High-resolution IR Research Articles

Purification and Opening of Carbon Nanotubes Using Steam

Purification and opening of carbon nanotubes has been carried out by treatment of as-made single-wall carbon nanotubes (SWNTs) with pure steam at 1 atm pressure. Treated samples have been characterized by high-resolution transmission electron microscopy and IR and Raman spectroscopy. Comparison between the steam purification and the standard nitric acid purification treatment shows that steam is less aggressive toward damage to the tubular nanotube wall structure and forms fewer functional groups.

Spitzer Space TelescopeInfrared Imaging and Spectroscopy of the Crab Nebula

We present 3.6, 4.5, 5.8, 8.0, 24, and 70 μm images of the Crab Nebula obtained with the Spitzer Space Telescope IRAC and MIPS cameras, low- and high-resolution Spitzer IRS spectra of selected positions within the nebula, and a near-infrared ground-based image made in the light of [Fe II] 1.644 μm. The 8.0 μm image, made with a bandpass that includes [Ar II] 7.0 μm, resembles the general morphology of visible Hα and near-IR [Fe II] line emission, while the 3.6 and 4.5 μm images are dominated by continuum synchrotron emission. The 24 and 70 μm images show enhanced emission that may be due to line emission or the presence of a small amount of warm dust in the nebula on the order of less than 1% of a solar mass. The ratio of the 3.6 and 4.5 μm images reveals a spatial variation in the synchrotron power-law index ranging from approximately 0.3 to 0.8 across the nebula. Combining this information with optical and X-ray synchrotron images, we derive a broadband spectrum that reflects the superposition of the flatter spectrum of the jet and torus with the steeper spectrum of the diffuse nebula. We also see suggestions of the expected pileup of relativistic electrons just before the exponential cutoff in the X-ray. The pulsar, and the associated equatorial toroid and polar jet structures seen in Chandra and Hubble Space Telescope images (Hester et al. 2002), can be identified in all of the IRAC images. We present the IR photometry of the pulsar. The forbidden lines identified in the high-resolution IR spectra are all double due to Doppler shifts from the front and back of the expanding nebula and give an expansion velocity of ≈1264 km s-1.

High-resolution Fourier-transform IR spectroscopic determination of impurities in silicon tetrafluoride and silane prepared from it

The impurity compositions of silicon tetrafluoride and silane prepared from it have been determined by high-resolution Fourier-transform IR spectroscopy. In the spectra of SiF4 samples differing in purity, we have identified rovibrational bands arising from Si2F6O, SiF3OH, HF, SiF3H, SiF2H2, SiH3F, CH4, CO2, and CO impurities. Their detection limits lie in the range 9 × 10−5 (CO2) to 3 × 10−3 mol % (Si2F6O). In the spectra of SiH4 samples of different purity, we have detected CH4, CO2, SiF3H, SiF2H2, and SiF4 impurities. Their detection limits lie in the range 8 × 10−5 (CO2) to 1 × 10−3 mol % (SiF4).

Isotopic abundances of Carbon and Oxygen in Oxygen-rich giant stars

Abstract16O/17O and 12C/13C ratios in 23 M giants are determined from high resolution IR spectra. The results are confronted with the current models on the convective mixing.

Synthesis and Characterization of CoFe2O4 Nanoparticles Dispersed in a Silica Matrix by a Sol−Gel Autocombustion Method

A very fast self-combustion reaction was applied for the first time to the synthesis of a series of magnetic CoFe2O4−SiO2 nanocomposites in a wide range of compositions (from 5 to 50 wt % CoFe2O4). Combining a gelation method that adopts metal nitrates, citric acid and tetraethoxysilane as precursors with controlled thermal treatments, a wide variety of samples with properties finely modulated were obtained. Particle formation and evolution of the structural and magnetic properties with the temperature were investigated by thermal analysis, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, nitrogen physisorption, IR, and magnetic susceptibility measurements. It was shown that the formation of metal ammonium carboxylate complexes takes place in all the gel precursors, contributing to the control of nucleation and growth of the nanoparticles. Spherical particles with narrow particle size distribution, uniformly dispersed in the matrix, are obtained in the...

