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Biomedical subjects

F Salama

Publications and source records attributed to F Salama.

At least 19 recordsLinked to original sources

Numerical investigation of the discharge characteristics of the pulsed discharge nozzle.

The characteristics of the plasma generated by a pulsed discharge slit nozzle (PDN) are investigated. The PDN source is designed to produce and cool molecular ions creating an astrophysically relevant environment in the laboratory. A discharge model is applied to this system to provide a qualitative as well as a quantitative picture of the plasma. We find that the plasma's properties and behavior are characteristic of those of a glow discharge. We model the electron density and energy, as well as the argon ion and metastable atom number density. The results reveal a high abundance of metastable argon atoms in the expansion region, which is more than one order of magnitude higher than the abundance of electrons and ions. These findings confirm experimental observations, which concluded that large molecular ions are dominantly formed through Penning ionization of the neutral molecular precursors seeded in the supersonic expansion of argon gas. The simulations presented here will help optimize the yield of formation of molecular ions and radicals in the PDN source; they will also provide key physical insight into the characteristics of interstellar molecules and ions analogs in laboratory experiments.

Journal Article↗

Validation of the spectrophotometric determination of omeprazole and pantoprazole sodium via their metal chelates.

Spectrophotometric procedures for the determination of two irriversible proton pump inhibitors, omeprazole (OMZ) and pantoprazole (PNZ) sodium have been developed, the procedures are based on the formation of 2:1 chelates of both drugs with different metal ions. Pantoprazole sodium is quantified by a stability-indicating procedure through chelation with iron (III) in aqueous-ethanol medium to form an orange chelate picked at 455 nm. The procedure retains its accuracy in presence of up to 70% of its degradate, sulfenic acid prepared by degrading the pure drug in borate buffer of pH 8 at 37 degrees C for 5 days. The colored chelates of OMZ in ethanol are determined spectrophotometrically at 411, 339 and 523 nm using iron (III), chromium (III) and cobalt (II), respectively. Regression analysis of Beer's plots showed good correlation in the concentration range of 15-95, 10-60 and 15-150 microml(-1) of pure OMZ using iron (III), chromium (III) and cobalt (II), respectively, and in the range of 30-300 microg ml(-1) of PNZ sodium using iron (III). The limits of detection are 0.22-3.65 microml(-1) while limits of quantitation range between 0.74 and 12.17 microg ml(-1). The optimum assay conditions are investigated and the recovery of the cited drugs from their dosage forms ranges from 97.2 to 100.3%. Good values of precision are obtained, intraday R.S.D. are 0.93-1.75% and the inter day R.S.D. are 0.51-3.29%.

2-Pyridinylmethylsulfinylbenzimidazoles↗

Polycyclic aromatic hydrocarbons and the diffuse interstellar bands: a survey.

We discuss the proposal relating the origin of some of the diffuse interstellar bands (DIBs) to neutral and ionized polycyclic aromatic hydrocarbons (PAHs) present in interstellar clouds. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices, are compared with the spectra of five reddened early-type stars selected from an extensive set of astronomical spectra. From this comparison, it is concluded that PAH ions are good candidates to explain some of the DIBS. Unambiguous assignments are difficult, however, because of the shift in wavelengths and the band broadening induced in the laboratory spectra by the solid matrix. This situation is illustrated by a comparison with the gas-phase spectra made available recently for two PAH ions. Definitive band assignments and, ultimately, the test of the proposal that PAH ions carry some of the DIBs must await the availability of a larger set of gas-phase measurements in the laboratory. The present assessment offers a guideline for future laboratory experiments by allowing the preselection of promising PAH molecules to be studied in jet expansions.

Astronomical Phenomena↗

Jet-discharge cavity ring-down spectroscopy of ionized polycyclic aromatic hydrocarbons: progress in testing the PAH hypothesis for the diffuse interstellar band problem.

