resolved. The results have provided new and more satisfactory values for the rotational constants Bi, and the centrifugal stretching constants Di, and their relative values for the two isotopic species agree closely with what is to be expected for the difference in mass. The positions of the lines in the pure rotational absorption spectrum have been calculated from the derived data, and agree closely with those recently observed. The bond lengths re for each isotopic species H35C1 and H37C1 is found to be 1-2744A.

Internal rotation in dimethylacetylene

The vibrational spectrum of dimethyl acetylene has been remeasured with better resolving power than hitherto, and the rotational fine structure of some perpendicular type bands has been partly analyzed. The energy levels of a molecule of this kind in which internal rotation of methyl groups may arise have been re-examined theoretically and the rotational structure of the absorption bands has been more clearly defined than previously. The experimental results are consistent with the assumption of unrestricted internal rotation of the methyl groups, and the Coriolis factors $\zeta _{i}$ for several vibrations have been determined.

The fundamental vibration-rotation bands of 13C16O and 12C18O

Rotation lines in the fundamental vibration bands of 13C16O and 12C180 have been measured, using very high resolving power and more accurate wavelength calibrations than previously. The molecular rotational and vibrational constants have been deduced and compared in relation to the mass differences between these molecules and the main species 12C160.

Chromatographic alignment of LC-MS and LC-MS/MS datasets by genetic algorithm feature extraction

Liquid chromatography-mass spectrometry (LC-MS) datasets can be compared or combined following chromatographic alignment. Here we describe a simple solution to the specific problem of aligning one LC-MS dataset and one LC-MS/MS dataset, acquired on separate instruments from an enzymatic digest of a protein mixture, using feature extraction and a genetic algorithm. First, the LC-MS dataset is searched within a few ppm of the calculated theoretical masses of peptides confidently identified by LC-MS/MS. A piecewise linear function is then fitted to these matched peptides using a genetic algorithm with a fitness function that is insensitive to incorrect matches but sufficiently flexible to adapt to the discrete shifts common when comparing LC datasets. We demonstrate the utility of this method by aligning ion trap LC-MS/MS data with accurate LC-MS data from an FTICR mass spectrometer and show how hybrid datasets can improve peptide and protein identification by combining the speed of the ion trap with the mass accuracy of the FTICR, similar to using a hybrid ion trap-FTICR instrument. We also show that the high resolving power of FTICR can improve precision and linear dynamic range in quantitative proteomics. The alignment software, msalign, is freely available as open source.

Multiplexed quantitative proteomics using differential metabolic 15N-labeling

There are several advantages of using metabolic labeling in quantitative proteomics. The early pooling of samples compared to post-labeling methods eliminates errors from different sample processing, protein extraction and enzymatic digestion. Metabolic labeling is also highly efficient and relatively inexpensive compared to commercial labeling reagents. However, methods for multiplexed quantitation in the MS-domain (or ‘non-isobaric’ methods), suffer from signal dilution at higher degrees of multiplexing, as the MS/MS signal for peptide identification is lower given the same amount of peptide loaded onto the column or injected into the mass spectrometer. This may partly be overcome by mixing the samples at non-uniform ratios, for instance by increasing the fraction of unlabeled proteins. We have developed an algorithm for arbitrary degrees of nonisobaric multiplexing for relative protein abundance measurements. We have used metabolic labeling with different levels of 15N, but the algorithm is in principle applicable to any isotope or combination of isotopes. Ion trap mass spectrometers are fast and suitable for LC-MS/MS and peptide identification. However, they cannot resolve overlapping isotopic envelopes from different peptides, which makes them less suitable for MS-based quantitation. Fourier-transform ion cyclotron resonance (FTICR) mass spectrometry is less suitable for LC-MS/MS, but provides the resolving power required to resolve overlapping isotopic envelopes. We therefore combined ion trap LC-MS/MS for peptide identification with FTICR LC-MS for quantitation using chromatographic alignment. We applied the method in a heat shock study in a plant model system (A. thaliana) and compared the results with gene expression data from similar experiments in literature.

