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91.
Numerical Algorithms - We construct approximate Fekete point sets for kernel-based interpolation by maximising the determinant of a kernel Gram matrix obtained via truncation of an orthonormal... 相似文献
92.
93.
Cells continuously produce reactive oxidative species that can modify all cellular components. In proteins, for example, cysteine, methionine, tryptophan (Trp), and tyrosine residues are particularly prone to oxidation. Here, we report two new approaches to distinguish two isomeric oxidation products of Trp residues, i.e. 5-hydroxytryptophan (5-HTP) and oxindolylalanine (Oia) residues, in peptides. First, 2-nitrobenzenesulfenyl chloride, known to derivatize Trp residues in position 2 of the indole ring, was used to label 5-HTP residues. The mass shift of 152.98 m/z units allowed identifying 5-HTP- besides Trp-containing peptides by mass spectrometry, whereas Oia residues were not labeled. Second, fragmentation of the Oia- and 5-HTP-derived immonium ions at m/z 175.08 produced ions characteristic for each residue that allowed their identification even in the presence of y(1) ions at m/z 175.12 derived from peptides with C-terminal arginine residues. The pseudo MS(3) spectra acquired on a quadrupole time-of-flight hybrid mass spectrometer displayed two signals at m/z 130.05 and m/z 132.05 characteristic for Oia-containing peptides and a group of six signals (m/z 103.04, 120.04, 130.04, 133.03, 146.04, and 148.04) for 5-HTP-cointaining peptides. In both cases, the relative signal intensities appeared to be independent of the sequence providing a specific fingerprint of each oxidative modification. 相似文献
94.
Toni Mäkinen 《Applied Acoustics》2010,71(10):902-913
Shooter localization and estimation of bullet trajectory, caliber and speed have become essential tasks for example in peacekeeping and police assignments. A novel approach for such estimation and localization is presented in this paper, as a numerical estimation method is applied to the problem. Both simulated and recorded gunshot data are considered, as a known bullet shock wave model and detected firing sounds are utilized in creating a likelihood function corresponding to different bullet states. For this, a state-space model of the underlying dynamic system is developed, and a well-known optimization algorithm is used to find the global maximum of the evaluated function. Two different criteria are used to measure the likelihood values, namely the Generalized Cross Correlation (GCC) and the Mean-Squared Error (MSE). The achieved localization and estimation results are accurate and applicable when considering the usability of the method against hostile snipers. The shooter position and bullet state estimation errors vary between 2% and 10%, depending on the estimated parameter at stake. 相似文献
95.
Johannes Kiefer Franziska Toni Karl‐Ernst Wirth 《Journal of Raman spectroscopy : JRS》2015,46(11):1124-1128
Raman spectroscopy is applied to study the interactions between carbon‐coated iron nanoparticles and ethanol. The spectra reveal changes in the vibrational structure of ethanol, despite dispersion of only a very small amount of nanoparticles. The hydrogen bonding network of ethanol is significantly affected in the presence of the particles. This is revealed by frequency shifts throughout the spectrum as well as the modification of the OH stretching band of the alcohol. The carbon shell of the nanoparticles does not exhibit polar groups, and hence the non‐polar interactions in the system are strengthened and the hydrogen bonding is weakened. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
96.
Toni Andersson Susanna Holappa Vladimir Aseyev Heikki Tenhu 《Journal of polymer science. Part A, Polymer chemistry》2003,41(13):1904-1914
The interactions between oppositely charged polyelectrolytes were studied in saline aqueous solutions as functions of the temperature and the salt and polymer concentrations. The polyanion was a diblock copolymer composed of a poly(ethylene oxide) block and a poly(sodium methacrylate) block. Two polycations were used, the homopolymer poly(methacryl oxyethyl trimethylammonium chloride) and its poly(ethylene oxide)‐grafted analogue. By dynamic light scattering and turbidity measurements, it was observed that the salt concentration, temperature, and counterion size had a significant effect on the formation of the polymer complexes in aqueous solutions. At a fixed salt concentration and a fixed temperature, it was possible to form completely soluble complexes of an ionic polymer in aqueous solutions between poly(ethylene oxide)‐grafted poly(methacryl oxyethyl trimethylammonium chloride)and the polyanion with a poly(ethylene oxide) block at a 1:1 anion/cation ratio. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1904–1914, 2003 相似文献
97.
Stereoselective synthesis of 2,3-di- and 2,2',3-tri-substituted aziridines in good yields and excellent diastereoselectivities are achieved through aza-Darzens reactions of a range of tert-butanesulfinyl aldimines and ketimines with ethyl bromoacetate. 相似文献
98.
We introduce a class of partially coherent beams with spatially varying correlation properties. It is shown that mathematically simple modifications in the coherence function of conventional Gaussian Schell-model beams lead to partially coherent fields with extraordinary free-space propagation characteristics, such as locally sharpened and laterally shifted intensity maxima. We study the properties of such fields based on an elementary-mode interpretation and by numerical simulations. The results demonstrate the potential of coherence modulation for beam shaping applications. 相似文献
99.
Münzel M Lischke U Stathis D Pfaffeneder T Gnerlich FA Deiml CA Koch SC Karaghiosoff K Carell T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13782-13788
5-Formylcytosine (fC or (5-CHO)dC) and 5-carboxylcytosine (caC or (5-COOH)dC) have recently been identified as constituents of mammalian DNA. The nucleosides are formed from 5-methylcytosine (mC or (5-Me)dC) via 5-hydroxymethylcytosine (hmC or (5-HOMe)dC) and are possible intermediates of an active DNA demethylation process. Here we show efficient syntheses of phosphoramidites which enable the synthesis of DNA strands containing these cytosine modifications based on Pd(0)-catalyzed functionalization of 5-iododeoxycytidine. The first crystal structure of fC reveals the existence of an intramolecular H-bond between the exocyclic amine and the formyl group, which controls the conformation of the formyl substituent. Using a newly designed in vitro mutagenicity assay we show that fC and caC are only marginally mutagenic, which is a prerequisite for the bases to function as epigenetic control units. 相似文献
100.
Liberato Brum Junior Manoela Guerra Leal Fl��via de Toni Uchoa Moacir Kaiser S��lvia Stani?uaski Guterres Teresa Dalla Costa 《Chromatographia》2011,73(11-12):1081-1088
A fast, sensitive, and specific LC?CMS?CMS method for determination of quinine (QN) and doxycycline (DOX) in rat plasma has been developed and validated. QN, DOX, and cimetidine (internal standard, IS) were extracted from the plasma by protein precipitation. The compounds were separated on a C18 column with methanol?C0.1% aqueous formic acid 70:30 (v/v) as mobile phase at a flow rate of 0.5 mL min?1 (split 1:3). Detection was by positive electrospray ionization (ESI+) in multiple reaction monitoring (MRM) mode, monitoring the transitions 325.0 ?? 307.0, 445.0 ?? 428.1, and 252.8 ?? 159.0, for QN, DOX, and IS, respectively. The analysis was carried out in 2.0 min and the method was linear in the plasma concentration range 5?C5,000 ng mL?1. The mean extraction recoveries for QN, DOX, and IS from plasma were 89.4, 90.5, and 86.3%, respectively. The method was validated for linearity, precision, accuracy, specificity, and stability; the results obtained were within the acceptable range. The proposed method was successfully applied to the determination of QN and DOX in rat plasma samples to support pharmacokinetic studies. 相似文献