Naphthalene cations (C10H+8) were produced in a slit jet coupled with an electronic discharge, and cavity ring down was used to obtain its absorption spectrum in the region 645-680 nm. Two of the strongest C10H+8 bands previously characterized by matrix isolation spectroscopy were found, both with a fractional blue shift of about 0.5%. This is the first gas-phase electronic absorption spectrum of an ionized polycyclic aromatic hydrocarbon (PAH). This work opens the way for a direct comparison of laboratory PAH spectra with the diffuse interstellar bands (DIB), the origin of which still constitutes an open problem in astrophysics.

Astronomical Phenomena↗

Carbon in the universe.

Carbon is a major player in the evolutionary scheme of the universe because of its abundance and its ability to form complex species. It is also a key element in the evolution of prebiotic molecules. The different forms of cosmic carbon are reviewed ranging from carbon atoms and carbon-bearing molecules to complex, solid-state, carbonaceous structures. The current state of knowledge is assessed on the observational and laboratory fronts. Fundamental astrophysical implications are examined as well as the impact of these studies on the hitherto poorly understood physical and chemical properties of carbon materials in space.

Astronomical Phenomena↗

The diffuse interstellar bands: a tracer for organics in the diffuse interstellar medium?

The diffuse interstellar bands (DIBs) are absorption bands seen in the spectra of stars obscured by interstellar dust. DIBs are recognized as a tracer for free, organic molecules in the diffuse interstellar medium (ISM). The potential molecular carriers for the DIBs are discussed with an emphasis on neutral and ionized polycyclic aromatic hydrocarbons (PAHs) for which the most focused effort has been made to date. From the combined astronomical, laboratory and theoretical study, it is concluded that a distribution of free neutral and ionized complex organics (PAHs, fullerenes, unsaturated hydrocarbons) represents the most promising class of candidates to account for the DIBs. The case for aromatic hydrocarbons appears particularly strong. The implied widespread distribution of complex organics in the diffuse ISM bears profound implications for our understanding of the chemical complexity of the ISM, the evolution of prebiotic molecules and its impact on the origin and the evolution of life on early Earth through the exogenous delivery (cometary encounters and metoritic bombardments) of prebiotic organics.

Astronomical Phenomena↗

Assessment of the polycyclic aromatic hydrocarbon-diffuse interstellar band proposal.

The potential link between neutral and/or ionized polycyclic aromatic hydrocarbons (PAHs) and the diffuse interstellar band (DIB) carriers is examined. Based on the study of the general physical and chemical properties of PAHs, an assessment is made of their possible contribution to the DIB carriers. It is found that, under the conditions reigning in the diffuse interstellar medium, PAHs can be present in the form of neutral molecules as well as positive and/or negative ions. The charge distribution of small PAHs is dominated, however, by two charge states at one time with compact PAHs present only in the neutral and cationic forms. Each PAH has a distinct spectral signature depending on its charge state. Moreover, the spectra of ionized PAHs are always clearly dominated by a single band in the DIB spectral range. In the case of compact PAH ions, the strongest absorption band is of type A (i.e., the band is broad, falls in the high-energy range of the spectrum, and possesses a large oscillator strength), and seems to correlate with strong and broad DIBs. For noncompact PAH ions, the strongest absorption band is of type I (i.e., the band is narrow, falls in the low-energy range of the spectrum, and possesses a small oscillator strength), and seems to correlate with weak and narrow DIBs. Potential molecular size and structure constraints for interstellar PAHs are derived by comparing known DIB characteristics to the spectroscopic properties of PAHs. It is found that (i) only neutral PAHs larger than about 30 carbon atoms could, if present, contribute to the DIBs. (ii) For compact PAHs, only ions with less than about 250 carbon atoms could, if present, contribute to the DIBs. (iii) The observed distribution of the DIBs between strong/moderate and broad bands on the one hand and weak and narow bands on the other can easily be interpreted in the context of the PAH proposal by a distribution of compact and noncompact PAH ions, respectively. A plausible correlation between PAH charge states and DIB "families" is thus provided by the PAH-DIB proposal. Following this proposal, DIB families would reflect conditions within a cloud which locally determine the relative importance of cations, anions, and neutral species, rather than tracers of a specific species. Observational predictions are given to establish the viability of the PAH hypothesis. It is concluded that small PAH ions are very promising candidates as DIB carriers provided their population is dominated by a finite number (100-200) of species. A key test for the PAH proposal, consisting of laboratory and astronomical investigations in the ultraviolet range, is called for.