Evolution of film temperature during magnetron sputtering

We report on the results of measurements of the temperature TFsurf which developed on the surface of films deposited by magnetron sputtering of chromium and copper targets on cooling and non-cooling silicon substrates. The TFsurf and substrate temperature (Ts) were simultaneously measured using high-resolution IR camera and thermocouple, respectively. We revealed that the TFsurf steeply grows, keeps constant when it achieves saturation level, and rapidly drops to the value of the Ts after stopping the deposition. At the same time, the Ts either does not change for the case of cooling substrate or increases to a certain level for noncooling substrate. However, in both cases the Ts remains several times lower than the TFsurf. The TFsurf is proportional to the flux of energy delivered to the growth surface by sputtered atoms and other fast particles, weakly depends on the depositing metal and can achieve several hundreds of °C. This phenomenon is explained by a model assuming formation of a hot thin surface layer (HTSL) on the top of the growing film, which exists only during film deposition and exhibits extremely low thermal conductivity. Due to this unique property the temperature TFsurf of HTSL is several times higher than the Ts. Variations in the TFsurf fairly correlate with structure changes of Cr films along thickness investigated in detail previously.

Morphologic and Volumetric Analysis of Amygdala, Hippocampus, Fornix and Mamillary Body with MRI in Patients with Temporal Lobe Epilepsy

Our aim was to demonstrate lateralization morphometrically and volumetrically measuring the main limbic structures like hippocampus, amygdala, fornix and mamillary bodies in patients with temporal lobe epilepsy (TLE) and to establish the contribution of each anatomical structure to lateralizing the pathological site. Forty-two patients with complex partial seizures originating from the temporal lobe and 42 control healthy volunteers were included in the study. T2-weighted FSE sequences in axial and oblique coronal planes and T1-weighted SE sequences in the sagittal plane were used. A high-resolution IR sequence was used for the volumetric analysis of amygdala and hippocampus and for the measurement of fornix and mamillary body thickness. Intensity changes and atrophy of limbic structures were observed qualitatively and measurement of these structures was performed quantitatively. Student's t test and Mann-Whitney U-test were used for the statistical analysis. The p values <0.05 was taken as statistically significant. Ten out of 42 patients had intracranial masses and were excluded from the study. Qualitative analysis revealed atrophy in 84% and intensity increase in 60% of cases. Quantitative measurement demonstrated that control cases had a larger hippocampus than the patients ( p<0.001). There was unilateral hippocampal volume loss in 88% and bilateral volume loss in 13% of patients. There was no difference in the volume of amygdala between the groups ( p>0.05). According to the difference in the volumes of the right and left sides, there was unilateral atrophy in 34% of patients. Bilateral atrophy was not observed. There was a significant difference in fornix and mamillary bodies of the patients and control subjects ( p<0.005). In 62.5% of cases, there were abnormalities in the fornix with bilateral involvement in 13% of cases. Mamillary bodies were abnormal in 37% of patients with bilateral involvement in 15%. Lateralization was accomplished in 65% of the patients according to the percentage difference ratios of fornix and in 38% of the patients according to the mamillary bodies. It is important to demonstrate hippocampus atrophy in patients with TLE. In the decision of lateralization of the epileptic side, evaluation of the fornix could be a good and practical solution. However, hippocampal volumetry is an indispensable criterion in demonstrating hippocampal atrophy more accurately. Atrophy of the amygdala and thickness of mamillary bodies have the least importance for lateralization.

Polyurethane anionomers synthesised with aromatic, aliphatic or cycloaliphatic diisocyanates, polyoxyethylene glycol and 2,2-bis(hydroxymethyl)propionic acid

Taking advantage of the step-growth polyaddition method, which has been developed earlier, and applying it in the reaction of aromatic, cycloaliphatic and aliphatic diisocyanates with polyoxyethylene glycol, 2,2-bis(hydroxymethyl)propionic acid and 1,6-hexamethylene-diamine, a few polyurethane anionomers were synthesised, which were recovered from aqueous dispersions in the form of thin polymeric films. Analytical chemistry methods, like gel permeation chromatography with N,N-dimethylacetamide as the polar eluent and high-resolution nuclear magnetic resonance and IR spectroscopy, were employed to confirm their chemical structures, to find molecular weights and their distribution and to characterise the polarity of the chemical structure of the polyurethane chain formed.

Structural elucidation of a tadalafil analogue found as an adulterant of a herbal product

A tadalafil analogue and hydroxyhomosildenafil were isolated from a herbal product marketed for erectile dysfunction. The structure of the tadalafil analogue was elucidated using LC-UV, high resolution MS, ESI-MS/MS, IR, and NMR. The compound was determined to be (6R,12aR)-2-amino-6-(1,3-benzodioxol-5-yl)-2,3,6,7,12,12a-hexahydropyrazino[1′,2′:1,6] pyrido[3,4-b]indole-1,4-dione. This compound should be included as a target compound when screening for adulterants in herbal products. This is the first published paper on a tadalafil analogue and hydroxyhomosildenafil found as adulterants of a herbal product.

