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141.
Glansdorp FG Spandl RJ Swatton JE Loiseleur O Welch M Spring DR 《Organic & biomolecular chemistry》2008,6(22):4120-4124
The antibacterial drug azithromycin has clinically beneficial effects at sub-inhibitory concentrations for the treatment of conditions characterized by chronic Pseudomonas aeruginosa infection, such as cystic fibrosis. These effects are, in part, the result of inhibition of bacterial biofilm formation. Herein, the efficient synthesis of azithromycin in 4 steps from erythromycin and validation of the drug's ability to inhibit biofilm formation at sub-MIC (minimum inhibitory concentration) values are reported. Furthermore, the synthesis of immobilized and biotin-tagged azithromycin analogues is described. These chemical probes were used in pull-down assays in an effort to identify azithromycin's binding partners in vivo. Results from these assays revealed, as expected, mainly ribosomal-related protein binding partners, suggesting that this is the primary target of the drug. This was further confirmed by studies using a P. aeruginosa strain containing plasmid-encoded ermC, which expresses a protein that modifies 23S rRNA and so blocks macrolide entry to the ribosome. In this strain, no biofilm inhibition was observed. This work supports the hypothesis that the sub-inhibitory effects of azithromycin are mediated through the ribosome. Moreover, the synthesis of these chemical probes, and proof of their utility, is of value in global target identification in P. aeruginosa and other species. 相似文献
142.
143.
The aim of this study was to add to the range of charged surfactants that can be used to form catanionic aggregates with oppositely charged surface active drug substances; and to apply these aggregates to prolong drug release from gels. The surfactants used in this study, lauric and capric acids are of natural origin-unlike traditionally used, synthetic, surfactants. The mixtures of drug substances and oppositely charged surfactants were studied visually and with cryogenic transmission electron microscopy. Drug release from gels was studied with a modified USP paddle method. This study shows that lauric and capric acids are as, or even more, active in forming catanionic aggregates than traditionally used surfactants such as sodium dodecyl sulfate. It is shown that the length of the hydrophobic part of the surfactant plays an important role in the formation of pharmaceutically interesting catanionic aggregates. As seen in previous studies, using catanionic vesicles prolongs the drug release from gels and decreases the apparent diffusion coefficient by a factor of 10-50, compared to a gel containing only drug substance. 相似文献
144.
Miller KA Welch TR Greshock TJ Ding Y Sherman DH Williams RM 《The Journal of organic chemistry》2008,73(8):3116-3119
The biomimetic total syntheses of both malbrancheamide and malbrancheamide B are reported. The synthesis of the two monochloro species enabled the structure of malbrancheamide B to be unambiguously assigned. The syntheses each feature an intramolecular Diels-Alder reaction of a 5-hydroxypyrazin-2(1H)-one to construct the bicyclo[2.2.2]diazaoctane core, which has also been proposed as the biosynthetic route to these compounds. 相似文献
145.
Design and Development of a Non-Enzymatic Electrochemical Biosensor for the Detection of Glutathione
Shrute Kannappan Lakshmishri Prabakaran Noel Nesakumar K. Jayanth Babu Arockia Jayalatha Kulandaisamy Prof. John Bosco Balaguru Rayappan 《Electroanalysis》2023,35(1):e202100650
Glutathione (GSH-reduced form) is a tripeptide that plays a vital role as an antioxidant to remove xenobiotics in the human body and changes in GSH levels are a marker for the progression of various diseases. In this context, a highly sensitive non-enzymatic electrochemical biosensor for the detection of GSH has been developed using reduced graphene oxide Manganese oxide (rGMnO) nanocomposite as the nano-interface. Initially, graphene oxide was synthesized by Hummer's method and then thermally reduced in the presence of MnO2 in a blast furnace to obtain rGMnO nanocomposite. The nanocomposite was characterized to validate its structure and morphological properties via Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry and amperometry studies showed that upon the addition of GSH, the Pt/rGMnO modified working electrode exhibited a linear response in the range of 1–100 μM at an input voltage of −0.62 V. The developed sensor was found to have a sensitivity of 0.3256 μA μM−1 and LOD of 970 nM with a recovery of 92–104 % in real blood serum samples. 相似文献
146.
Mhaske Harshad P. Vaidya Vikas V. Menon Sasikumar N. Shailajan Sunita Gomes Noel A. 《平面色谱法杂志一现代薄层色谱法》2008,21(3):217-219
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
147.