Astronomical Phenomena↗

Polycyclic aromatic hydrocarbon ions and the diffuse interstellar bands.

Neutral naphthalene (C10H8), phenanthrene (C14H10), and pyrene (C16H10) absorb strongly in the ultraviolet and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these PAHs absorb in the visible. C10H8+ has 12 discrete absorption bands which fall between 6800 and 5000 angstroms. The strongest band at 6741 angstroms falls close to the weak 6742 angstroms diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8+ is responsible for some of the DIBs can be tested by searching for new DIBs at 6520, 6151, and 5965 angstroms, other moderately strong naphthalene cation band positions. If C10H8+ is indeed responsible for the 6742 angstroms feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10+ is dominated by a strong band at 4435 angstroms in an Ar matrix and 4395 angstroms in a Ne matrix, a position which falls very close to the strongest DIB, that at 4430 angstroms. If C16H10+, or a closely related pyrene-like ion is indeed responsible for the 4430 angstroms feature, it accounts for 0.2% of the cosmic carbon. We also report an intense, very broad UV-to-visible continuum which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR.

Argon↗

Electronic absorption spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. II. The phenanthrene cation (C14H10+) and its 1-methyl derivative.

The ultraviolet, visible, and near infrared absorption spectra of phenanthrene (C14H10), 1-methylphenanthrene [(CH3)C14H9], and their radical ions [C14H10+; (CH3)C14H9+], formed by vacuum-ultraviolet irradiation, were measured in neon matrices at 4.2 K. The associated vibronic band systems and their spectroscopic assignments are discussed. The oscillator strengths were calculated for the phenanthrene ion and found lower than the theoretical predictions. This study presents the first spectroscopic data for phenanthrene and its methyl derivative trapped in a neon matrix where the perturbation of the isolated species by its environment is minimum; a condition crucial to astrophysical applications.

Argon↗

Is H2O present on Io? The detection of a new strong band near 3590 cm-1 (2.79 micrometers).

A strong absorption band at 3590 +/- 20 cm-1 (2.790 +/- 0.015 micrometers) has been discovered in the spectrum of Io using the Kuiper Airborne Observatory (KAO). The 2 nu1 + nu3 combination mode of solid SO2 falls at this position. Since SO2 is abundant on Io it must contribute to the new band. However, a band due to H2O was predicted near this frequency in Io's spectrum based on laboratory experiments of H2O:SO2 mixed Io ice analogs which were used to assign the two weak, variable features of 3370 and 3170 cm-1 (2.97 and 3.15 micrometers) to trace amounts of H2O frozen in solid SO2 on Io. The new band probably originates from both SO2 and H2O. Unfortunately, the spectral resolution of the data is insufficient to settle the issue of whether there are two resolvable components.

Aircraft↗

Is a pyrene-like molecular ion the cause of the 4,430-angstroms diffuse interstellar absorption band?

The diffuse interstellar bands (DIBs), ubiquitous absorption features in astronomical spectra, have been known since early this century and now number more than a hundred. Ranging from 4,400 angstroms to the near infrared, they differ markedly in depth, width and shape, making the concept of a single carrier unlikely. Whether they are due to gas or grains is not settled, but recent results suggest that the DIB carriers are quite separate from the grains that cause visual extinction. Among molecular candidates the polycyclic aromatic hydrocarbons (PAHs) have been proposed as the possible carriers of some of the DIBs, and we present here laboratory measurements of the optical spectrum of the pyrene cation C16H10+ in neon and argon matrices. The strongest absorption feature falls at 4,435 +/- 5 angstroms in the argon matrix and 4,395 +/- 5 angstroms in the neon matrix, both close to the strong 4,430-angstroms DIB. If this or a related pyrene-like species is responsible for this particular band, it must account for 0.2% of all cosmic carbon. The ion also shows an intense but puzzling broad continuum, extending from the ultraviolet to the visible, similar to what is seen in the naphthalene cation and perhaps therefore a common feature of all PAH cations. This may provide an explanation of how PAHs convert a large fraction of interstellar radiation from ultraviolet and visible wavelengths down to the infrared.