Application of high-resolution IR and microwave spectroscopies for investigation of the impurity composition of silicon tetrafluoride

The possibility of combined application of gas chromatography, high-resolution IR spectroscopy, and transient microwave gas spectroscopy (TMGS) for investigation of the impurity composition of silicon tetrafluoride is studied. Using high-resolution IR Fourier spectroscopy, the lines of a number of impurities are observed in the region from 4500 to 550 cm−1. The absorption lines of some of the main well-known impurities in silicon tetrafluoride in the 2-mm wavelength range are analyzed. The advantages of the TMGS method for investigating the multicomponent SiF4-impurities system are demonstrated. Using the TMGS method, the freons CHF3, CH2F2, and CH3F are experimentally detected in silicon tetrafluoride.

CH stretch/internal rotor dynamics in ethyl radical: High-resolution spectroscopy in the CH3-stretch manifold

High-resolution IR absorption spectra of supersonically cooled ethyl radicals (Trot approximately 20 K) have been obtained in a slit supersonic jet discharge expansion, revealing first rotationally resolved data for CH-stretch excitation of the methyl group. Three different vibrational bands are observed, one parallel (k=0<--0) and two perpendicular (/k/1<--0), which for a nearly decoupled methyl rotor framework would correspond to symmetric and (nearly degenerate) asymmetric CH-stretch excitations. However, the splitting between the two asymmetric CH-stretch excitations is anomalously large (approximately 125 cm(-1)), signaling the presence of interactions between the CH2 radical moiety and the opposing CH bond on the methyl group. This suggests an improved zeroth-order vibrational description as an isolated CH stretch, strongly redshifted by hyperconjugation, with localized vibrations in the remaining CH bonds split into symmetric and asymmetric stretches. Such a dynamical picture highlights a remarkably strong coupling between methyl CH-stretch vibrations and C-C torsional geometry and begins to elucidate discrepancies with previous matrix observations.

High-resolution IR cavity ring-down spectroscopy of jet-cooled free radicals and other species

Initial spectral results are reported from a newly constructed cavity ringdown spectrometer. The apparatus incorporates a slit-jet expansion, with or without a discharge, to produce cold sample molecules. High spectral resolution in both the near- and mid-IR is obtained by using stimulated Raman scattering of the pulsed amplified output of a cw Ti:Sa ring laser. Molecular spectra presented include the electronic near-IR transitions a (1)Delta(g)(-)<-- X (3)Sigma(g)(-) of O(2) and B (3)Pi(g)<-- A (3)Sigma(u)(+) of metastable N(2) and vibrational overtones of H(2)O (polyad 2) and the OH radical. Fundamental vibrational transitions of CH(3) (nu(3)) in the mid-IR are also observed. This apparatus has demonstrated the potential for obtaining high-resolution spectra of both reactive and non-reactive species throughout the entire IR region.

Prediction of accurate anharmonic experimental vibrational frequencies for water clusters, (H2O)n, n=2-5.

Accurate anharmonic experimental vibrational frequencies for water clusters consisting of 2-5 water molecules have been predicted on the basis of comparing different methods with MP2/aug-cc-pVTZ calculated and experimental anharmonic frequencies. The combination of using HF/6-31G* scaled frequencies for intramolecular modes and anharmonic frequencies for intermolecular modes gives excellent agreement with experiment for the water dimer and trimer and are as good as the expensive anharmonic MP2 calculations. The water trimer, the cyclic Ci and S4 tetramers, and the cyclic pentamer all have unique peaks in the infrared spectrum between 500 and 800 cm-1 and between 3400 and 3700 cm-1. Under the right experimental conditions these different clusters can be uniquely identified using high-resolution IR spectroscopy.

Evaluation of AIRS cloud properties using MPACE data

Retrieval of cloud properties from the Atmospheric Infrared Sounder (AIRS) aboard the NASA Aqua satellite has been investigated. The cloud products from the collocated MODerate resolution Imaging Spectroradiometer (MODIS) data are used to characterize the AIRS sub‐pixel cloud information such as cloud phase, cloud coverage, and cloud layer information. A Minimum Residual (MR) approach is used to retrieve cloud microphysical properties once the cloud top pressure (CTP) and effective cloud amount (ECA) are determined from AIRS CO2 absorption channels between 720 and 790 cm−1. The cloud microphysical properties can be retrieved by minimizing the differences between the observations and the calculations using AIRS longwave window channels between 790 and 1130 cm−1. AIRS is used to derive cloud properties during the Mixed Phase Arctic Cloud Experiment (MPACE) field campaign. Comparison with measurements obtained from lidar data is made for a test day, showing that AIRS cloud property retrievals agree with in situ lidar observations. Due to the large solar zenith angle, the MODIS operational retrieval approach is not able to provide cloud microphysics north of Barrow, Alaska; however, AIRS provides cloud microphysical properties with its high spectral resolution IR measurements.

