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111.
Jonathan P. Williams Julie Ann Lough Iain Campuzano Keith Richardson Peter J. Sadler 《Rapid communications in mass spectrometry : RCM》2009,23(22):3563-3569
We report the development of an enhanced algorithm for the calculation of collision cross‐sections in combination with Travelling‐Wave ion mobility mass spectrometry technology and its optimisation and evaluation through the analysis of an organoruthenium anticancer complex [(η6‐biphenyl)RuII(en)Cl]+. Excellent agreement was obtained between the experimentally determined and theoretically determined collision cross‐sections of the complex and its major product ion formed via collision‐induced dissociation. Collision cross‐sections were also experimentally determined for adducts of this ruthenium complex with the single‐stranded oligonucleotide hexamer d(CACGTG). Ion mobility tandem mass spectrometry measurements have allowed the binding sites for ruthenium on the oligonucleotide to be determined. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
112.
Hermann Staudinger V. Grignardt G. Dupont R. Loquin A. Guillaumin Ch. Courtot F. S. Kipping J. Doeuvre und P. Baud 《Fresenius' Journal of Analytical Chemistry》1939,117(1-2):72-73
Ohne Zusammenfassung 相似文献
113.
Yue Xuan Andrew J. Creese Julie A. Horner Helen J. Cooper 《Rapid communications in mass spectrometry : RCM》2009,23(13):1963-1969
We have applied high‐field asymmetric waveform ion mobility spectrometry (FAIMS) to the analysis of the phosphopeptides APLpSFRGSLPKSYVK, APLSFRGpSLPKSYVK, and APLSFRGSLPKpSYVK. The peptides have identical amino acid sequences and differ only in the site of phosphorylation. The results show that FAIMS is capable of at least partially separating these species. Separation was confirmed by coupling FAIMS with high‐resolution electron transfer dissociation (ETD) mass spectrometry. Phosphorylation is retained on the ETD peptide fragments thereby allowing assignment of the site of the modification. Co‐eluting phosphopeptides which differ only in the site of modification are frequently observed in liquid chromatography/tandem mass spectrometry phosphoproteomics experiments, and therefore these proof‐of‐principle results have implications for the application of FAIMS in that field. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
114.
Angelo C. Pinto Barbara Vasconcellos da Silva Jaïrton Dupont 《Tetrahedron letters》2008,49(39):5639-5641
An efficient method was developed for the preparation of isatin-3-oxime derivatives with Bronsted and/or Lewis acids in imidazolium-based ionic liquids. Isatin-3-oxime bearing the electron donating methoxy group was equally obtained in good yields. The pronounced ionic liquid effect avoids the direct formation of isatin in the acidified media and the reaction leads exclusively to isatin-3-oxime derivatives. 相似文献
115.
A. Butenandt W. N. Haworth F. Kögl E. Späth L. Zechmeister K. Freudenberg Y. Asahina H. Rudy C. R. Harington E. L. Hirst G. Zemplén G. Töth F. Kuffner V. Grignard G. Dupont R. Locquin F. Salmon-Legagneur R. Padova und H. J. Goudet 《Fresenius' Journal of Analytical Chemistry》1939,118(5-6):171-172
Ohne Zusammenfassung 相似文献
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Julie Wang Alexander Wood Chao Gao Kayvan Najarian Jonathan Gryak 《Entropy (Basel, Switzerland)》2021,23(4)
The spleen is one of the most frequently injured organs in blunt abdominal trauma. Computed tomography (CT) is the imaging modality of choice to assess patients with blunt spleen trauma, which may include lacerations, subcapsular or parenchymal hematomas, active hemorrhage, and vascular injuries. While computer-assisted diagnosis systems exist for other conditions assessed using CT scans, the current method to detect spleen injuries involves the manual review of scans by radiologists, which is a time-consuming and repetitive process. In this study, we propose an automated spleen injury detection method using machine learning. CT scans from patients experiencing traumatic injuries were collected from Michigan Medicine and the Crash Injury Research Engineering Network (CIREN) dataset. Ninety-nine scans of healthy and lacerated spleens were split into disjoint training and test sets, with random forest (RF), naive Bayes, SVM, k-nearest neighbors (k-NN) ensemble, and subspace discriminant ensemble models trained via 5-fold cross validation. Of these models, random forest performed the best, achieving an Area Under the receiver operating characteristic Curve (AUC) of 0.91 and an F1 score of 0.80 on the test set. These results suggest that an automated, quantitative assessment of traumatic spleen injury has the potential to enable faster triage and improve patient outcomes. 相似文献
119.