Phylogenetic systematics of Sternbergia (Amaryllidaceae) based on plastid and ITS sequence data

The phylogenetics of Sternbergia (Amaryllidaceae) were studied using DNA sequences of the plastid ndhF and matK genes and nuclear internal transcribed spacer (ITS) ribosomal region for 38, 37 and 32 ingroup and outgroup accessions, respectively. All members of Sternbergia were represented by at least one accession, except S. minoica and S. schubertii, with additional taxa from Narcissus and Pancratium serving as principal outgroups. Sternbergia was resolved and supported as sister to Narcissus and composed of two primary subclades: S. colchiciflora sister to S. vernalis, S. candida and S. clusiana, with this clade in turn sister to S. lutea and its allies in both Bayesian and bootstrap analyses. A clear relationship between the two vernal flowering members of the genus was recovered, supporting the hypothesis of a single origin of vernal flowering in Sternbergia. However, in the S. lutea complex, the DNA markers examined did not offer sufficient resolving power to separate taxa, providing some support for the idea that S. sicula and S. greuteriana are conspecific with S. lutea

Precision of quasi-optical null-balanced bridge techniques for transmission and reflection coefficient measurements

The precision of quasioptical null-balanced bridge instruments for transmission and reflection coefficient measurements at millimeter and submillimeter wavelengths is analyzed. A Jones matrix analysis is used to describe the amount of power reaching the detector as a function of grid angle orientation, sample transmittance/reflectance and phase delay. An analysis is performed of the errors involved in determining the complex transmission and reflection coefficient after taking into account the quantization error in the grid angle and micrometer readings, the transmission or reflection coefficient of the sample, the noise equivalent power of the detector, the source power and the post-detection bandwidth. For a system fitted with a rotating grid with resolution of 0.017 rad and a micrometer quantization error of 1 μm, a 1 mW source, and a detector with a noise equivalent power 5×10−9 W Hz−1/2, the maximum errors at an amplitude transmission or reflection coefficient of 0.5 are below ±0.025.

One-port de-embedding technique for the quasi-optical characterization of integrated components

We describe a one-port de-embedding technique suitable for the quasi-optical characterization of terahertz integrated components at frequencies beyond the operational range of most vector network analyzers. This technique is also suitable when the manufacturing of precision terminations to sufficiently fine tolerances for the application of a TRL de-embedding technique is not possible. The technique is based on vector reflection measurements of a series of easily realizable test pieces. A theoretical analysis is presented for the precision of the technique when implemented using a quasi-optical null-balanced bridge reflectometer. The analysis takes into account quantization effects in the linear and angular encoders associated with the balancing procedure, as well as source power and detector noise equivalent power. The precision in measuring waveguide characteristic impedance and attenuation using this de-embedding technique is further analyzed after taking into account changes in the power coupled due to axial, rotational, and lateral alignment errors between the device under test and the instruments' test port. The analysis is based on the propagation of errors after assuming imperfect coupling of two fundamental Gaussian beams. The required precision in repositioning the samples at the instruments' test-port is discussed. Quasi-optical measurements using the de-embedding process for a WR-8 adjustable precision short at 125 GHz are presented. The de-embedding methodology may be extended to allow the determination of S-parameters of arbitrary two-port junctions. The measurement technique proposed should prove most useful above 325 GHz where there is a lack of measurement standards.

On the nature of ULF wave power during nightside auroral activations and substorms: 2. temporal evolution