Argon↗

Laboratory studies of the newly discovered infrared band at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io: the tentative identification of CO2.

We discuss over 120 laboratory experiments pertaining to the identification of the new absorption band discovered by Trafton et al. (1991) at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io. It is shown that this band is not due to overtones or combinations of the fundamental bands associated with the molecules (or their chemical complexes) already identified on Io, namely, SO2, H2S, and H2O. Thus, this band is due to a new, previously unidentified, component of Io. Experiments also demonstrate that the band is not due to molecular H2 frozen in SO2 frosts. Since the frequency of this band is very close to the first overtone of the nu 3 asymmetric stretching mode of CO2, we have investigated the spectral behavior of CO2 under a variety of conditions appropriate for Io. The profile of the Io band is not consistent with the rotational envelope expected for single, freely rotating, gaseous CO2 under Io-like conditions. It was found that pure, solid CO2 and CO2 intimately mixed in a matrix of solid SO2 and H2S produce bands with similar widths (5-10 cm-1), but that these bands consistently fall at frequencies about 10-20 cm-1 (approximately 0.007 micrometer) lower than the Io band. CO2 in SO2 : H2S ices also produces several additional bands that are not in the Io spectra. The spectral fit improves, however, as the CO2 concentration in SO2 increases, suggesting that CO2-CO2 interactions might be involved. A series of Ar : CO2 and Kr : CO2 matrix isolation experiments, as well as laboratory work done elsewhere, show that CO2 clustering shifts the band position to higher frequencies and provides a better fit to the Io band. Various laboratory experiments have shown that gaseous CO2 molecules have a propensity to cluster between 80 and 100 K, temperatures similar to those found on the colder regions of Io. We thus tentatively identify the newly discovered Io band at 4705.2 cm-1 (2.1253 micrometers) with CO2 multimers or "clusters" on Io. Whether these clusters are buried within an SO2 frost, reside on the surface, or are in a residual, steady-state "atmospheric aerosol" population over local coldtraps is not entirely clear, although we presently favor the latter possibility. The size of these clusters is not well defined, but evidence suggests groups of more than four molecules are required. The absorption strength of the 2 nu 3 CO2 cluster overtone determined in the laboratory, in conjunction with the observed strength of the Io band, suggests that the disk-integrated abundance of CO2 is less than 1% that of the SO2. Studies of the sublimation behavior of CO2 indicate that it probably resides predominantly in the cooler areas (< 100 K) of Io. The relative constancy of the Io feature over a variety of orbital phases suggests that the polar regions may contain much of the material. Some consequences of the physical properties of CO2 under conditions pertinent to Io are discussed. The presence of CO2 clusters on Io could be verified by the detection of any one of several other infrared bands associated with the CO2 molecule, of which the strongest are the nu 3 12CO2 asymmetric stretch fundamental near 2350 cm-1 (4.25 micrometers) and the nu 2 bending mode fundamental near 660 cm-1 (15.1 micrometers). Weaker bands that may also be detectable include the nu 3 13CO2 asymmetric stretch fundamental near 2280 cm-1 (4.39 micrometers), the 2 nu 2 + nu 3 combination/overtone band near 3600 cm-1 (2.78 micrometers), and the nu 1 + nu 3 combination band near 3705 cm-1 (2.70 micrometers).

Astronomical Phenomena↗

A new class of absorption feature in Io's near-infrared spectrum.