State-resolved collisional quenching of vibrationally excited pyrazine (Evib=37900cm−1) by D35Cl(v=)

Supercollision relaxation of highly vibrationally excited pyrazine (E(vib) = 37,900 cm(-1)) with D35Cl is investigated using high-resolution transient IR diode laser absorption spectroscopy at 4.4 microm. Highly excited pyrazine is prepared by pulsed UV excitation at 266 nm, followed by rapid radiationless decay to the ground electronic state. The rotational energy distribution of the scattered DCl (v = 0,J) molecules with J = 15-21 is characterized by T(rot) = 755+/-90 K. The relative translational energy increases as a function of rotational quantum number for DCl with T(rel) = 710+/-190 K for J = 15 and T(rel) = 1270+/-240 K for J = 21. The average change in recoil velocity correlates with the change in rotational angular momentum quantum number and highlights the role of angular momentum in energy gain partitioning. The integrated energy-transfer rate for appearance of DCl (v = 0,J = 15-21) is k(2)(int) = 7.1x10(-11) cm3 molecule(-1) s(-1), approximately one-eighth the Lennard-Jones collision rate. The results are compared to earlier energy gain measurements of CO2 and H2O.

29Si CPMAS NMR and near-IR study of sol–gel microporous silica with tunable surface area

High-resolution solid-state NMR and IR techniques were used to investigate the surface structure of microporous silica with tunable surface areas, obtained by a sol gel method acting on a variation of gelation time. 29Si MAS NMR and Med-IR evidenced a similar number of silanol groups in all the silicas. Near-IR results revealed the existence of a different ratio of hydrogen bonded silanols and free silanols as a function of surface area. 29Si CP-MAS experiments, including CP spin dynamics studies, were employed to probe hydrogen bonding and local structural environments of various hydroxyl groups of silica surface. These studies showed that for high surface area silicas both free and hydrogen bonded silanols are present at the surface of the samples and the amount of free silanol groups increases with the increasing of the surface area of the samples.

Terrestrins A—G: p‐Terphenyl Derivatives from the Inedible Mushroom Thelephora terrestris.

Seven p-terphenyl derivatives named terrestrins A-G together with three known ganbajunin B, thelephantins F and H, were isolated from the methanol extract of fruiting bodies of the Japanese inedible mushroom Thelephora terrestris (Thelephoraceae). Their structures were elucidated by means of high-resolution MS, 2D NMR, IR and UV spectroscopy, and X-ray crystallographic analysis.

Spitzer Detections of New Dust Components in the Outflow of the Red Rectangle

We present Spitzer high spectral resolution IRS spectroscopy of three positions in the carbon-rich outflow of post-AGB star HD 44179, better known as the Red Rectangle. Surprisingly, the spectra show some strong unknown mid-infrared resonances, in the 13-20 micron range. The shape and position of these resonances varies with position in the nebula, and are not correlated with the PAH features. We conclude these features are due to oxygen-rich minerals, located in a region which is believed to be predominantly carbon-rich. We provide possible explanations for the presence of oxygen-rich dust in the carbon-rich outflows. Simple Mg-Fe-oxides are suggested as carriers of these unidentified features.

Real-time trace-level detection of carbon dioxide and ethylene in car exhaust gases

A direct-absorption spectrometer, based on a pulsed, distributed feedback, quantum cascade laser with a 10.26-microm wavelength and an astigmatic Herriott cell with a 66-m path length, has been developed for high-resolution IR spectroscopy. This spectrometer utilizes the intrapulse method, an example of sweep integration, in which the almost linear wavelength up-chirp obtained from a distributed feedback, quantum cascade laser yields a spectral microwindow of as many as 2.5 wave numbers/cm(-1). Within this spectral microwindow, molecular fingerprints can be monitored and recorded in real time. This system allows both the detection of carbon dioxide and ethylene and the real-time observation of the evolution of these gases in the exhaust by-products from several cars.

Terrestrins A–G: p-Terphenyl derivatives from the inedible mushroom Thelephora terrestris

Seven p-terphenyl derivatives named terrestrins A–G together with three known ganbajunin B, thelephantins F and H, were isolated from the methanol extract of fruiting bodies of the Japanese inedible mushroom Thelephora terrestris (Thelephoraceae). Their structures were elucidated by means of high-resolution MS, 2D NMR, IR and UV spectroscopy, and X-ray crystallographic analysis.