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41.
Chambers C Smith F Williams C Marcos S Liu ZH Hayter P Ciaramella G Keighley W Gribbon P Sewing A 《Combinatorial chemistry & high throughput screening》2003,6(4):355-362
The measurement of intracellular calcium fluxes in real time is widely applied within the pharmaceutical industry to measure the activation of G-protein coupled receptors (GPCRhyp;s), either for pharmacological characterisation or to screen for new surrogate ligands. Initially restricted to G(q) coupled GPCRs, the introduction of promiscuous and chimeric G-proteins has further widened the application of these assays. The development of new calcium sensitive dyes and assays has provided sensitive, homogeneous assays which can be readily applied to high throughput screening (HTS). In this paper we describe the full automation of this assay type using a fluorometric imaging plate reader (FLIPR ) integrated into a Beckman/Sagian system to establish a simple robotic system that is well suited for the current medium throughput screening in this area of lead discovery. Using a recently completed HTS we discuss important determinants for FLIPR based screening, highlight some limitations of the current approach, and look at the requirements for future automated systems capable of keeping up with expanding compound files. 相似文献
42.
de Souza BM Marques MR Tomazela DM Eberlin MN Mendes MA Palma MS 《Rapid communications in mass spectrometry : RCM》2004,18(10):1095-1102
The social wasp P. paulista is relatively common in southeast Brazil causing many medically important stinging incidents. The seriousness of these incidents is dependent on the amount of venom inoculated by the wasps into the victims, and the characteristic envenomation symptoms are strongly dependent on the types of peptides present in the venom. In order to identify some of these naturally occurring peptides available in very low amounts, an analytical protocol was developed that uses a combination of reversed-phase and normal-phase high-performance liquid chromatography (HPLC) of wasp venom for peptide purification, with matrix-assisted laser desorption/ionization time-of-flight post-source decay mass spectrometry (MALDI-Tof-PSD-MS) and low-energy collision-induced dissociation (CID) in a quadrupole time-of-flight tandem mass spectrometry (QTof-MS/MS) instrument for peptide sequencing at the sub-picomole level. The distinction between Leu and Ile was achieved both by observing d-type fragment ions obtained under CID conditions and by comparison of retention times of the natural peptides and their synthetic counterparts (with different combinations of I and/or L at N- and C-terminal positions). To distinguish the isobaric residues K and Q, acetylation of peptides was followed by Q-Tof-MS analysis. The primary sequences obtained were INWLKLGKMVIDAL-NH(2) (MW 1611.98 Da) and IDWLKLGKMVMDVL-NH(2) (MW 1658.98 Da). Micro-scale bioassay protocols characterized both peptides as presenting potent hemolytic action, mast cell degranulation, and chemotaxis of polymorphonucleated leukocyte (PMNL) cells. The primary sequences and the bioassay results suggest that these toxins constitute members of a new sub-class of mastoparan toxins, directly involved in the occurrence of inflammatory processes after wasp stinging. 相似文献
43.
In this work, we present a topological study of the Laplacian of the electronic density using a 6-311++G basis set, at Hartree-Fock (HF) and second-order M?ller-Plesset (MP2) (full-electron and frozen-core) levels of theory, for the carbocations 2-C-n-butonium generated upon the insertion of a proton into the secondary C-C bond during the protonation of n-butane. The charge concentration, CC, critical points of the Laplacian distribution at each valence shell, VS, of carbon atoms, and the charge concentration closer to hydrogen atoms are studied. Also, the bonding critical points of the electronic density are analyzed. We analyze some effects that Coulomb correlation has on topological features of the electronic distribution. It is shown that they are mainly reflected in a decreasing of the charge concentrations at the VS and in a contraction of the VS to the nuclei. They are more pronounced over C-C bonds than in C-H bonds. The sensitivity of some parameters derived from this topological analysis to the correlation effect of core electrons and subtle effects related to hyperconjugative interactions are shown. Some consequences of different schemes (double and triple split-valence basis set with diffuse and polarization functions) in the definition of subtle VS charge concentrations at 3c-2e bond paths are presented. It is also demonstrated here how the facts that allow us to understand the MP2 stability order found in the carbocationic species 2-C-n-butonium > 1-C-n-butonium > 2-H-n-butonium > 1-H-n-butonium are similarly depicted at correlated and uncorrelated levels of calculation. 相似文献
44.
Eduardo Corts Corts Eduardo Corts Romero Alicia Domínguez Taylor 《Journal of heterocyclic chemistry》1994,31(4):725-727
The preparation of nine novel 6H-2,7,7-trimethyl-4(o-,p-R-phenylamino)-7,8-dihydrofuro[3,2-c]-azepines with possible pharmacological activity is described. The structure of all products was corroborated by ir, 1H-nmr and ms. 相似文献
45.
Hctor Salgado Zamora Benito Rizo Elena Campos Rogelio Jimnez Alicia Reyes 《Journal of heterocyclic chemistry》2004,41(1):91-94
The imidazo[1,2‐a]pyridine system was investigated as a synthon for the building of very attractive fused triazines, a planar, angular tri‐heterocycle with potential biological activity. Thus ethyl 3‐nitroimidazo[1,2‐a]pyridine‐2‐carboxylate was treated with ammonia or with an excess of primary amines to generate the corresponding substituted nitro carboxamidoimidazopyridines. The nitro substituent in the latter products, was reduced to yield 3‐amino‐2‐carboxamidoimidazo[1,2‐a]pyridine derivatives, which in turn were treated with nitrous acid to furnish 1‐oxo‐2‐substituted pyrido(1′,2′:1,2)imidazo[5,4‐d]‐1,2,3‐triazines. 相似文献
46.
