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141.
A sheath-flow capillary electrophoresis-mass spectrometry (CE-MS) system utilizing a fully integrated large-bore stainless-steel emitter electrode tapered at the end for micro-ionspray operation has been developed and evaluated. A separation capillary with an outer diameter of up to 360 microm was inserted into the electrode thus forming a void volume of less than 15 nL between the capillary end and the electrospray ionisation (ESI) tip. The sheath liquid, usually methanol-water (80:20) with 0.1% formic acid for positive ion mode or methanol for negative ion mode, was delivered at 0.5-1.0 microL/min. Unlike previously reported CE-MS interfaces, the CE-MS probe was incorporated directly onto an Applied Biosystems/MDS SCIEX orthogonal-spray Turbo "V" ion source for ease of use and automatic operation. This integration enables fast and facile coupling and replacement of the separation capillary without interrupting the ion source configuration, and the sheath liquid supply. The reusable electrospray electrode was precisely fabricated and aligned with the length of the nebulizing gas tube for improved reproducibility. Automation was achieved through software control of both CE and tandem MS (MS/MS) for unattended batch sample analysis. The system was evaluated for attomole- to low femtomole-level profiling of model peptides and protein mixtures, bisphosphates, as well as antiviral nucleosidic drugs in cellular extracts. 相似文献
142.
During bacterial chemotaxis, the histidine autokinase CheA interacts with the chemotaxis receptors with the help of the coupling protein CheW. This interaction is typical of many macromolecular complexes where protein-protein interactions play an important role. In this case, a relatively small protein, CheW, becomes part of a much larger complex. Here we describe a new method to map the residues at a protein-protein interface for macromolecular complexes of molecular weight greater than 100 kD. 相似文献
143.
Christian Amatore Anny Jutand Serge Negri Jean-Francois Fauvarque 《Journal of organometallic chemistry》1990,390(3):389-398
4,4′-Unsymmetrically substituted biphenyls can be synthesized by cross-coupling reactions of substituted aromatic organometallic reagents and aromatic halides catalyzed by palladium complexes. This two-step method from commercially available aromatic halides has been used for the synthesis of a series of donor/acceptor para-substituted biphenyls, D---C6H4---C6H4---A, where D is an electron donor group and A an electron acceptor group, which are of interest as liquid crystal precursors and as having potential in non-linear optics. Biaryls in which the donor-phenyl moiety is replaced by a 2-furyl or 2-thienyl can be synthesized similarly. The method can also be used for the convergent synthesis of previously unreported unsymmetrically substituted polyparaphenylenes
(n = 3,4). 相似文献
144.
Dr. Xingjuan Zhao Prof. Dr. Yuechen Jia Dr. Gregory Q. Wallace Prof. Dr. C. Geraldine Bazuin Prof. Dr. Jean-Francois Masson 《Chemphyschem》2023,24(13):e202200842
Detailed mechanistic investigations of the interrelated roles of multiple key structure-directing agents in the growth solution of Au nanoparticles (AuNPs) is required for the optimization of synthetic protocols. Here, we report a robust seed-mediated growth strategy for synthesizing multibranched NPs (MB-AuNPs) with monodispersed size distribution, and investigate the roles of Ag ions and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES) based on an overgrowth synthesis approach. The intertwining roles of Ag+, surface-capping stabilizers, and reducing agents were elucidated, and used to control the morphology of MB-AuNPs. The overgrowth of MB-AuNPs involves two distinct underlying pathways, namely, directional and anisotropic growth of Au branches on specific facets of Au seeds as well as an aggregation and growth mechanism governed by HEPES. In addition to Ag ions and HEPES, morphology tunability can also be achieved by pre-modification of the Au seeds with molecular probes. Optimized probe-containing MB-AuNPs prove to be excellent surface-enhanced Raman scattering (SERS) substrates and nanozymes. Taken together, the results of this work reveal the mechanistic evolution of nanocrystal growth which should stimulate the development of new synthetic strategies, improve the capabilities of tuning the optical, catalytic, and electronic properties of NPs, and further advance their applications in biolabeling, imaging, biosensing, and therapy. 相似文献
145.
