Pure component spectral analysis of surface adsorbed species measured under real conditions. BTEM-DRIFTS study of CO and NO reaction over a Pd/gamma-Al2O3 catalyst

The adsorption of NO and CO was studied on an alumina-supported palladium catalyst by in situ diffuse reflectance infrared spectroscopy (DRIFTS). The temperature range was 50-160 degrees C and a wide variety of partial pressures was used. The band-target entropy minimization (BTEM) algorithm was applied to the DRIFTS data sets resulting in the pure component spectra of numerous species adsorbed on both the Pd (primarily a variety of Pd-CO and Pd-NO species, in various oxidation states and coordinations) and alumina surface species (i.e. nitrates, nitrites, carbonates, bicarbonates, formates, and isocyanates) as well as gas phase species. Twenty seven previously known species were identified as well as three new and previously unreported or previously unassigned spectra. The present study indicates that BTEM can be meaningfully applied to Pd/Al2O3 DRIFTS in order to provide enhanced spectroscopic analysis. Moreover, the present results are compared in detail with the recent BTEM analysis of CO and NO adsorption on Pt/Al2O3 using DRIFTS (Phys. Chem. Chem. Phys. 2008, 10, 3535).     

Exiguaquinol: a novel pentacyclic hydroquinone from Neopetrosia exigua that inhibits Helicobacter pylori MurI

Bioassay-guided fractionation of the methanol extract of the Australian sponge Neopetrosia exigua led to the isolation of exiguaquinol (2), a new pentacyclic hydroquinone that inhibited Helicobacter pylori glutamate racemase (MurI) with an IC(50) of 4.4 microM. Its structure and relative configuration were assigned on the basis of spectroscopic data. Exiguaquinol (2), bearing a novel pentacyclic ring skeleton, is the first natural product to show inhibition of H. pylori MurI. Its protein-ligand modeling is also discussed.     

Deuterium isotope effect on molar heat capacities and apparent molar heat capacities in dilute aqueous solutions: A multi-channel heat-flow microcalorimeter study

The molar heat capacities of chloroform, dichloromethane, methanol, acetonitrile, acetone, dimethyl sulfoxide, benzene, dimethylformamide, toluene, and cyclohexane, as well as their deuterated isotopologues, were measured using a multi-channel heat conduction TAM (Thermal Activity Monitor) III microcalorimeter. In addition, the apparent molar heat capacities of some of the associated dilute aqueous solutions (0.0039 < solute mole fraction, x_i < 0.0210) were also measured. A temperature drop method from (298.15 to 297.15) K at 0.1 MPa was employed. The corresponding heat capacities were determined from the integration of the measured heat flow. The heat capacity results are shown to be in good to very good agreement with the available literature values. In addition, good correlations were obtained for the effect of isotopic substitution on both molar heat capacity and apparent molar heat capacity in aqueous solutions. These correlations should be useful in the prediction of the molar heat capacities or the apparent molar heat capacities of other deuterated compounds. Since these measurements were conducted with ampoules, the effects of heat of condensation and/or vapor space on the accuracy of the heat capacity determinations are discussed. The overall results from this study demonstrate the utility of a multi-channel heat conduction microcalorimeter in obtaining good reproducibility and good accuracy for molar heat capacities as well as apparent molar heat capacities from simultaneous samples.     

On the existence of nanojoins with given parameters

Nanojoins are parts of large carbon molecules joining several nanotubes with the same or different parameters and chemical and electrical properties. It is known that Euler’s formula implies that such nanojoins must contain faces that are not hexagons if at least three tubes are joined. As the atoms in a nanojoin are carbon atoms preferring hexagonal rings, it is normally assumed that apart from hexagons only pentagons and heptagons occur. In this paper we will give necessary and sufficient conditions for the existence of nanojoins joining nanotubes with given parameters and given numbers of pentagons and heptagons.     

Comparative study of Factor Xa fluorogenic substrates and their influence on the quantification of LMWHs

Low molecular weight heparins (LMWHs) are recognised as the preferred anticoagulants in the prevention and treatment of venous thromboembolism. Anti-Factor Xa (anti-FXa) levels are used to monitor the anticoagulant effect of LMWHs and such assays are routinely employed in hospital diagnostic laboratories. In this study, a fluorogenic anti-FXa assay was developed using a commercially available fluorogenic substrate with an attached 6-amino-1-naphthalene-sulfonamide (ANSN) fluorophore and was used for the determination of two LMWHs, enoxaparin and tinzaparin and the heparinoid, danaparoid. The assay was based on the complexation of heparinised plasma with 100 nM exogenous FXa and 25 μM of the fluorogenic substrate Mes-D-LGR-ANSN (C₂H₅)₂ (SN-7). The assay was tested with pooled plasma samples spiked with anticoagulant concentrations in the range 0–1.6 U mL⁻¹. The statistically sensitive assay range was 0–0.4 U mL⁻¹ for enoxaparin and tinzaparin and 0–0.2 U mL⁻¹ for danaparoid, with assay variation typically below 10.5%. This assay was then compared with a previously published fluorogenic anti-FXa assay developed with the peptide substrate, methylsulfonyl-d-cyclohexylalanyl-glycyl-arginine-7-amino-4-methylcoumarin acetate (Pefafluor FXa). Both assays were compared in terms of fluorescence intensity, lag times and sensitivity to anticoagulants.     

