Mass-independent Dunham analysis of the known electronic states of platinum sulfide, PtS, and analysis of the electronic field-shift effect.

Several new vibrational bands of the [12.5] Ω = 0+-X3Σ- Ω=0+ and the [15.9] B Ω = 0+-X3Σ- Ω=0+ transitions have been observed in high resolution absorption measurements recorded using Intracavity Laser Spectroscopy (ILS). These new bands have been rotationally analyzed and incorporated into a comprehensive PtS dataset that was fit to a mass-independent Dunham expression using PGOPHER. The comprehensive dataset included all reported field-free, gas phase spectroscopic data for PtS, including 32 Fourier transform microwave transitions (estimated accuracy: 1 kHz), 9 microwave/optical double resonance transitions (25 kHz), 51 millimeter and submillimeter transitions (25-50 kHz), 469 molecular beam-laser induced fluorescence transitions (0.003 cm-1), and 4870 ILS transitions (0.005 cm-1). The determined equilibrium constants have been used with the Rydberg-Klein-Rees method to produce potential energy curves for the four known electronic states of PtS. Isotopic shifts in electronic transition energy beyond expectations from the Born-Oppenheimer approximation were observed and treated as electronic field-shift effects due to the difference in the nuclear charge radius between Pt isotopes. The magnitude and sign of the determined field-shift parameters are rationalized through the analysis of the previously reported ab initio calculations.

The spin-forbidden a 4Σ--X 2Π1/2 transition of GeH detected in absorption using intracavity laser spectroscopy.

The a 4Σ--X 2Π1/2 transition of GeH has been recorded in absorption for the first time using Intracavity Laser Spectroscopy (ILS). The GeH molecules were produced in a 0.40-0.60 A DC plasma discharge inside an aluminum hollow cathode, using 500 mTorr of Ar, 100 mTorr of H2, and 200 mTorr of GeH4. This cathode is located within the resonator cavity of a Coherent Verdi™ V-10 pumped dye laser. Effective path lengths for this series of measurements using the ILS method ranged from 2 to 7 km. Spectra were calibrated using the absorption spectrum of I2 collected from an extracavity cell, the I2 transmission spectrum from Salami and Ross, J. Mol. Spectrosc. 223(1), 157 (2005) and PGOPHER's [C. M. Western, J. Quant. Spectrosc. Radiat. Transfer 186, 221-242 (2016)] calibration feature. Differences in peak positions between calibrated experimental spectra and the reference data were on average less than ±0.002 cm-1. All eight branches expected to have appreciable intensity for the transition have been identified, and isotopologue splitting was observed in features of 5 of the 8 identified rotational branches. Molecular constants have been obtained for the a 4Σ- states of 70GeH (20.84% abundant), 72GeH (27.54% abundant), and 74GeH (36.28% abundant). The transitions were fit using PGOPHER, holding the ground state constants fixed to the values reported by Towle and Brown [Mol. Phys. 78(2), 249 (1993)]. The constants for the a 4Σ- state of 74GeH determined by the fit are T0 = 16 751.5524(13) cm-1, B0 = 6.764 912(33) cm-1, D0 = 0.459 60(17) × 10-3 cm-1, λSS = 9.7453(12) cm-1, λD = 0.468(14) × 10-3 cm-1, γ = 0.077 878(84), and γS = -0.361(77) × 10-3 cm-1.

Analysis of a new MoO transition in the near-IR: a combined theoretical and experimental study.

The near-infrared electronic spectrum of MoO has been recorded in emission using the Fourier transform spectrometer associated with the National Solar Observatory at Kitt Peak, AZ. The gas phase MoO molecules were produced in a neon-based electric discharge using a molybdenum hollow cathode and a trace amount of oxygen. One MoO molecular band was observed in the spectrum with a red-degraded bandhead at 6735 cm(-1) and is assigned as the (0,0) band of the c (3)Π1 - a (3)Σ(-) 0+ transition. The assignment is based upon isotopologue shifts and ab initio calculations. Results from the ab initio calculations and analysis are presented. The new calculations support the assignment of the observed transition and have led to reassignment of several electronic states from previous work.

High resolution electronic spectroscopy of the A (2)Σ- - X (2)Π1/2 transition of PtN.

The (2,0) vibrational band of the A (2)Σ(-) - X (2)Π1/2 transition of platinum nitride, PtN, was recorded at Doppler-limited resolution using intracavity laser absorption spectroscopy (ILS) and at sub-Doppler resolution using molecular beam laser induced fluorescence (LIF) spectroscopy. Isotopologue structure for (194)PtN, (195)PtN, and (196)PtN, magnetic hyperfine splitting due to (195)Pt (I = ½), and nuclear quadrupole splitting due to (14)N (I = 1) were observed in the spectrum. Molecular constants for the ground and excited states are derived. The hyperfine interactions are used to illuminate the nature of the A (2)Σ(-) excited electronic state.

Chloride-led disruption of the intestinal mucous layer impedes Salmonella invasion: evidence for an 'enteric tear' mechanism.

