Molecular structure of S-ethylthioacrylate Combined vibrational spectroscopic and abinitioSCF-MO study

Ab initio 6-31G* SCF-MO calculations have been carried out on S-ethyl thioacrylate [CH2CHC(O)SCH2CH3]. Fully optimized geometries, relative stabilities, dipole moments and harmonic force fields for several conformers of this molecule have been determined and the results compared with those for similar molecules. Together with FTIR and Raman spectroscopic data, the theoretical results demonstrate that S-ethyl thioacrylate exists in two different conformations about the Cα–C bond (the s-cis and s-trans forms, with CC–CO dihedral angles equal to 0° and 180°, respectively); the s-cis conformation being more stable than the s-trans form by ca. 6 kJ mol-1 for the isolated molecule. Comparison of the experimental and theoretical vibrational spectra confirms that, as concluded from our previous study on the analogous trans-S-ethyl thiocrotonate molecule (R. Fausto, P. J. Tonge and P. R. Carey, J. Chem. Soc., FaradayTrans., 1994, 90, 3491), the presence of the s-trans isomer of an α,β-unsaturated thioester can be successfully monitored by the IR band at ca. 1170 cm-1, ascribed to the Cα–C stretching mode of this form. In addition, we were also able to identify some IR bands sensitive to the conformation of the ethyl group that may be used as spectroscopic probes to study conformational equilibria associated with this internal degree of freedom in more complex S-ethyl thioester

GALEX Observations of CS and OH Emission in Comet 9P/Tempel 1 During Deep Impact

GALEX observations of comet 9P/Tempel 1 using the near ultraviolet (NUV) objective grism were made before, during and after the Deep Impact event that occurred on 2005 July 4 at 05:52:03 UT when a 370 kg NASA spacecraft was maneuvered into the path of the comet. The NUV channel provides usable spectral information in a bandpass covering 2000 - 3400 A with a point source spectral resolving power of approximately 100. The primary spectral features in this range include solar continuum scattered from cometary dust and emissions from OH and CS molecular bands centered near 3085 and 2575 A, respectively. In particular, we report the only cometary CS emission detected during this event. The observations allow the evolution of these spectral features to be tracked over the period of the encounter. In general, the NUV emissions observed from Tempel 1 are much fainter than those that have been observed by GALEX from other comets. However, it is possible to derive production rates for the parent molecules of the species detected by GALEX in Tempel 1 and to determine the number of these molecules liberated by the impact. The derived quiescent production rates are Q(H2O) = 6.4e27 molecules/s and Q(CS2) = 6.7e24 molecules/s, while the impact produced an additional 1.6e32 H2O molecules and 1.3e29 CS2 molecules, a similar ratio as in quiescent outgassing.Comment: 15 pages, 4 figures, accepted for publication in the Astrophysical Journa

Benzoylamidoacetonitrile is bound as a thioimidate in the active site of papain.

13C NMR spectroscopy has been used to demonstrate that 13CN-labeled benzoylamidoacetonitrile forms a covalent adduct with the thiol group of cysteine 25 in the active site of papain. Spectral comparison with model compounds indicates that the adduct is a thioimidate. On the basis of a proposed mechanism for the formation of the thioimidate, it is concluded that the -CH2C(= NH)S--imino nitrogen does not sit in the active site in the same manner as the thiol ester carbonyl oxygen of the thiol acyl enzyme (or the oxyanion of the tetrahedral intermediate). Thus, in this sense the stabilization of the thioimidate does not reflect a similarity in structure between the bound thioimidate and the transition state

Identity of acyl group conformations in the active sites of papain and cathepsin B by resonance Raman spectroscopy.