Two isomorphous transition metal complexes containing a protonated diaminopurine ligand: diaquabis(2,6‐diamino‐7H‐purin‐1‐ium‐κN9)bis(homophthalato‐κO)nickel(II) tetrahydrate and the cobalt(II) analogue

The two isomorphous title compounds, [M(C₅H₇N₆)₂(C₉H₆O₄)₂(H₂O)₂]·4H₂O or M²⁺(Hdap⁺)₂(hpt²⁻)₂(H₂O)₂·4H₂O {where dap is 2,6‐diaminopurine, H₂hpt is homophthalic acid [2‐(2‐carboxyphenyl)acetic acid] and M is Ni^II or Co^II}, consist of neutral M²⁺(Hdap⁺)₂(hpt²⁻)₂(H₂O)₂ monomers, where the M^II cation lies on an inversion centre and its MN₂O₄ octahedral environment is defined by one N atom (from Hdap⁺), two O atoms (from one hpt²⁻ dianion and one water molecule) and their inversion images. The structures are unusual in that the Hdap⁺ cation occurs in an uncommon protonated state (as 2,6‐diamino‐7H‐purin‐1‐ium) and both ligands bind in an unprecedented monodentate fashion. The existence of a large number of donors and acceptors for hydrogen bonding, together with π–π interactions, leads to a rather complex three‐dimensional structure.     

Surface plasmon resonance as a probe of interactions between a thin‐film gold electrode and an aqueous supporting electrolyte containing 1‐ethyl‐3‐methyl‐imidazolium ethyl sulfate ionic liquid

Surface plasmon resonance (SPR) and electrochemical measurements are combined in this work to study the interactions of a gold film electrode with aqueous electrolytes of an ionic liquid (IL), 1‐ethyl‐3‐methyl‐imidazolium ethyl sulfate. The optical response of the bulk electrolyte strongly affects the SPR angles, and the critical angle data help to separate these bulk effects from those arising strictly from the electrode surface. The optical parameters of the Au‐electrolyte system are determined by fitting the SPR angle‐spectra to calculated results of a multilayer reflectivity model. Both in the absence and in the presence of externally applied voltages, the SPR signal of the experimental interface is dominated by the dielectric behavior of the bulk electrolyte. No significant chemisorptions are detected for the IL contents (0.036–0.087 mole fraction) of the electrolytes used. The results demonstrate how angle resolved SPR measurements can be employed to determine the suitability of specific ILs as solutes for aqueous background electrolytes in electrochemical SPR sensing experiments. Copyright © 2011 John Wiley & Sons, Ltd.     

Pure component Raman spectral reconstruction from glazed and unglazed Yuan,Ming, and Qing shards: a combined Raman microscopy and BTEM study

Raman mapping measurements were performed on the glazed and unglazed surfaces of shards excavated from Yuan, Ming, and Qing dynasty strata. A number of areas on each surface were chosen. Circa 21 × 21 pixels were measured for each area using both 514 and 785‐nm laser as the Raman excitation. Data were collected from 100–3600 cm⁻¹. Many sets of spectra exhibited very intense fluorescence. In spite of the intense fluorescence, the resulting sets of spectra were collated and analyzed together using the band‐target entropy minimization (BTEM) algorithm. Pure component spectral estimates of many of the major components were achieved, without the use of any a priori information such as spectral libraries. These include α‐silica quartz, carbon, anatase, cobalt oxides, hematite, glassy silicate, and lanthanide complexes. In addition, two further unidentified pure component spectra A and B were recovered as well as an interference pattern due to the microscopic texture of the shards (associated with small particle/thin layer domains). The carbon was primarily present in elemental form, i.e. mixture of amorphous and graphitic (unordered and ordered domains); however there is an evidence of some partial oxidation, i.e. formation of carboxylates. The interference patterns and the lanthanide complexes were only observed when using the longer wavelength red laser. The cobalt oxides and the anatase were only observed when using the green laser. In summary, the combination of Raman microscopy and BTEM has allowed the enumeration of many of the underlying spectral patterns present and hence unambiguous identification of the major individual components present in the archaeological samples. This approach would appear applicable to other classes of archaeological materials as well. Limitations and extensions of the present approach are discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Teaching Science as Science Is Practiced: Opportunities and Limits for Enhancing Preservice Elementary Teachers' Self‐Efficacy for Science and Science Teaching

Science teaching in elementary schools, or the lack thereof, continues to be an area of concern and criticism. Preservice elementary teachers' lack of confidence in teaching science is a major part of this problem. In this mixed‐methods study, we report the impacts of an inquiry‐based science course on preservice elementary teachers' self‐efficacy for science and science teaching, understanding of science, and willingness to teach it in their future careers. Our findings suggest that for some students, the inquiry‐based science course positively influenced their self‐efficacy for science and science teaching. Gains were made in a majority of students' conceptual understanding of science, understanding of the science process and scientific research, and confidence with science and science teaching. The subjects did not experience the course uniformly, however. Rather, there appeared to be two distinct groups, one on a trajectory of improving their outlook on science teaching and one worsening. The results presented here therefore provoke some interesting questions regarding preservice elementary teachers' preparation for science teaching.