Noel A. Gomes Ashutosh M. Pudage Santosh S. Joshi Vikas V. Vaidya Sagar A. Parekh 《Chromatographia》2008,68(7-8):541-550
A rapid and sensitive LC–MS–MS method has been developed and validated for simultaneous analysis of abacavir (ABA) and lamivudine (LAM) in human plasma. The analytes were extracted from human plasma by SPE. Nelfinavir (NEL) and emtricitabine (EMT) were used as the internal standards for ABA and LAM, respectively. An RP18 column enabled chromatographic separation of the analytes. The method involves simple isocratic chromatography and MS detection in positive-ionization mode. Validation of the method showed response was a linear function of concentration in the ranges 100.0–7000.0 ng mL?1 for ABA and 80.0–5000.0 ng mL?1 for LAM. At the LOQ levels, inter-run and intra-run precision were within 5.80 and 3.51%, respectively, for ABA and within 4.68 and 3.16%, respectively, for LAM. Overall recovery for ABA and LAM was 59.32 and 105.18%, respectively. Total elution time was 2 min only, which enabled quantification of more than 200 plasma samples per day. This validated method was used successfully for analysis of plasma samples from a bioequivalence study. 相似文献
148.
Salts of methylated 5-aminotetrazoles with energetic anions 总被引:4,自引:0,他引:4
Karaghiosoff K Klapötke TM Mayer P Sabaté CM Penger A Welch JM 《Inorganic chemistry》2008,47(3):1007-1019
1-methyl-5-aminotetrazole (4, MAT) can easily be protonated by strong acids, yielding known but largely uninvestigated 1-methyl-5-aminotetrazolium nitrate (4a) and perchlorate (4b). Methylation, rather than protonation, of 4 with iodomethane followed by the exchange of the iodide (5a) for nitrate (5b), perchlorate (5c), azide (5d), and dinitramide (5e) yields a new family of energetic methylated aminotetrazole salts. In all cases, stable salts were obtained and fully characterized by vibrational (IR, Raman) spectroscopy, multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray structure determination. Compounds 4a, 4b, and 5c crystallize in the monoclinic space group P2(1)/n, whereas compounds 5b and 5e crystallize in the orthorhombic space group P2(1)2(1)2(1) and 5d in the orthorhombic Fddd. Initial safety testing (impact, friction, and electrostatic sensitivity) and thermal stability measurements (DSC) were also carried out. The MAT salts all exhibit good thermal stabilities (decomposition above 150 degrees C). The constant volume energies of combustion (DeltacU) of 4a, 5b, 5d, and 5e were determined to be -2510(10) cal/g, -3190(30) cal/g, -4500(100) cal/g, and -2570(70) cal/g, respectively, experimentally using oxygen bomb calorimetry. From the experimentally determined density, chemical composition and energies of formation (back calculated from the heats of combustion), the detonation pressures and velocities of 4a (8100 m/s, 25.6 GPa), 5b (7500 m/s, 20.2 GPa), 5d (8200 m/s, 21.7 GPa), and 5e (7500 m/s, 21.2 GPa) were predicted using the EXPLO5 code. 相似文献
149.
The pyrolysis of the simplest azides HN(3) and CH(3)N(3) has been studied computationally. Nitrogen extrusion leads to the production of NH or CH(3)N. The azides have singlet ground states but the nitrenes CH(3)N and NH have triplet ground states. The competition between spin-allowed decomposition to the excited state singlet nitrenes and the spin-forbidden N(2) loss is explored using accurate electronic structure methods (CASSCF/cc-pVTZ and MR-AQCC/cc-pVTZ) as well as statistical rate theories. Nonadiabatic rate theories are used for the dissociation leading to the triplet nitrenes. For HN(3), (3)NH formation is predicted to dominate at low energy, and the calculated rate constant agrees very well with energy-resolved experimental measurements. Under thermal conditions, however, the singlet and triplet pathways are predicted to occur competitively, with the spin-allowed product increasingly favored at higher temperatures. For CH(3)N(3) thermolysis, spin-allowed dissociation to form (1)CH(3)N should largely dominate at all temperatures, with spin-forbidden formation of (3)CH(3)N almost negligible. Singlet methyl nitrene is very unstable and should rearrange to CH(2)NH immediately upon formation, and the latter species may lose H(2) competitively with vibrational cooling, depending on temperature and pressure. 相似文献
150.
The mechanism for the interaction of thioflavin T (ThT) with amyloid fibrils at the molecular level is not known. Here, we used 1H NMR spectroscopy to determine the binding mode of ThT on the surface of fibrils from lysozyme and insulin. Relayed rotating‐frame Overhauser enhancements in ThT were observed, indicating that the orientation of ThT is orthogonal to the fibril surface. Importantly, the assembly state of ThT on both surfaces is different. On the surface of insulin fibrils, ThT is oligomeric, as indicated by rapid 1H spin‐lattice relaxation rate in the rotating frame (R1ρ), presumably due to intermolecular dipole–dipole interactions between ThT molecules. In contrast, ThT on the surface of lysozyme fibrils is a monomer, as indicated by slower 1H R1ρ. These results shed new light into the mechanism for the enhancement of ThT fluorescence and may lead to more efficient detectors of amyloid assemblies, which have escaped detection by ThT in monomer form. 相似文献