Resonance Raman spectroscopic data provide conclusive evidence for the existence of an acyl-enzyme intermediate during the reaction of a thionoester substrate, N-methyloxycarbonylphenylalanylglycine methyl thionoester (CH3OC(=O)-Phe-NHCH2C(=S) OCH3), with cathepsin B from porcine spleen. The resonance Raman spectrum of CH3OC(=O)-Phe-NHCH2C(=S)S-cathepsin B, where the thiol S is from the active-site cysteine residue, is compared to that of the corresponding papain acyl-enzyme. Within the limits of experimental error (+/-2 cm-1 for peak positions), there are no detectable spectral differences. Since the resonance Raman spectrum is sensitive to the torsional angles in the glycinic bonds and the cysteine linkages, the conformations are identical in those parts of the acyl-enzymes where chemical transformation occurs. A conformational analysis of the model compound CH3OC(=O)-Phe-NHCH2C(=S)SC2H5 demonstrates that the dithioacyl group in both dithioacyl-enzymes is present as a single population of a form known as conformer B. Conformer B is characterized by a small torsional angle about the glycinic NHCH2-CS(thiol) bond such that the nitrogen and S (thiol) atoms are in close contact. This conformer is widespread among the dithioacyl intermediates of plant cysteine proteinases, and it is apparent that the same chemistry is retained in a mammalian cysteine proteinase. Steady-state kinetic parameters are also reported for CH3OC(=O)-Phe-NHCH2C(=S)OCH3 reacting with papain and cathepsin B. The similarity of the Kcat values, 0.53 and 1.15 s-1, for papain and cathepsin B, respectively, provides further evidence for a conserved deacylation process

Twofold efficiency increase in nanocrystalline-TiO2/polymer photovoltaic devices by interfacial modification with a lithium salt

Modification of the interface of titanium dioxide/poly[2-(2-ethylhexyloxy)-5-methoxy-1,4,-phenylenevinylene] (TiO2/MEH-PPV) nanocomposite photovoltaic devices with a lithium salt, Li[CF3SO2](2)N, is shown to result in a twofold increase in device efficiency. The devices are of the type ITO/TiO2/MEH-PPV/Au. The TiO2 layer is deposited by doctor blading a colloidal anatase paste, and the polymer is then spin-coated on top followed by thermal evaporation of gold contacts. Careful control of manufacturing conditions and use of a 35 nm polymer layer leads to a device efficiency of 0.48% for un-modified devices. The increased efficiency following Li treatment is the result of a 40% increase in both the short-circuit current and fill factor, while the open-circuit voltage remains unchanged. A maximum efficiency of 1.05% has been achieved under 80% sun illumination. This represents a record efficiency for this type of cell. Photoconductivity experiments show a substantial increase in conductivity of the TiO2 layer following Li modification. Interfacial modification is done via a simple soaking procedure, and the effect of varying the concentration of Li[CF3SO2](2)N is discussed. We report investigations into optimization and the mechanism of such improvement, for example by varying processing parameters of the modification procedure or the ionic species themselves

A modeling tool to evaluate regional coral reef responses to changes in climate and ocean chemistry

This is the published version.We developed a spreadsheet-based model for the use of managers, conservationists, and biologists for projecting the effects of climate change on coral reefs at local-to-regional scales. The COMBO (Coral Mortality and Bleaching Output) model calculates the impacts to coral reefs from changes in average SST and CO2 concentrations, and from high temperature mortality (bleaching) events. The model uses a probabilistic assessment of the frequency of high temperature events under a future climate to address scientific uncertainties about potential adverse effects. COMBO offers data libraries and default factors for three selected regions (Hawai’i, Great Barrier Reef, and Caribbean), but it is structured with user-selectable parameter values and data input options, making possible modifications to reflect local conditions or to incorporate local expertise. Preliminary results from sensitivity analyses and simulation examples for Hawai’i demonstrate the relative importance of high temperature events, increased average temperature, and increased CO2 concentration on the future status of coral reefs; illustrate significant interactions among variables; and allow comparisons of past environmental history with future predictions

Convective Fingering of an Autocatalytic Reaction Front

We report experimental observations of the convection-driven fingering instability of an iodate-arsenous acid chemical reaction front. The front propagated upward in a vertical slab; the thickness of the slab was varied to control the degree of instability. We observed the onset and subsequent nonlinear evolution of the fingers, which were made visible by a {\it p}H indicator. We measured the spacing of the fingers during their initial stages and compared this to the wavelength of the fastest growing linear mode predicted by the stability analysis of Huang {\it et. al.} [{\it Phys. Rev. E}, {\bf 48}, 4378 (1993), and unpublished]. We find agreement with the thickness dependence predicted by the theory.Comment: 11 pages, RevTex with 3 eps figures. To be published in Phys Rev E, [email protected], [email protected], [email protected]

Infrared Dark Clouds in the Small Magellanic Cloud?