We present a statistical analysis of the time evolution of ground magnetic fluctuations in three (12–48 s, 24–96 s and 48–192 s) period bands during nightside auroral activations. We use an independently derived auroral activation list composed of both substorms and pseudo-breakups to provide an estimate of the activation times of nightside aurora during periods with comprehensive ground magnetometer coverage. One hundred eighty-one events in total are studied to demonstrate the statistical nature of the time evolution of magnetic wave power during the ∼30 min surrounding auroral activations. We find that the magnetic wave power is approximately constant before an auroral activation, starts to grow up to 90 s prior to the optical onset time, maximizes a few minutes after the auroral activation, then decays slightly to a new, and higher, constant level. Importantly, magnetic ULF wave power always remains elevated after an auroral activation, whether it is a substorm or a pseudo-breakup. We subsequently divide the auroral activation list into events that formed part of ongoing auroral activity and events that had little preceding geomagnetic activity. We find that the evolution of wave power in the ∼10–200 s period band essentially behaves in the same manner through auroral onset, regardless of event type. The absolute power across ULF wave bands, however, displays a power law-like dependency throughout a 30 min period centered on auroral onset time. We also find evidence of a secondary maximum in wave power at high latitudes ∼10 min following isolated substorm activations. Most significantly, we demonstrate that magnetic wave power levels persist after auroral activations for ∼10 min, which is consistent with recent findings of wave-driven auroral precipitation during substorms. This suggests that magnetic wave power and auroral particle precipitation are intimately linked and key components of the substorm onset process.

Note: Active optical detection of cloud from a balloon platform

A disposable backscatter instrument is described for optical detection of cloud in the atmosphere from a balloon-carried platform. It uses an ultra-bright light emitting diode (LED) illumination source with a photodiode detector. Scattering of the LED light by cloud droplets generates a small optical signal which is separated from background light fluctuations using a lock-in technique. The signal to noise obtained permits cloud detection using the scattered LED light, even in daytime. The response is interpreted in terms of the equivalent visual range within the cloud. The device is lightweight (150 g) and low power (∼30 mA), for use alongside a conventional meteorological radiosonde.

Coupling between gamma-band power and cerebral blood volume during recurrent acute neocortical seizures

Characterization of neural and hemodynamic biomarkers of epileptic activity that can be measured using noninvasive techniques is fundamental to the accurate identification of the epileptogenic zone (EZ) in the clinical setting. Recently, oscillations at gamma-band frequencies and above (N30 Hz) have been suggested to provide valuable localizing information of the EZ and track cortical activation associated with epileptogenic processes. Although a tight coupling between gamma-band activity and hemodynamic-based signals has been consistently demonstrated in non-pathological conditions, very little is known about whether such a relationship is maintained in epilepsy and the laminar etiology of these signals. Confirmation of this relationship may elucidate the underpinnings of perfusion-based signals in epilepsy and the potential value of localizing the EZ using hemodynamic correlates of pathological rhythms. Here, we use concurrent multi-depth electrophysiology and 2- dimensional optical imaging spectroscopy to examine the coupling between multi-band neural activity and cerebral blood volume (CBV) during recurrent acute focal neocortical seizures in the urethane-anesthetized rat. We show a powerful correlation between gamma-band power (25–90 Hz) and CBV across cortical laminae, in particular layer 5, and a close association between gamma measures and multi-unit activity (MUA). Our findings provide insights into the laminar electrophysiological basis of perfusion-based imaging signals in the epileptic state and may have implications for further research using non-invasive multi-modal techniques to localize epileptogenic tissue

Long-latency reductions in gamma power predict hemodynamic changes that underlie the negative BOLD signal

Studiesthat use prolonged periods of sensory stimulation report associations between regional reductions in neural activity and negative blood oxygenation level-dependent (BOLD) signaling. However, the neural generators of the negative BOLD response remain to be characterized. Here, we use single-impulse electrical stimulation of the whisker pad in the anesthetized rat to identify components of the neural response that are related to “negative” hemodynamic changes in the brain. Laminar multiunit activity and local field potential recordings of neural activity were performed concurrently withtwo-dimensional optical imaging spectroscopy measuring hemodynamic changes. Repeated measurements over multiple stimulation trials revealed significant variations in neural responses across session and animal datasets. Within this variation, we found robust long-latency decreases (300 and 2000 ms after stimulus presentation) in gammaband power (30 – 80 Hz) in the middle-superficial cortical layers in regions surrounding the activated whisker barrel cortex. This reduction in gamma frequency activity was associated with corresponding decreases in the hemodynamic responses that drive the negative BOLD signal. These findings suggest a close relationship between BOLD responses and neural events that operate over time scales that outlast the initiating sensory stimulus, and provide important insights into the neurophysiological basis of negative neuroimaging signals.