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51.
Mathijs Siemerink Nils Helge Schebb André Liesener Anna‐Maria Perchuc Reto Schöni Marianne Wilmer Heiko Hayen Uwe Karst Martin Vogel 《Rapid communications in mass spectrometry : RCM》2010,24(5):687-697
A new robust high‐performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI‐MS)‐based screening method for angiotensin‐converting enzyme (ACE)‐inhibiting substances in crude samples is described. The ACE assay is carried out in a typical offline setup by incubation of the samples with ACE and angiotensin I (AI), followed by stopping the reaction with acetonitrile containing val5‐AI serving as internal standard (I.S.). AI and the product angiotensin II (AII) are extracted from the incubation mixture by turbulent‐flow chromatography (TFC) applied in backflush mode as online solid‐phase extraction and are directly quantified by ESI(+)‐MS. The presence of ACE inhibitors (ACEi) is detected by an increase in AI signal intensity and a corresponding decrease of AII signal, as compared to the blank assay. The overall time of analysis of the TFC/ESI‐MS method was 5 min, thus making the described setup suitable for a rapid screening method. The assay was validated using a known ACE inhibitor and the IC50 values found were in good accordance with a common HPLC/UV method and literature data. The method was successfully applied for the screening of size‐exclusion chromatography fractions of the venom of the pitviper Bothrops moojeni. Three of 18 analyzed fractions inhibited ACE, due to peptides present as components of this snake venom. These compounds were extracted from the two most‐active fractions by means of TFC and isolated by means of HPLC. Three peptides with ACE inhibitory activity were characterized and their structures were elucidated with ESI‐MS/MS‐based de novo sequencing to be ZKWPPGKVPP, ZKWPRPGPEIPP and ZNWPRPGPEIPP, respectively (Z = pyroglutamic acid). Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
52.
Dieter Gramberg Christoph Weber Reto Beeli Janice Inglis Christian Bruns John A. Robinson 《Helvetica chimica acta》1995,78(6):1588-1606
The synthesis of a cis-Phe-Pro dipeptide mimetic is described, which adopts a type-VIβ-turn conformation. In this mimetic, the α-positions of Phe and Pro are joined by a CH2CH2 bridge, thereby forming a fused bicyclic system, and fixing a geometry similar to that seen in cis-Phe-Pro units in protein crystal structures. The dipeptide mimetic 20 was synthesized in optically pure form starting from (R)-α-allylproline ( 6 ; Schemes 1, 3, and 4), with a free carboxylic acid and an Fmoc-protected N-terminus, thereby allowing its incorporation into linear and cyclic peptides using standard solid-phase methods. The mimetic 20 was incorporated into the cyclic somatostatin analogue cyclo(-Phe = Pro-Phe-D -Trp-Lys-Thr-), where Phe = Pro represents the mimetic. This analogue shows a high affinity (pIC50 8.6) for somatostatin receptors on rat-brain cortex membranes. Based on NMR studies in aqueous solution, likely low-energy conformations for this analogue were deduced using restrained dynamic simulated annealing. The conformations found, which include a distorted type-II′ turn at D -Trp-Lys, are similar to low-energy conformations deduced elsewhere for cyclo(-Phe-Pro-Phe-D -Trp-Lys-Thr-), as well as to those seen in crystal structures of the somatostatin analogue octreotide. 相似文献
53.
Werner?SeebacherEmail author Marcel?Kaiser Reto?Brun Robert?Saf Robert?Weis 《Monatshefte für Chemie / Chemical Monthly》2005,136(4):625-634
Summary. The synthesis of new bicyclo[2.2.2]octane derivatives is described and their structures were established by NMR experiments. All compounds were tested in in vitro assays for their activities against causative organisms of malaria and African sleeping sickness and compared to those of former synthesized compounds. 相似文献
54.
Lamerz J Crameri R Scapozza L Mohring T Selle H Zucht HD 《Combinatorial chemistry & high throughput screening》2005,8(8):789-799
During the course of biosynthesis, processing and degradation of a peptide, many structurally related intermediate peptide products are generated. Human body fluids and tissues contain several thousand peptides that can be profiled by reversed-phase chromatography and subsequent MALDI-ToF-mass spectrometry. Correlation-Associated Peptide Networks (CAN) efficiently detect structural and biological relations of peptides, based on statistical analysis of peptide concentrations. We combined CAN with recognition of probable cleavage sites for peptidases and proteases in cerebrospinal fluid, resulting in a model able to predict the sequence of unknown peptides with high accuracy. On the basis of this approach, identification of peptide coordinates can be prioritized, and a rapid overview of the peptide content of a novel sample source can be obtained. 相似文献
55.
