Excess electrons bound to H2S trimer and tetramer clusters.

We have prepared the hydrogen sulfide trimer and tetramer anions, (H2S)3- and (H2S)4-, measured their anion photoelectron spectra, and applied high-level quantum chemical calculations to interpret the results. The sharp peaks at low electron binding energies in their photoelectron spectra and their diffuse Dyson orbitals are evidence for them both being dipole-bound anions. While the dipole moments of the neutral (H2S)3 and (H2S)4 clusters are small, the excess electron induces structural distortions that enhance the charge-dipolar attraction and facilitate the binding of diffuse electrons.

Quantum for pressure.

Jay Hendricks tells about ongoing work to change the realization and dissemination of the pascal, which will lead to the elimination of mercury-barometer pressure standards.

Recommended practice for calibrating vacuum gauges of the ionization type.

This article represents a recommended practice for the calibration of ionization gauges using the comparison method. In this method, ionization gauges are compared to a working standard that has an SI traceable calibration. The ionization gauge is either of the hot-cathode ionization type or the cold-cathode ionization type. Details of the calibration apparatus, the principle of operation of the gauges, data analysis, uncertainty budget, and reporting the uncertainty are given.

Quantum-based vacuum metrology at NIST.

The measurement science in realizing and disseminating the unit for pressure in the International System of Units (SI), the pascal (Pa), has been the subject of much interest at NIST. Modern optical-based techniques for pascal metrology have been investigated, including multi-photon ionization and cavity ringdown spectroscopy. Work is ongoing to recast the pascal in terms of quantum properties and fundamental constants and in so doing, make vacuum metrology consistent with the global trend toward quantum-based metrology. NIST has ongoing projects that interrogate the index of refraction of a gas using an optical cavity for low vacuum, and count background particles in high vacuum to extreme high vacuum using trapped laser-cooled atoms.

Cell-based refractometer for pascal realization.

We describe a method for determining the density of helium via measurements of optical refractivity. In combination with the equation of state, this allows realization of the pascal. Our apparatus is based on the integration of a gas triple-cell into a quasi-monolithic heterodyne interferometer: the stability of the interferometer is ±50 pm over 10 h. We claim the contribution of cell window thinning to pathlength uncertainty can be canceled within an uncertainty of 0.37 fm/Pa per window pass, of which for our 25 cm cell length corresponds to a fractional error of 9.3×10-6 in the measure of helium refractivity. We report the ratio (n-1)N2 /(n-1)He=8.570354(13) at p=367.420(4) kPa, T=293.1529(13) K and λ=632.9908(6) nm, which can be used to calibrate less-accurate refractometers. By measuring helium refractivity at known temperature and pressure, we determined the Boltzmann constant with standard uncertainty kB=1.380652(17)×10-23 JK-1.

Final Report on the Key Comparison CCM.P-K4.2012 in Absolute Pressure from 1 Pa to 10 kPa.

The report summarizes the Consultative Committee for Mass (CCM) key comparison CCM.P-K4.2012 for absolute pressure spanning the range of 1 Pa to 10 000 Pa. The comparison was carried out at six National Metrology Institutes (NMIs), including National Institute of Standards and Technology (NIST), Physikalisch-Technische Bundesanstalt (PTB), Czech Metrology Institute (CMI), National Metrology Institute of Japan (NMIJ), Centro Nacional de Metrología (CENAM), and DI Mendeleyev Institute for Metrology (VNIIM). The comparison was made via a calibrated transfer standard measured at each of the NMIs facilities using their laboratory standard during the period May 2012 to September 2013. The transfer package constructed for this comparison preformed as designed and provided a stable artifact to compare laboratory standards. Overall the participants were found to be statistically equivalent to the key comparison reference value.

Comparison measurements of low-pressure between a laser refractometer and ultrasonic manometer.

We have developed a new low-pressure sensor which is based on the measurement of (nitrogen) gas refractivity inside a Fabry-Perot cavity. We compare pressure determinations via this laser refractometer to that of well-established ultrasonic manometers throughout the range 100 Pa to 180 000 Pa. The refractometer demonstrates 10(-6) ⋅ p reproducibility for p > 100 Pa, and this precision outperforms a manometer. We also claim the refractometer has an expanded uncertainty of U(pFP) = [(2.0 mPa)(2) + (8.8 × 10(-6) ⋅ p)(2)](1/2), as realized through the properties of nitrogen gas; we argue that a transfer of the pascal to p < 1 kPa using a laser refractometer is more accurate than the current primary realization.

Performance of a dual Fabry-Perot cavity refractometer.

We have built and characterized a refractometer that utilizes two Fabry-Perot cavities formed on a dimensionally stable spacer. In the typical mode of operation, one cavity is held at vacuum, and the other cavity is filled with nitrogen gas. The differential change in length between the cavities is measured as the difference in frequency between two helium-neon lasers, one locked to the resonance of each cavity. This differential change in optical length is a measure of the gas refractivity. Using the known values for the molar refractivity and virial coefficients of nitrogen, and accounting for cavity length distortions, the device can be used as a high-resolution, multi-decade pressure sensor. We define a reference value for nitrogen refractivity as n-1=(26485.28±0.3)×10(-8) at p=100.0000 kPa, T=302.9190 K, and λ(vac)=632.9908 nm. We compare pressure determinations via the refractometer and the reference value to a mercury manometer.

Differential induction of isolated lymphoid follicles in the gut by 18ß-glycyrrhetinic acid.