METHODS: The intestinal epithelial layer can switch from a net absorptive state to one of net secretion in the presence of luminal toxins and pathogens. This suggests an innate defence role for regulated secretion of mucus, electrolytes and water. We hypothesised that chloride-led fluid secretion across the mucus-covered intestinal epithelium alters barrier properties by influencing the overlying mucous-gel layer. RESULTS: We demonstrated that chloride-led disruption of the epithelial-associated mucus-gel covering HT29-MTX-E12 (E12) human colonic epithelial monolayers, a goblet-cell like line derived from parental HT29 cells, resulted in reduction of associated mucus as well as a reduction in mucous-gel density and barrier properties. Changes in epithelial secretory state were accompanied by increased water transport, and the resulting loss of gel integrity reduced Salmonella typhimurium invasion of epithelia in both E12 monolayers and of isolated rat ileal mucosae. However, neither chloride secretion nor mucus disruption altered numbers of adhering bacteria. CONCLUSION: These data suggest a role for chloride led fluid secretion in the shedding of the adherent mucous-gel layer, possibly as a rate-limiting innate defence mechanism, and offer evidence for "enteric tears" in intestinal host defence.

The Pt2 (1,0) band of System VI in the near infrared by intracavity laser absorption spectroscopy.

Intracavity laser absorption spectroscopy has been used to record rotationally resolved electronic spectra of Pt(2) in the near infrared. The metal dimers were created using a 50 mm-long, platinum-lined hollow cathode plasma discharge. The observed transition at 12 937 cm(-1) is identified as the (1,0) band of System VI, with state symmetries Ω = 0 - X Ω = 0.

Rat, ovine and bovine Peyer's patches mounted in horizontal diffusion chambers display sampling function.

Freshly excised rat, ovine and bovine ileal Peyer's patch (PP) and non-Peyer's patch tissues (NPP) were mounted in modified horizontal polyethylene diffusion chambers with a range of window areas. Rat tissue was initially used to establish that barrier function and histology were maintained for up to 60 min. Horse-radish peroxidase (HRP) fluxes and S. Typhimurium adherence and invasion were significantly higher in rat PP over NPP. Particle uptake was shown to be a rapid, energy-, time-, and size-dependent process, occurring more readily in PP than NPP tissue in each species. In a kinetic analysis, particles were localized initially in the follicle-associated epithelium and then in the dome region. For NPP uptake, particles were initially localized to villous epithelium, and were then detected in the crypts and lamina propria. Electrophysiological parameters including pharmacologically-stimulated inward short-circuit current responses were determined in isolated PP and NPP from each species mounted under identical conditions in Ussing chambers. In conclusion, comparative functional and histological characteristics of PP from several species were demonstrated in horizontal diffusion chambers. Horizontal diffusion chambers are therefore a useful in vitro model in which a range of functions including transport of particulate formulations by PP may be examined.

Oral delivery of pathogens from the intestine to the nervous system.

Most therapeutic agents are delivered orally. Consequently, the major classes of therapeutically useful chemicals are partially lipophilic, small molecular weight compounds. They have reasonable permeability coefficient values across cell membranes, including those of intestinal epithelia and vascular endothelia. In contrast, large molecular weight biotechnology compounds have limited usefulness by non-injected routes as a consequence of their low membrane permeability and variable solubility. However, a wide range of infectious agents have developed strategies or have hijacked physiological routings in order to enter the host by the oral route. Efforts to address such issues have refreshed interest in mechanisms by which different types of payloads (including particulates and microorganisms) translocate across gut epithelia and then distribute to target tissues. Special attention is given to the potential role of the enteric nervous system and its plasticity.

The electronic spectrum of AuO: a combined theoretical and experimental study.

The near-infrared electronic spectrum of AuO(1) has been re-examined in light of the new microwave data on the v = 0 and v = 1 vibrations of the X(2)Pi(3/2) state of AuO. The two observed bands in the spectrum, with red-degraded bandheads located at 10726 and 10665 cm(-1), have been reanalyzed. New theoretical work on AuO clarifies the electronic structure, and the bands in the infrared are now assigned as the (0,1) and (1,2) bands of the a(4)Sigma(-)(3/2) - X(2)Pi(3/2) transition, respectively.

Molecular Constants for the v=0, b(1)Sigma(g)(+) Excited State of O(2): Improved Values Derived from Measurements of the Oxygen A-Band Using Intracavity Laser Spectroscopy.

High-resolution intracavity laser spectroscopy (ILS) absorption measurements have been made on the b-X oxygen electronic transition (the A-band) which has bandheads occurring in the region of 13 165 cm(-1). The positions of the lines were determined to an accuracy that is based on calibration with I(2) absorption lines using the Laboratoire Aimé Cotton (Orsay) Atlas as reference. Based on the ILS measurements and the more accurately determined positions given by L. R. Brown and C. Plymate (J. Mol. Spectrosc. 199, 166-179 (2000)) and with the (3)Sigma(g)(-) ground state molecular constants fixed at the values determined by G. Rouillé et al. (J. Mol. Spectrosc. 154, 372-382 (1992)), the following values (in cm(-1)) were found for the molecular constants: T(0)=13122.2524(1); B(0)=1.391244(2); D(0)=5.352(4)x10(-6); and H(0)=-1.2(2)x10(-11). These results are compared with values derived from fits of the line positions listed in several other studies of this transition. Copyright 2001 Academic Press.