Bringmann G Menche D Kraus J Mühlbacher J Peters K Peters EM Brun R Bezabih M Abegaz BM 《The Journal of organic chemistry》2002,67(16):5595-5610
The "lactone concept" has been efficiently employed for the first atropo-enantioselective synthesis of knipholone and related natural phenylanthraquinones. Besides the regio- and stereoselective construction of the biaryl axis, another important step was the "synthetically late" introduction of the C-acetyl group, either by a Friedel-Crafts type acetylation or by an ortho-selective Fries rearrangement first tested on simplified model systems and subsequently applied to the highly atroposelective preparation of the natural products and of simplified analogs thereof for biotesting. The synthetic availability of these natural biaryls, their precursors, and their unnatural analogs permitted a broader investigation of the antiplasmodial activities of these interesting biaryls. 相似文献
56.
57.
The reversible photointerconversion in the above system was investigated in a wide range of temperatures and wavelengths of irradiation. The tetrahydropyrenes are obtainable only photochemically. The unmethylated and the mono-methylated compound are oxidized with iodine quantitatively to 4,5-dihydropyrene, even at ?30°. This makes it possible to estimate the absolute concentration of the tetrahydropyrenes, and thereby their molar extinction coefficients and complete electronic absorption spectra. The quantum yields in both directions do not vary appreciably with the temperature, down to ?190°. This is the first case in which the photocyclization yield of a cis-stilbenelike compound is not attenuated on cooling, and reflects the special character of highly constrained structures. No emission was observed in solution. 1H-NMR.-spectra of both modifications of the dimethylated compound were taken. They support the structures assumed for both modifications, and also allow an estimate of their relative concentrations. 相似文献
58.
Nguyen B Lee MP Hamelberg D Joubert A Bailly C Brun R Neidle S Wilson WD 《Journal of the American Chemical Society》2002,124(46):13680-13681
A combination of biophysical techniques has been used to characterize the interaction of an antitrypanosomal agent, CGP 40215A, with DNA. The results from a broad array of methods (DNase I footprinting, surface plasmon resonance, X-ray crystallography, and molecular dynamics) indicate that this compound binds to the minor groove of AT DNA sequences. Despite its unusual linear shape that is not complementary to that of the DNA groove, a high binding affinity was observed in comparison with other similar but more curved diamidine compounds. The amidine groups at both ends of the ligand and the -NH groups on the linker are involved in extensive and dynamic H-bonds to the DNA bases. Complementary and consistent results were obtained from both the X-ray and molecular dynamics studies; both of these methods reveal direct and water-mediated H-bonds between the ligand and the DNA. 相似文献
59.
Prof. Dr. Gerhard Bringmann Guoliang Zhang Tobias Büttner Gabi Bauckmann Dr. Thomas Kupfer Prof. Dr. Holger Braunschweig Prof. Dr. Reto Brun Prof. Dr. Virima Mudogo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):916-923
A new dimeric naphthylisoquinoline alkaloid, jozimine A2 ( 2 ), was isolated from the root bark of an Ancistrocladus species from the Democratic Republic of Congo. Its absolute stereostructure was determined by chemical, spectroscopic, and chiroptical methods, and confirmed by X‐ray crystallography. Jozimine A2 ( 2 ) is one of the as yet very rare naphthylisoquinoline dimers whose central biaryl axis is rotationally hindered. Moreover, it is the first natural dimer of a Dioncophyllaceae‐type alkaloid, that is, lacking oxygen functions at C6, and bearing R configurations at C3 in its two isoquinoline portions. Despite this decreased steric hindrance, the outer biaryl axes are chiral, too, so that jozimine A2 ( 2 ) has three consecutive stereogenic axes and, together with the four stereogenic centers, seven elements of chirality and is C2‐symmetric. The new dimer exhibits excellent, and specific, antiplasmodial activity. To further confirm its stereostructure and for likewise testing the bioactivities of its (unnatural) atropo‐diastereomer, compound 2 was prepared by semi‐synthesis from the co‐occurring (and likewise synthetically available) dioncophylline A ( 5 ), along with its atropo‐diastereomer, 3′‐epi‐ 2 . 相似文献
60.