In libraries and archives some of the items which, upon ageing, have acidified considerably since their production are so brittle that they cannot be handled without risking loss of material. In contrast to current deacidification processes, aminoalkylakoxysilanes (AAAS) improve the mechanical properties of paper. A simple AAAS, aminopropylmethyldiethoxysilane (AMDES) was used as a model to better understand previous observations made on these systems (hydrolysis, condensation and possible reactions with the organic substrate). The evaluation of the mechanical properties of papers that were treated with AMDES showed that there was no formation of a polymer network on the fibres’ surface. However, treated papers not only exhibited a high alkaline reserve, but also a significant increase in both their tensile breaking length and their folding endurance. Treatment of hygrothermally aged papers with AMDES provided improved folding endurance as well as a good resistance to ageing. Various oxidation treatments of the model papers using sodium hypochlorite led to the conclusion that the nature of the oxidised groups formed on cellulose did not seem to play a significant role in the strengthening mechanism but rather that this effect of AMDES mainly arose from hydrogen bonding between the two molecules. 相似文献
120.
Guihaumé J Clot E Eisenstein O Perutz RN 《Dalton transactions (Cambridge, England : 2003)》2010,39(43):10510-10519
Fagnou et al. reported direct arylation reactions that use palladium catalysts to couple Ar(1)-X to Ar(2)-H with the aid of a coordinated base. These reactions are particularly favourable for polyfluorinated arenes Ar(2)-H (see S. I. Gorelsky, D. Lapointe and K. Fagnou, J. Am. Chem. Soc. 2008, 130, 10848). In this paper, we show by means of a DFT analysis how the energetics and activation energies vary with fluorine substitution and examine the structures of intermediates and transition states. The reactant is modelled by Pd(OAc)(Ph)(PMe(3))(DMA) (DMA = dimethylacetamide). The sequence consists of (a) replacement of DMA by arene, (b) Concerted Deprotonation Metallation (CMD), (c) decoordination of AcOH, (d) reductive elimination of biaryl. Many of the variations are dominated by the number of fluorine substituents ortho to the C-H bond and fall into three groups labelled accordingly: Set0Fo, Set1Fo, and Set2Fo. In the first step a coordinated solvent is replaced by the arene. The arenes of Set0Fo and Set1Fo coordinate in a conventional η(2)-CH=CH mode, whereas the arenes of Set2Fo coordinate in an η(1)-CH mode assisted by an OH-C hydrogen bond from the coordinated acetate. Both the energy barriers to CMD and the product energies fall into the three typical sets with the highest barrier and highest product energy being for Set0Fo. They correlate more satisfactorily with the variations in Pd-C bond energies than with the C-H acidities. The barriers to reductive elimination from Pd(Ph)(Ar(F))(PMe(3))(AcOH) increase systematically from Set0Fo to Set2Fo as the Pd-C bond becomes stronger in a regular fashion from Set0Fo to Set2Fo. Again there is a strong correlation between the energy barriers to reductive elimination and the Pd-C bond energies. It is found overall that the key aspects of the reactions are: (a) the lowering of the energy of the CMD step by the ortho fluorine substituents, (b) the regioselective activation of C-H bonds ortho to fluorine which is also determined at the CMD step, (c) the decoordination of AcOH, which maintains the transition state for reductive elimination at low Gibbs free energy. The presence of fluorine increases the effectiveness of the reaction in the sense of points a and b via the increasing strength of the palladium-carbon bond. 相似文献