We have applied the unsharp-masking technique to the 24 $\mu$m image of the Small Magellanic Cloud (SMC), obtained with the Spitzer Space Telescope, to search for high-extinction regions. This technique has been used to locate very dense and cold interstellar clouds in the Galaxy, particularly infrared dark clouds (IRDCs). Fifty five candidate regions of high-extinction, namely high-contrast regions (HCRs), have been identified from the generated decremental contrast image of the SMC. Most HCRs are located in the southern bar region and mainly distributed in the outskirts of CO clouds, but most likely contain a significant amount of H2. HCRs have a peak-contrast at 24 $\mu$m of 2 - 2.5 % and a size of 8 - 14 pc. This corresponds to the size of typical and large Galactic IRDCs, but Galactic IRDCs are 2 - 3 times darker at 24 $\mu$m than our HCRs. To constrain the physical properties of the HCRs, we have performed NH3, N2H+, HNC, HCO+, and HCN observations toward one of the HCRs, HCR LIRS36-EAST, using the Australia Telescope Compact Array and the Mopra single-dish radio telescope. We did not detect any molecular line emission, however, our upper limits to the column densities of molecular species suggest that HCRs are most likely moderately dense with n ~ 10^{3} cm-3. This volume density is in agreement with predictions for the cool atomic phase in low metallicity environments. We suggest that HCRs may be tracing clouds at the transition from atomic to molecule-dominated medium, and could be a powerful way to study early stages of gas condensation in low metallicity galaxies. Alternatively, if made up of dense molecular clumps < 0.5 pc in size, HCRs could be counterparts of Galactic IRDCs, and/or regions with highly unusual abundance of very small dust grains.Comment: accepted for publication in the Astronomical Journa

Bradyzoite pseudokinase 1 is crucial for efficient oral infectivity of the Toxoplasma gondii tissue cyst.

The tissue cyst formed by the bradyzoite stage of Toxoplasma gondii is essential for persistent infection of the host and oral transmission. Bradyzoite pseudokinase 1 (BPK1) is a component of the cyst wall, but nothing has previously been known about its function. Here, we show that immunoprecipitation of BPK1 from in vitro bradyzoite cultures, 4 days postinfection, identifies at least four associating proteins: MAG1, MCP4, GRA8, and GRA9. To determine the role of BPK1, a strain of Toxoplasma was generated with the bpk1 locus deleted. This BPK1 knockout strain (Δbpk1) was investigated in vitro and in vivo. No defect was found in terms of in vitro cyst formation and no difference in pathogenesis or cyst burden 4 weeks postinfection (wpi) was detected after intraperitoneal (i.p.) infection with Δbpk1 tachyzoites, although the Δbpk1 cysts were significantly smaller than parental or BPK1-complemented strains at 8 wpi. Pepsin-acid treatment of 4 wpi in vivo cysts revealed that Δbpk1 parasites are significantly more sensitive to this treatment than the parental and complemented strains. Consistent with this, 4 wpi Δbpk1 cysts showed reduced ability to cause oral infection compared to the parental and complemented strains. Together, these data reveal that BPK1 plays a crucial role in the in vivo development and infectivity of Toxoplasma cysts

WISE/NEOWISE Preliminary Analysis and Highlights of the 67P/Churyumov-Gerasimenko Near Nucleus Environs

On January 18-19 and June 28-29 of 2010, the Wide-field Infrared Survey Explorer (WISE) spacecraft imaged the Rosetta mission target, comet 67P/Churyumov-Gerasimenko. We present a preliminary analysis of the images, which provide a characterization of the dust environment at heliocentric distances similar to those planned for the initial spacecraft encounter, but on the outbound leg of its orbit rather than the inbound. Broad-band photometry yields low levels of CO2 production at a comet heliocentric distance of 3.32 AU and no detectable production at 4.18 AU. We find that at these heliocentric distances, large dust grains with mean grain diameters on the order of a millimeter or greater dominate the coma and evolve to populate the tail. This is further supported by broad-band photometry centered on the nucleus, which yield an estimated differential dust particle size distribution with a power law relation that is considerably shallower than average. We set a 3-sigma upper limit constraint on the albedo of the large-grain dust at <= 0.12. Our best estimate of the nucleus radius (1.82 +/- 0.20 km) and albedo (0.04 +/- 0.01) are in agreement with measurements previously reported in the literature