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81.
Assimopoulou AN Sturm S Stuppner H Papageorgiou VP 《Biomedical chromatography : BMC》2009,23(2):182-198
Alkannin and shikonin (A/S) and their derivatives have been found in the roots of several Boraginaceous species and are also produced through plant tissue cultures. The chiral compounds A/S are potent pharmaceutical substances with a wide spectrum of biological and pharmacological activities like wound healing, antimicrobial, anti-inflammatory, anticancer and antioxidant activity. High-speed counter-current chromatography (HSCCC) was applied for the first time to the separation, preparative isolation and purification of A/S and their esters from extracts of Alkanna tinctoria roots, as well as commercial samples. The constituents of HSCCC fractions and their purity were determined by high-performance liquid chromatography-diode array detection-mass spectrometry (HPLC-DAD-MS), since DAD cannot detect oligomeric A/S derivatives that are present in most of the samples containing the respective monomeric derivatives. The purity of HSCCC fractions was compared with the one of fractions isolated by column chromatography (CC) using as stationary phases silica gel and Sephadex LH-20. As shown, the purity of monomeric alkannin/shikonin was greater by HSCCC than CC separation of commercial A/S samples. 相似文献
82.
83.
Lumbierres M Palomo JM Kragol G Roehrs S Müller O Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7405-7415
A new flexible and efficient methodology for the solid-phase synthesis of lipidated peptides has been developed. The approach is based on the use of previously synthesized building blocks and overcomes the limitations of previously reported methods, since long doubly lipidated peptides can be synthesized by using this route. Furthermore, it was thus possible to prepare a large number of N- and H-Ras peptides bearing a wide range of reporter and/or linking groups--efficient tools for the investigation of biological processes. In terms of efficiency and flexibility this solid-phase method is superior to the solution-phase synthesis. It gives pure peptides in multimilligram amounts within a much shorter time and with superior overall yield. 相似文献
84.
We consider a system formulation for Sturm–Liouville operators with formally self-adjoint boundary conditions on a graph. An M-matrix associated with the boundary value problem is defined and related to the matrix Prüfer angle associated with the system boundary value problem, and consequently with the boundary value problem on the graph. Asymptotics for the M-matrix are obtained as the eigenparameter tends to negative infinity. We show that the boundary conditions may be recovered, up to a unitary equivalence, from the M-matrix and that the M-matrix is a Herglotz function. This is the first in a series of papers devoted to the reconstruction of the Sturm–Liouville problem on a graph from its M-matrix. 相似文献
85.
86.
Peter Max Gehrig Bernd Roschitzki Dorothea Rutishauser Sonja Reiland Ralph Schlapbach 《Rapid communications in mass spectrometry : RCM》2009,23(10):1435-1445
In order to investigate gas‐phase fragmentation reactions of phosphorylated peptide ions, matrix‐assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) tandem mass (MS/MS) spectra were recorded from synthetic phosphopeptides and from phosphopeptides isolated from natural sources. MALDI‐TOF/TOF (TOF: time‐of‐flight) spectra of synthetic arginine‐containing phosphopeptides revealed a significant increase of y ions resulting from bond cleavages on the C‐terminal side of phosphothreonine or phosphoserine. The same effect was found in ESI‐MS/MS spectra recorded from the singly charged but not from the doubly charged ions of these phosphopeptides. ESI‐MS/MS spectra of doubly charged phosphopeptides containing two arginine residues support the following general fragmentation rule: Increased amide bond cleavage on the C‐terminal side of phosphorylated serines or threonines mainly occurs in peptide ions which do not contain mobile protons. In MALDI‐TOF/TOF spectra of phosphopeptides displaying N‐terminal fragment ions, abundant b–H3PO4 ions resulting from the enhanced dissociation of the pSer/pThr–X bond were detected (X denotes amino acids). Cleavages at phosphoamino acids were found to be particularly predominant in spectra of phosphopeptides containing pSer/pThr–Pro bonds. A quantitative evaluation of a larger set of MALDI‐TOF/TOF spectra recorded from phosphopeptides indicated that phosphoserine residues in arginine‐containing peptides increase the signal intensities of the respective y ions by almost a factor of 3. A less pronounced cleavage‐enhancing effect was observed in some lysine‐containing phosphopeptides without arginine. The proposed peptide fragmentation pathways involve a nucleophilic attack by phosphate oxygen on the carbon center of the peptide backbone amide, which eventually leads to cleavage of the amide bond. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
87.
88.
Anne Chartogne Marco Gaspari Sonja Jespersen Brigitte Buscher Elwin Verheij Robert van der Heijden Rv Ubbo Tjaden Jan van der Greef 《Rapid communications in mass spectrometry : RCM》2002,16(3):201-207
In the present work, we describe a collection system for the off-line coupling of capillary isoelectric focusing (CIEF) with matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. In this system, the capillary effluent is directly deposited in fractions onto the MALDI target via the use of a sheath liquid. The collected fractions are subsequently supplemented with matrix and further analysed by MALDI-TOF mass spectrometry for mass assignment. The experimental set-up includes a fiber optic based UV detector operating at 280 nm, which allows the study of the influence of the sheath liquid composition on the CIEF separation. The influence of the carrier ampholyte concentration on the protein MALDI spectra was also evaluated and the feasibility of the collection method was finally demonstrated with a mixture of four standard proteins. 相似文献
89.
90.
Jung U Kuhn S Cornelissen U Tuczek F Strunskus T Zaporojtchenko V Kubitschke J Herges R Magnussen O 《Langmuir : the ACS journal of surfaces and colloids》2011,27(10):5899-5908
Adlayers of different azobenzene-functionalized derivatives of the triazatriangulenium (TATA) platform on Au(111) surfaces were studied by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), gap-mode surface-enhanced Raman spectroscopy (gap-mode SERS), and cyclic voltammetry (CV). The chemical composition of the adlayers is in good agreement with the molecular structure, i.e., different chemical groups attached to the azobenzene functionality were identified. Furthermore, the presence of the azobenzene moieties in the adlayers was verified by the vibration spectra and electrochemical data. These results indicate that the molecules remain intact upon adsorption with the freestanding functional groups oriented perpendicularly to the TATA platform and thus also to the substrate surface. 相似文献