Li P Evans CD Wu Y Cao B Hamel E Joullié MM 《Journal of the American Chemical Society》2008,130(7):2351-2364
Ustiloxins A-F are antimitotic heterodetic cyclopeptides containing a 13-membered cyclic core structure with a synthetically challenging chiral tertiary alkyl-aryl ether linkage. The first total synthesis of ustiloxin D was achieved in 31 linear steps using an S(N)Ar reaction. An NOE study of this synthetic product showed that ustiloxin D existed as a single atropisomer. Subsequently, highly concise and convergent syntheses of ustiloxins D and F were developed by utilizing a newly discovered ethynyl aziridine ring-opening reaction in a longest linear sequence of 15 steps. The approach was further optimized to achieve a better macrolactamization strategy. Ustiloxins D, F, and eight analogues (14-MeO-ustiloxin D, four analogues with different amino acid residues at the C-6 position, and three (9R,10S)-epi-ustiloxin analogues) were prepared via the second-generation route. Evaluation of these compounds as inhibitors of tubulin polymerization demonstrated that variation at the C-6 position is tolerated to a certain extent. In contrast, the S configuration of the C-9 methylamino group and a free phenolic hydroxyl group are essential for inhibition of tubulin polymerization. 相似文献
146.
Kong Y Grembecka J Edler MC Hamel E Mooberry SL Sabat M Rieger J Brown ML 《Chemistry & biology》2005,12(9):1007-1014
Targeting the microtubule system represents an attractive strategy for the development of anticancer agents. In this study, we report a class of combretastatin A-4 (CA-4) analogs derivatized with a boronic acid moiety replacing the hydroxyl group on the C-ring of CA-4. Docking studies of the X-ray structures of our aryl-boronic analogs onto an X-ray structure of the alpha,beta-tubulin heterodimer suggested that cis-6 was a potent inhibitor of the colchicine binding. The model indicated that there would be strong hydrogen bonding between the boronic acid moiety and Thr-179 and Val-181 of alpha-tubulin. We demonstrate that the cis-6 boronic acid bioisostere of CA-4: (1) inhibits tubulin assembly, (2) competitively displaces colchicine, and (3) is a low-nanomolar inhibitor of human cancer cell lines. We present this isostere as a class of potent analogs of CA-4. 相似文献
147.
Shin Y Fournier JH Balachandran R Madiraju C Raccor BS Zhu G Edler MC Hamel E Day BW Curran DP 《Organic letters》2005,7(14):2873-2876
[structure: see text] (-)-16-Normethyldictyostatin has been made by total synthesis and is a potent antitumor agent in cells expressing wild-type tubulin and in one mutant cell line that is resistant to paclitaxel, but it is much less active than dictyostatin in another paclitaxel-resistant cell line where Val is substituted for Phe270. This provides strong evidence that the C16 methyl group of the dictyostatins is oriented toward Phe270 in the paclitaxel-binding site on beta-tubulin. 相似文献
148.
F.W. Büsser L. Camilleri L. Di Lella B.G. Pope A.M. Smith B.J. Blumenfeld S.N. White A.F. Rothenberg S.L. Segler M.J. Tannenbaum M. Banner J.B. Chèze J.L. Hamel H. Kasha J.P. Pansart G. Smadja J. Teiger H. Zaccone A. Zylberstejn 《Physics letters. [Part B]》1975,56(5):482-486
In an experiment performed at the CERN Intersecting Storage Rings (ISR), 11 e+e? pairs of high invariant mass value (> 2.5 GeV/c2) have been observed. Of these events, 9 can be interpreted as arising from the reaction p + p → J (3.1) + anything. the cross-section for this reaction is estimated and compared with the result obtained at lower centre-of-mass energies. 相似文献
149.
Georg Hamel 《Mathematische Annalen》1964,78(1):257-269
Ohne ZusammenfassungDas Manuskript dieser Arbeit lief im Februar, 1917 bei der Redaktion ein. Das Juniheft des Bd. 147 von Crelles Journal brachte unter dem Titel Über Potenzreihen, die im Inneren des Einheitskreises beschränkt sind (S. 205–232) eine größere Veröffentlichung von Herrn I. Schur, die u. a. den weitaus größten Teil der Ausführungen des Herrn Hamel enthält. Zu seinem Bedauern lernte dieser die Arbeit des Herrn Schur erst nach der Korrektur seiner Arbeit kennen, sonst würde die Veröffentlichung unterblieben sein. 相似文献
150.