| 1. |
- Hellman, A, et al.
(author)
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Predicting catalysis : understanding ammonia synthesis from first-principles calculations
- 2006
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In: Journal of Physical Chemistry B. - 1520-6106 .- 1520-5207. ; 110, s. 17719-17735
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Journal article (peer-reviewed)abstract
- Here, we give a full account of a large collaborative effort toward an atomic-scale understanding of modern industrial ammonia production over ruthenium catalysts. We show that overall rates of ammonia production can be determined by applying various levels of theory (including transition state theory with or without tunneling corrections, and quantum dynamics) to a range of relevant elementary reaction steps, such as N(2) dissociation, H(2) dissociation, and hydrogenation of the intermediate reactants. A complete kinetic model based on the most relevant elementary steps can be established for any given point along an industrial reactor, and the kinetic results can be integrated over the catalyst bed to determine the industrial reactor yield. We find that, given the present uncertainties, the rate of ammonia production is well-determined directly from our atomic-scale calculations. Furthermore, our studies provide new insight into several related fields, for instance, gas-phase and electrochemical ammonia synthesis. The success of predicting the outcome of a catalytic reaction from first-principles calculations supports our point of view that, in the future, theory will be a fully integrated tool in the search for the next generation of catalysts.
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| 2. |
- Aad, G., et al.
(author)
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The ATLAS Experiment at the CERN Large Hadron Collider
- 2008
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In: Journal of Instrumentation. - 1748-0221. ; 3:S08003
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Research review (peer-reviewed)abstract
- The ATLAS detector as installed in its experimental cavern at point 1 at CERN is described in this paper. A brief overview of the expected performance of the detector when the Large Hadron Collider begins operation is also presented.
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| 3. |
- Alsmeyer, H, et al.
(author)
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Ex-vessel core melt stabilization research (ECOSTAR)
- 2005
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In: Nuclear Engineering and Design. - : Elsevier BV. - 0029-5493 .- 1872-759X. ; 235:2-4, s. 271-284
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Journal article (peer-reviewed)abstract
- The project on ex-vessel core melt stabilization research (ECOSTAR) started in January 2000 to be concluded by end of 2003. The project is performed by 14 partner institutions from five European countries and involves a large number of experiments with low- and high-temperature simulant melts and real corium at different scales. Model development and scaling analysis allows application of the research results to existing and to future LWRs in the area of reactor design and accident mitigation. The project is oriented toward the analysis and mitigation of severe accident sequences that could occur in the ex-vessel phase of a postulated core melt accident. The issues are: (1) the release of melt form the pressure vessel, (2) the transfer and spreading of the melt on the basement, (3) the analysis of the physical-chemical processes that are important for corium behavior especially during concrete erosion with onset of solidification, and (4) stabilization of the melt by cooling through direct water contact. The results achieved so far resolve a number of important issues: the amount of melt that could be transferred at RPV failure from the RPV into the containment can be substantially reduced by lowering the residual pressure in the primary circuit. It is found that melt dispersion also strongly depends on the location of the RPV failure, and that lateral failure results in substantially less melt dispersion. During melt release, the impinging melt jet could erode parts of the upper basement surface. Jet experiments and a derived heat transfer relation allow estimation of its contribution to concrete erosion. Spreading of the corium melt on the available basement surface is an important process, which defines the initial conditions for concrete attack or for the efficiency of cooling in case of water contact, respectively. Validation of the spreading codes based on a large-scale benchmark experiment is underway and will allow determination of the initial conditions, for which a corium melt can be assumed to spread homogeneously over the available surface. Experiments with UO(2)-based corium melts highlight the role of phase segregation during onset of melt solidification and during concrete erosion. To cool the spread corium melt, the efficacy of top flooding and bottom flooding is investigated in small-scale and in large-scale experiments, supported by model developments. Project assessment is continuing to apply the results to present and future reactors.
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| 4. |
- Charles, Nicolas, et al.
(author)
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Lyn Kinase Controls Basophil GATA-3 Transcription Factor Expression and Induction of Th2 Cell Differentiation
- 2009
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In: Immunity. - : Elsevier BV. - 1074-7613 .- 1097-4180. ; 30:4, s. 533-543
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Journal article (peer-reviewed)abstract
- T helper 1 (Th1)-Th2 cell balance is key to host defense and its dysregulation has pathophysiological consequences. Basophils are important in Th2 cell differentiation. However, the factors controlling the onset and extent of basophil-mediated Th2 cell differentiation are unknown. Here, we demonstrate that Lyn kinase dampened basophil expression of the transcription factor GATA-3 and the initiation and extent of Th2 cell differentiation. Lyn-deficient mice had a marked basophilia, a constitutive Th2 cell skewing that was exacerbated upon in vivo challenge of basophils, produced antibodies to a normally inert antigen, and failed to appropriately respond to a Th1 cell-inducing pathogen. The Th2 cell skewing was dependent on basophils, immunoglobulin E, and interleukin-4, but was independent of mast cells. Our findings demonstrate that basophil-expressed Lyn kinase exerts regulatory control on Th2 cell differentiation and function.
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| 5. |
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| 6. |
- Marten, Tobias, 1979-, et al.
(author)
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Double-segregation effect in AgxPd1-x/Ru(0001) thin film nanostructures
- 2008
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In: Physical Review B. Condensed Matter and Materials Physics. - : APS. - 1098-0121 .- 1550-235X. ; 77:12
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Journal article (peer-reviewed)abstract
- We study the structural properties of ultrathin AgxPd1-x films on top of a Ru(0001) substrate. Effective interatomic interactions, obtained from first-principles calculations, have been used in Monte Carlo simulations to derive the distribution of the alloy components in a four-monolayer (4-ML) Ag-Pd film. Though Ag-Pd alloys show complete solubility in the bulk, the thin film geometry leads to a pronounced segregation between Ag and Pd atoms with a strong preference of Ag atoms toward the surface and Pd atoms toward the interface. The theoretical prediction of this double-segregation effect is strongly supported by photoelectron spectroscopy experiments carried out for 4-ML thin films. We also show, in an additional experiment, that even in the case where initially 1 ML Ag is buried under 6 ML Pd, the whole Ag ML segregates to the surface.
