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11.
Phosphatidyl inositol 4,5-bisphosphate (PIP2) and phosphatidyl inositol 3,4,5-trisphosphate (PIP3) labeled with 4,4-difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-indacene-3-propionic acid (BODIPY FL) on the acyl chain or a phosphatidyl ethanolamine head group were separated by CE with LIF detection. Several methods and capillary-coating procedures were tested for the separation of these phosphatidyl inositol phosphates (PIPs) at 20 degrees C. Separation of the PIPs in less than 20 min with excellent resolution was achieved using a buffer containing sodium deoxycholate (SDC), 1-propanol, MgCl2 and the polymer coating reagent, EOTrol LR. The efficiency of the optimized method was as high as 1.3x10(5) plates. The dependence of the separation on the concentration of 1-propanol, SDC, and MgCl2 was determined. The separation of PIP2 and PIP3 was primarily due to differential binding of the lipids to Mg2+ rather than to different solubilities in the micellar phase. The role of the SDC was to prevent adsorption of the hydrophobic lipids to the capillary wall and thus enhance the efficiency. The fluorescent PIPs are of value for both in vitro and in vivo assays of phospholipid metabolism. In particular, the use of these lipids with the optimized capillary-based separation will be of utility for drug screening as well as cell-based assays. 相似文献
12.
The rate constant of the comparably slow bimolecular NCN radical reaction NCN + O2 has been measured for the first time under combustion relevant conditions using the shock tube method. The thermal decomposition of cyanogen azide (NCN3) served as a clean high‐temperature source of NCN radicals. NCN concentration–time profiles have been detected by narrow‐bandwidth laser absorption at cm?1. The experiments behind incident shock waves have been performed with up to 17% O2 in the reaction gas mixture. At such high O2 mole fractions, it was necessary to take O2 relaxation into account that caused a gradual decrease of the temperature during the experiment. Moreover, following fast decomposition of NCN3 and collision‐induced intersystem crossing of the initially formed singlet NCN to its triplet ground state, an unexpected and slow additional formation of triplet NCN has been observed on a 100‐μs timescale. This delayed NCN formation was attributed to a fast recombination of 1NCN with O2 forming a 3NCNOO adduct acting as a reservoir species for NCN. Rate constant data for the reaction NCN + O2 have been measured at temperatures between 1674 and 2308 K. They are best represented by the Arrhenius expression . No pressure dependence has been observed at pressures between 216 and 706 mbar. 相似文献
13.
Karina González‐Segura Paulina Cañete‐Rosales Rodrigo del Rio Claudia Yáñez Nancy F. Ferreyra Gustavo A. Rivas Soledad Bollo 《Electroanalysis》2012,24(12):2317-2323
The electrochemical response of a glassy carbon electrode modified with carbon nanotubes (CNT) dispersed in two solvents, water and DMF, and two polymers, chitosan and Nafion is reported. The films were homogeneous when the dispersing agent was water or DMF. In the case of polymers, the surfaces present areas with different density of CNTs. A more sensitive electrochemical response was obtained when CNTs are dispersed in the solvents. In the case of CNT dispersed with polymers, the nature of the polymer demonstrated to be a critical parameter not only for dispersing the nanotubes but also for the electrochemical activity of the resulting electrodes. 相似文献
14.
Roy A. Meoded Dr. Reiko Ueoka Dr. Eric J. N. Helfrich Dr. Katja Jensen Nancy Magnus Prof. Dr. Birgit Piechulla Prof. Dr. Jörn Piel 《Angewandte Chemie (International ed. in English)》2018,57(36):11644-11648
Enzymatic core components from trans‐acyltransferase polyketide synthases (trans‐AT PKSs) catalyze exceptionally diverse biosynthetic transformations to generate structurally complex bioactive compounds. Here we focus on a group of oxygenases identified in various trans‐AT PKS pathways, including those for pederin, oocydins, and toblerols. Using the oocydin pathway homologue (OocK) from Serratia plymuthica 4Rx13 and N‐acetylcysteamine (SNAC) thioesters as test surrogates for acyl carrier protein (ACP)‐tethered intermediates, we show that the enzyme inserts oxygen into β‐ketoacyl moieties to yield malonyl ester SNAC products. Based on these data and the identification of a non‐hydrolyzed oocydin congener with retained ester moiety, we propose a unified biosynthetic pathway of oocydins, haterumalides, and biselides. By providing access to internal ester, carboxylate pseudostarter, and terminal hydroxyl functions, oxygen insertion into polyketide backbones greatly expands the biosynthetic scope of PKSs. 相似文献
15.