We report our discovery of an absorption feature in the infrared spectrum of Io centered at 2.1253 micrometers (4705.2 cm-1). This band is marginally resolved at resolving power 1200 with a deconvolved full width at half-maximum (FWHM) of about 4 cm-1. This contrasts with the 30- to 50-cm-1 widths of the broad absorption features previously detected at longer wavelengths which arise from mixtures of SO2 with H2S and H2O. This newly discovered feature is relatively weak, having a core only 5% below the continuum at this resolving power. Our survey from 1.98 to 2.46 micrometers (5050-4065 cm-1) at this same resolving power revealed no other feature greater than 1% of the continuum level shortward of 2.35 micrometers, and 3% elsewhere. The feature does not correspond to any gas- or solid-phase absorption that might be expected from previously identified constituents of Io's surface. No temporal or longitudinal variation has been detected in the course of 18 nights of observation over the past year and no significant variation in the strength of the feature was seen during an emergence from eclipse. These observations indicate that the source material of the feature is reasonably stable, and is more uniformly distributed in longitude than Io's hot spots. These characteristics all indicate that the feature belongs to a class different from those characterizing other known absorption features in Io's spectrum. Consequently, it should reveal important new information about Io's atmosphere-surface composition and interaction. A series of laboratory experiments of plausible surface ices indicates that (i) the band does not arise from overtones or combinations of any of the molecular vibrations associated with species already identified on Io (SO2, H2S, H2O) or from chemical complexes of these molecules, (ii) the band does not arise from H2 trapped in SO2, and (iii) the band may arise from the 2 nu3 mode of CO2. If the band arises from CO2, it is clear from its detailed shape and position that the molecules are not embedded in an SO2 matrix, as are H2S and H2O, but may be present as multimers or "clusters."

Atmosphere↗

The 2.5-5.0 micrometers spectra of Io: evidence for H2S and H2O frozen in SO2.

Infrared spectra of Io in the region 2.5-5.0 micrometers, including new observational data, are analyzed using detailed laboratory studies of plausible surface ices. Besides the absorption bands attributable to sulfur dioxide frosts, four infrared spectral features of Io are shown to be unidentified. These unidentified features show spatial and temporal band strength variations. One pair is centered around 3.9 micrometers (3.85 and 3.91 micrometers) and the second pair is centered around 3.0 micrometers (2.97 and 3.15 micrometers). These absorptions fall close to the fundamental stretching modes in H2S and H2O, respectively. The infrared absorption spectra of an extensive set of laboratory ices ranging from pure materials, to binary mixtures of H2S and H2O (either mixed at different concentrations or layered), to H2O:H2S:SO2 mixtures are discussed. The effects of ultraviolet irradiation (120 and 160 nm) and temperature variation (from 9 to 130 K) on the infrared spectra of the ices are examined. This comparative study of Io reflectance spectra with the laboratory mixed ice transmission data shows the following: (1) Io's surface most likely contains H2S and H2O mixed with SO2. The 3.85- and 3.91-micrometers bands in the Io spectra can be accounted for by the absorption of the S-H stretching vibration (nu 1) in H2S clusters and isolated molecules in an SO2-dominated ice. The weak 2.97- and 3.15-micrometers bands which vary spatially and temporally in the Io spectra coincide with the nu 3 and nu 1 O-H stretching vibrations of clusters of H2O molecules complexed, through hydrogen bonding and charge transfer interactions, with SO2. (2) The observations are well matched qualitatively by the transmission spectra of SO2 ices containing about 3% H2S and 0.1% H2O which have been formed by the condensation of a mixture of the gases onto a 100 K surface. (3) No new features are produced in the region 2.5 to 5.0 micrometers in the spectrum of these ices under prolonged ultraviolet irradiation or temperature variation up to 120 K. (4) Comparison of the Io spectra to transmission spectra of both mixed molecular ices and layered ices indicates that only the former can explain the shifts and splitting of the absorption bands seen in the Io spectrum and additionally can account for the fact that solid H2S is observed in the surface material of Io at temperature and pressure conditions above the sublimation point of pure H2S.

Astronomical Phenomena↗