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| 7. |
- Roblick, U.J., et al.
(author)
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Undifferentiated pelvic adenocarcinomas : diagnostic potential of protein profiling and multivariate analysis
- 2008
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In: International Journal of Colorectal Disease. - : Springer Science and Business Media LLC. - 0179-1958 .- 1432-1262. ; 23:5, s. 483-491
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Journal article (peer-reviewed)abstract
- BACKGROUND AND AIMS: Despite improved techniques, the determination of tumor origin in poorly differentiated adenocarcinomas still remains a challenge for the pathologist. Here we report the use of protein profiling combined with principal component analysis to improve diagnostic decision-making in tumor samples, in which standard pathologic investigations cannot present reliable results. MATERIALS AND METHODS: A poorly differentiated adenocarcinoma of unknown origin located in the pelvis, infiltrating the sigmoid colon as well as the ovary, served as a model to evaluate our proteomic approach. Firstly, we characterized the protein expression profiles from eight advanced colon and seven ovarian adenocarcinomas using two-dimensional gel electrophoresis (2-DE). Qualitative and quantitative patterns were recorded and compared to the tumor of unknown origin. Based on these protein profiles, match sets from the different tumors were created. Finally, a multivariate principal component analysis was applied to the entire 2-DE data to disclose differences in protein patterns between the different tumors. RESULTS: Over 89% of the unknown tumor sample spots could be matched with the colon standard gel, whereas only 63% of the spots could be matched with the ovarian standard. In addition, principal component analysis impressively displayed the clustering of the unknown case within the colon cancer samples, whereas this case did not cluster at all within the group of ovarian adenocarcinomas. CONCLUSION: These results show that 2-DE protein expression profiling combined with principal component analysis is a sensitive method for diagnosing undifferentiated adenocarcinomas of unknown origin. The described approach can contribute greatly to diagnostic decision-making and, with further technical improvements and a higher throughput, become a powerful tool in the armentarium of the pathologist.
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| 8. |
- Bardales, José R., et al.
(author)
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CK2-mediated phosphorylation of a type II regulatory subunit of cAMP-dependent protein kinase from the mollusk Mytilus galloprovincialis
- 2007
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In: Archives of Biochemistry and Biophysics. - : Elsevier BV. - 0003-9861 .- 1096-0384. ; 461:1, s. 130-137
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Journal article (peer-reviewed)abstract
- Two isoforms of regulatory (R) subunit of cAMP-dependent protein kinase (PKA), named R(myt1) and R(myt2), were identified so far in the sea mussel Mytilus galloprovincialis. Out of them, only R(myt2) was phosphorylated in vitro by casein kinase 2 (CK2) using GTP as phosphate donor. CK2 catalytic subunit (CK2alpha) itself was sufficient to phosphorylate R(myt2), but phosphorylation was enhanced by the presence of the regulatory subunit CK2beta. Even in the absence of CK2, R(myt2) was phosphorylated to a certain extent when it was incubated with GTP. This basal phosphorylation was partially abolished by the known inhibitors apigenin and emodin, which suggests the presence of a residual amount of endogenous CK2 in the preparation of purified R subunit. CK2-mediated phosphorylation significantly decreases the ability of R(myt2) to inhibit PKA catalytic (C) subunit activity in the absence of cAMP. On the other hand, the sequence of several peptides obtained from the tryptic digestion of R(myt2) showed that mussel protein contains the signature sequence common to all PKA family members, within the "phosphate binding cassette" (PBC) A and B. Moreover, the degree of identity between the sequences of peptides from R(myt2), as a whole, and those from type II R subunits was 68-75%, but the global identity percentage with type I R subunits was only about 30%, so that R(myt2) can be classified as a type II R subunit.
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| 9. |
- Bardales, José R., et al.
(author)
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Identification of multiple isoforms of the cAMP-dependent protein kinase catalytic subunit in the bivalve mollusc Mytilus galloprovincialis
- 2008
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In: The FEBS Journal. - : Wiley. - 1742-464X .- 1742-4658. ; 275:18, s. 4479-4489
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Journal article (peer-reviewed)abstract
- Several isoforms of the cAMP-dependent protein kinase catalytic subunit (C-subunit) were separated from the posterior adductor muscle and the mantle tissues of the sea mussel Mytilus galloprovincialis by cation exchange chromatography, and identified by: (a) protein kinase activity; (b) antibody recognition; and (c) peptide mass fingerprinting. Some of the isozymes seemed to be tissue-specific, and all them were phosphorylated at serine and threonine residues and showed slight but significant differences in their apparent molecular mass values, which ranged from 41.3 to 44.5 kDa. The results from the MS analysis suggest that at least some of the mussel C-subunit isoforms arise as a result of alternative splicing events. Furthermore, several peptide sequences from mussel C-subunits, determined by de novo sequencing, showed a high degree of homology with the mammalian Calpha-isoform, and contained some structural motifs that are essential for catalytic function. On the other hand, no significant differences were observed in the kinetic parameters of C-subunit isoforms, determined by using synthetic peptides as substrate and inhibitor. However, the C-subunit isoforms separated from the mantle tissue differed in their ability to phosphorylate in vitro some proteins present in a mantle extract.
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| 10. |
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