Keck GE Kraft MB Truong AP Li W Sanchez CC Kedei N Lewin NE Blumberg PM 《Journal of the American Chemical Society》2008,130(21):6660-6661
Highly potent bryostatin analogues which contain the complete bryostatin core structure have been synthesized using a pyran annulation approach as a key strategic element. The A ring pyran was assembled using a pyran annulation reaction between a C1-C8 hydroxy allylsilane and an aldehyde comprising C9-C13. This pyran was transformed to a new hydroxy allylsilane and then coupled with a preformed C ring aldehyde subunit in a second pyran annulation, with concomitant formation of the B ring. This tricyclic intermediate was elaborated to bryostatin analogues which displayed nanomolar to subnanomolar affinity for PKC, but displayed properties indistinguishable from a phorbol ester in a proliferation/attachment assay. 相似文献
16.
Wei ZL Sakamuri S Petukhov PA George C Lewin NE Blumberg PM Kozikowski AP 《Organic letters》2002,4(13):2169-2172
[structures: see text] Both (2S,5R,6R)- and (2S,5R,6S)-6-hydroxy-8-(1-decynyl)benzolactam-V8 were designed and synthesized as PKC modulators. Biological assays reveal the (6R)-ligand to be 20-fold more potent than its (6S)-counterpart in binding to PKC alpha. 相似文献
17.
Cortez-Espinosa N Aviña-Verduzco JA Ramírez-Chávez E Molina-Torres J Ríos-Chávez P 《Natural product communications》2011,6(6):857-861
Acmella radicans (Asteraceae) produces at least seven alkamides, most with either an isobutyl- or phenylethyl group as the amine moiety. These moieties suggest that the amino acids valine and phenylalanine are the biosynthetic precursors of these alkamides. On the basis of labeled feeding experiments using either L-[2H8]valine or L-[2H8]phenylalanine we present evidence for the involvement of these two amino acids in the biosynthesis of (2E,6Z,8E)-N-isobutyl-2,6,8-decatrienamide (affinin) (1), (2Z,4E)-N-(2-phenylethyl)-2,4-octadienamide (2), (2E)-N-(2-phenylethyl)-nona-2-en-6,8-diynamide (3), and 3-phenyl-N-(2-phenylethyl)-2-propenamide (4). Alkamides were isolated from young A. radicans plants and analyzed by gas chromatography-mass spectrometry (GC-MS). Additionally, in cell free in vitro experiments based on isobutyl and phenylethylamide biosynthesis, using a colorimetric assay and GC-MS, valine and phenylalanine decarboxylase activities were assayed in the soluble extract of A. radicans leaves. 相似文献
18.
19.
Knowledge and understanding of the stability profile of a drug is important as it affects its safety and efficacy. In the present work, besifloxacin, a new, fourth‐generation fluoroquinolone antibiotic, was subjected to different forced‐degradation conditions as per International Conference on Harmonization (ICH) guidelines such as hydrolysis (acid, base and neutral), oxidation, thermal and photolysis. The drug degraded under acidic, basic, oxidative and photolytic conditions while it was found to be stable under dry heat and neutral hydrolytic conditions. In total, five degradation products (DPs) were formed under different conditions—DP1 and DP2 (photolysis), DP3 (oxidation), DP4 (acidic), DP3 and DP5 (basic). The chromatographic separation of besifloxacin and its degradation products was achieved on a Sunfire C18 (250 mm × 4.6 mm, 5 μm) column with 0.1% aqueous formic acid–acetonitrile as a mobile phase. The gradient RP‐HPLC method was developed and validated as per ICH guidelines. The degradation products were characterized with the help of LC–ESI–QTOF mass spectrometric studies and the most likely degradation pathway of the drug was proposed. In silico toxicity assessment of the drug and its degradation products was carried out, which indicated that DP3 and DP4 carry a mutagenicity alert. 相似文献
20.
Sara Luisa Rodríguez De Luna Luis Ángel GarzaSylvain Bernès Perla ElizondoBlanca Nájera Nancy Pérez 《Polyhedron》2010
A series of mononuclear complexes based on lanthanide ions has been synthesized and X-ray characterized. The compounds [LnIIIL2(NO3)3(H2O)2] (Ln = La, Ce, Pr, Nd, Sm, Gd and Tm; L = 2,6-bis(2-formylphenoxymethyl)pyridine) are found to be isomorphous and isostructural. Ligand L systematically coordinates through one carbonyl functionality, and the resulting complexes are placed on a twofold axis in crystals belonging to C2/c space-group. Emission spectra for Ln = La, Pr, Nd revealed a correlation between the Ln–O coordination bond length and the photoluminescent properties of the complexes, in line with a Förster–Dexter mechanism for intramolecular energy transfer. Ligand L is therefore a suitable sensitizer for lanthanide ions. 相似文献