18ß-glycyrrhetinic acid (GRA) is a pharmacologically active component of licorice root with documented immunomodulatory properties. We reported that GRA administered orally to mice induces B cell recruitment to isolated lymphoid follicles (ILF) in the small intestine and shortens the duration of rotavirus antigen shedding. ILF are dynamic lymphoid tissues in the gut acquired post-natally upon colonization with commensal bacteria and mature through B cell recruitment to the follicles, resulting in up-regulation of IgA synthesis in response to changes in the composition of microbiota. In this study, we investigated potential mechanisms by which GRA induces ILF maturation in the ileum and the colon using mice depleted of enteric bacteria and a select group of mice genetically deficient in pattern recognition receptors. The data show GRA was unable to induce ILF maturation in ileums of mice devoid of commensal bacteria, MyD88-/- or NOD2-/- mice, but differentially induced ILF in colons. Increased expression of chemokine and chemokine receptor genes that modulate B and T cell recruitment to the mucosa were in part dependent on NOD2, TLR, and signaling adaptor protein MyD88. Together the results suggest GRA induces ILF through cooperative signals provided by bacterial ligands under normal conditions to induce B cell recruitment to ILF to the gut, but that the relative contribution of these signals differ between ileum and colon.

18ß-Glycyrrhetinic acid inhibits methicillin-resistant Staphylococcus aureus survival and attenuates virulence gene expression.

Methicillin-resistant Staphylococcus aureus (MRSA) has become a major source of infection in hospitals and in the community. Increasing antibiotic resistance in S. aureus strains has created a need for alternative therapies to treat disease. A component of the licorice root Glycyrrhiza spp., 18ß-glycyrrhetinic acid (GRA), has been shown to have antiviral, antitumor, and antibacterial activity. This investigation explores the in vitro and in vivo effects of GRA on MRSA pulsed-field gel electrophoresis (PFGE) type USA300. GRA exhibited bactericidal activity at concentrations exceeding 0.223 µM. Upon exposure of S. aureus to sublytic concentrations of GRA, we observed a reduction in expression of key virulence genes, including saeR and hla. In murine models of skin and soft tissue infection, topical GRA treatment significantly reduced skin lesion size and decreased the expression of saeR and hla genes. Our investigation demonstrates that at high concentrations GRA is bactericidal to MRSA and at sublethal doses it reduces virulence gene expression in S. aureus both in vitro and in vivo.

18ß-glycyrrhetinic acid delivered orally induces isolated lymphoid follicle maturation at the intestinal mucosa and attenuates rotavirus shedding.

Glycyrrhizin, an abundant bioactive component of the medicinal licorice root is rapidly metabolized by gut commensal bacteria into 18ß-glycyrrhetinic acid (GRA). Either or both of these compounds have been shown to have antiviral, anti-hepatotoxic, anti-ulcerative, anti-tumor, anti-allergenic and anti-inflammatory activity in vitro or in vivo. In this study, the ability of GRA to modulate immune responses at the small intestinal mucosa when delivered orally was investigated. Analysis of cytokine transcription in duodenal and ileal tissue in response to GRA treatment revealed a pattern of chemokine and chemokine receptor gene expression predictive of B cell recruitment to the gut. Consistent with this finding, GRA induced increases in CD19(+) B cells in the lamina propria and B220(+) B cell aggregates framed by CD11c(+) dendritic cells in structures resembling isolated lymphoid follicles (ILF). Using a mouse model of rotavirus infection, GRA reduced the duration of viral antigen shedding, and endpoint serum antibody titers were higher in GRA-treated animals. Together the data suggest GRA delivered orally augments lymphocyte recruitment to the intestinal mucosa and induces maturation of B cell-rich ILF independently of ectopic antigenic stimulus. These results provide further support a role for dietary ligands in modulation of dynamic intestinal lymphoid tissue.

18ß-glycyrrhetinic acid inhibits rotavirus replication in culture.

BACKGROUND: Glycyrrhizin (GA) and primary metabolite 18ß-glycyrrhetinic acid (GRA) are pharmacologically active components of the medicinal licorice root, and both have been shown to have antiviral and immunomodulatory properties. Although these properties are well established, the mechanisms of action are not completely understood. In this study, GA and GRA were tested for the ability to inhibit rotavirus replication in cell culture, toward a long term goal of discovering natural compounds that may complement existing vaccines. METHODS: Epithelial cells were treated with GA or GRA various times pre- or post-infection and virus yields were measured by immunofluorescent focus assay. Levels of viral proteins VP2, VP6, and NSP2 in GRA treated cells were measured by immunoblot to determine if there was an effect of GRA treatment on the accumulation of viral protein. RESULTS: GRA treatment reduced rotavirus yields by 99% when added to infected cultures post-- virus adsorption, whereas virus yields in GA treated cultures were similar to mock treated controls. Time of addition experiments indicated that GRA-mediated replication inhibition likely occurs at a step or steps subsequent to virus entry. The amounts of VP2, VP6 and NSP2 were substantially reduced when GRA was added to cultures up to two hours post-entry. CONCLUSIONS: GRA, but not GA, has significant antiviral activity against rotavirus replication in vitro, and studies to determine whether GRA attenuates rotavirus replication in vivo are underway.

Lithium cluster anions: photoelectron spectroscopy and ab initio calculations.

Structural and energetic properties of small, deceptively simple anionic clusters of lithium, Li(n)(-), n = 3-7, were determined using a combination of anion photoelectron spectroscopy and ab initio calculations. The most stable isomers of each of these anions, the ones most likely to contribute to the photoelectron spectra, were found using the gradient embedded genetic algorithm program. Subsequently, state-of-the-art ab initio techniques, including time-dependent density functional theory, coupled cluster, and multireference configurational interactions methods, were employed to interpret the experimental spectra.