A series of diaryl ketones have been synthesized in good yields (40-78%) through the catalyst-free reaction of trimethylarylstannanes with aroyl chlorides in chlorobenzene as solvent. In addition, an attractive feature is that these reactions are completely regioselective making possible the synthesis of diarylketones which are not usually available under the influence of the directing forces of the substituents present in the aromatic ring. Also, the reaction conditions are mild enough to be applied to acid sensitive molecules. 相似文献
47.
Marcos Mandaji Tiago Buckup Rafael Rech Ricardo Rego Bordalo Correia Tarso Ledur Kist 《Talanta》2007,71(5):1998-2002
The performance of fluorescence detectors in capillary electrophoresis is maximized when the excitation light intensity is modulated in time with optimal frequencies. This is especially true when photomultiplier tubes are used to detect the fluorescent light. The photomultiplier tube amplified raw output signal can in principle be captured directly by a personal computer sound card (PCSC) and processed by a lock-in emulated by software. This possibility is demonstrated in the present work and the performance of this new setup is compared with a traditional data acquisition system. The results obtained with this “PCSC and lock-in emulated by software” were of the same quality or even better compared to that obtained by conventional time integrators (Boxcars) and data acquisition boards. With PCSC the limits of detection (LOD) found for both naphthalene-2,3-dicarboxaldehyde-derivatized tyrosine and alanine were 3.3 and 3.5 fmol (injection of 5 nL of samples at 0.66 and 0.70 μmol/L), respectively. This is at least three times better compared to conventional systems when light emitting diodes (LEDs) are used as the excitation source in fluorescence detectors. The PCSC linear response range was also larger compared to conventional data acquisition boards. This scheme showed to be a practical and convenient alternative of data acquisition and signal processing for detection systems used in capillary electrophoresis. 相似文献
48.
The reaction of the alkyne HCCC(O)OMe with 7 sep 1,2-(Cp*RuH)2B3H7 leads to hydroboration plus hydroruthenation to produce nido-1,3-mu-Me{C(O)OMe}C-1,2-(Cp*Ru)2B3H7, a compound with an exocluster ruthenium-boron mu-alkylidene that exists in two isomeric forms. Both isomers undergo rearrangement with intramolecular chelation of the carbonyl oxygen at a boron site, thereby opening the cluster and generating arachno-2,3,-mu(C)-5-eta1(O)-Me{C(O)OMe}C-1,2-(Cp*Ru)2B3H7. Further heating leads to deoxygenation of the carbonyl fragment by a boron center concurrent with insertion of the carbon atom into the metallaborane cage to give nido-1,2-(Cp*RuH)2-3-HOB-4-MeC-5-MeOC-BH3. 相似文献
49.
Nilo Zanatta Elizandra C. S. Lopes Leonardo Fantinel Helio G. Bonacorso Marcos A. P. Martins 《Journal of heterocyclic chemistry》2002,39(5):943-947
The synthesis of a novel series of twelve 4‐(trihalomethyl)dipyrimidin‐2‐ylamines, from the cyclo‐condensation reaction of 4‐(trichloromethyl)‐2‐guanidinopyrimidine, with β‐alkoxyvinyl trihalomethyl ketones, of general formula: X3C‐C(O)‐C(R2)=C(R1)‐OR, where: X = F, Cl; R = Me, Et, ‐(CH2)2‐, ‐(CH2)3‐; R1 = H, Me; R2 = H, Me, ‐(CH2)2‐, ‐(CH2)3‐, is reported. The reactions were carried out in acetonitrile under reflux for 16 hours, leading to the dipyrimidin‐2‐ylamines in 65‐90% yield. Depending on the substituents of the vinyl ketone, tetrahydropyrimidines or aromatic pyrimidine rings were obtained from the cyclization reaction. When X = Cl, elimination of the trichloromethyl group was observed during the cyclization step. The structure of 4‐(trihalomethyl)dipyrimidin‐2‐ylamines was studied in detail by 1H‐, 13C‐ and 2D‐nmr spectroscopy. 相似文献
50.
The development of useful synthetic tools to label amino acids within a peptide framework for the ultimate modification of proteins in a late-stage fashion is a challenging task of utmost importance within chemical biology. Herein, we report the first Pd-catalyzed C–H acylation of a collection of Tyr-containing peptides with aldehydes. This water-compatible tagging technique is distinguished by its site-specificity, scalability and full tolerance of sensitive functional groups. Remarkably, it provides straightforward access to a high number of oligopeptides with altered side-chain topology including mimetics of endomorphin-2 and neuromedin N, thus illustrating its promising perspectives toward the diversification of structurally complex peptides and chemical ligation.A novel Pd-catalyzed C–H acylation reaction with readily available aldehydes under an aqueous environment towards the assembly of non-protegenic acylated Tyr-containing oligopeptides is presented. 相似文献