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91.
Several multicomponent assembly processes have been developed for the synthesis of intermediates that may be elaborated by a variety of cyclizations to generate a diverse array of highly functionalized heterocycles from readily-available starting materials. The overall approach enables the efficient preparation of libraries of small molecules derived from fused, privileged scaffolds. 相似文献
92.
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94.
Low-energy ion scattering with monolayer sensitivity was applied to investigate ultrathin films of zinc on Pd(1?1?1). Uptake curves taken at 150?K indicate the simultaneous growth of multilayers with negligible interlayer transport. Annealing experiments for two-monolayer films reveal a rapid decrease in the zinc content on the surface layer at temperatures above 300?K, forming a metastable state with a Pd:Zn surface ratio of approx. 1:1 in the temperature region between 400 and 550?K. This state is most easily explained as a slightly buckled p(2?×?1)-PdZn surface alloy, with Zn atoms located approx. 0.25?? above their Pd counterparts. 相似文献
95.
The output regulation problem is solved for an ODE plant driven by a parabolic actuator with spatially varying coefficients. Applying the backstepping transformation to the actuator allows the solution of the regulator equations in closed-form and thus the formulation of the solvability condition. An output feedback regulator is obtained by designing a disturbance observer using delayed measurement and a reference observer that both achieve finite-time convergence. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
96.
This contribution discusses the non-linear dynamic behaviour of a rotor system equipped with a compliant seal. The investigated model consists of a Laval-Rotor and a stiff seal ring which is visco-elastically supported. The fluid forces stemming from the turbulent incompressible lubricant film are accounted for by the non-linear Muszynska model. The added compliance leads to an improved stability behaviour of the steady state. Within the post-critical regime the additional compliance gives rise to bifurcations of the stationary vibration: Hopf bifurcations lead to limit cycles which can loose their stability via Neimark-Sacker bifurcations. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
97.
Abstract Macrocyclic molecules capable of selective recognition of ionic or neutral guests are of considerable current interest. The design and synthesis of host molecules that contain phosphorus have been developed recently. Typically, the model compound A is modified to the more rigid molecule B which can exist as two exo/endo isomers. B represents a new family of preorganized ligands that can involve the phosphorus group during complexation of various guests. The exo/endo isomerisni was investigated by NMR studies. The complexing properties of B were studied by NMR and extraction method with alkaline and ammonium cations. The complexation constants mainly depend on the molecular geometry and the size of the cavity. The highest Ka constants are obtained with the endo isomer where the P=O bond is directed toward the center of the macrocycle. Complex formation and detailed stereochemical data for A and B will be presented. 相似文献
98.
G. Becker M. Mayer O. Mundt H. Riffel H. J. Wessely A. Simon 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract In (dimethylaminomethylidene)phosphines (1) [1] and -arsines (2) the internal rotation of the dimethylamino group is hindered by a barrier of 50 to 55 kJmol?1? analogous to the corresponding amidines. In order to evaluate the influence of this conjugative effect upon the P=C and (P)-C-N bond lengths, single crystal x-ray structure determinations of 1a and 2a have been carried out. For comparison, the cyclic (aminomethylidene)phosphine 1H-1,3-benzazaphosphole 5 [2] as well as the dimeric compounds 3a, 3b, and 3c [3] have been analyzed, too, while the arsenic derivative 6 was studied by others [4]. The diarsetanes 4 could not yet be isolated. The structural results indicate the E=C bonds in 1a, 2a, 5, and 6 to be scarcely elongated, the (E)-C-N bonds, however, to be shortened considerably with respect to the dimers. 相似文献
99.
Nathaniel W. Alcock Adam J. Clarke William Errington Ana Maria Josceanu Peter Moore Simon C. Rawle 《Supramolecular chemistry》2013,25(3-4):281-291
Abstract A series of azamacrocycles which have been N-functionalised with pendent pyridylmethyl-(pyCH2-), bipyridylmethyl-(bipyCH2-) and terpyridylmethyl- (terpyCH2-) arms have been synthesised and characterised, and some of their coordination chemistry with transition metal ions is reported. By attaching the pendent-arms at the 5- rather than the 6-position of the py, bipy and terpy, new ligands are generated which can be used to form polynuclear metal complexes in a controlled and systematic fashion. Fluorescent pH and transition metal ion sensors have been developed by reacting the azamacrocyclic N-pendent bipyCH2 arm(s) with cis-[Ru(bipy)2Cl2], to give macrocycles with up to four attached [Ru(bipy)3]2+ groups. That based on 1,4,7-triazacyclononane (9N3), with three attached [Ru(bipy)3]2+ groups, has a first photo excited state pKa of 7.1, and is a useful fluorescent sensor for physiological pH at below micromolar concentrations. The analogous derivative of cyclam (1,4,8,11-tetraazacyclotetradecane) carrying four [Ru(bipy)3]2+ groups has a first photo excited state pKa of 5.7, allowing kinetic and thermodynamic fluorescence studies of metal ion uptake by an azamacrocycle at neutral pH without complications from protonated species. A pre-organised hexadentate tris(2,2′-bipyridyl) chelating ligand, 1,4,7-tris(2′,2″-bipyridyl-5′-ylmethyl)-1,4,7-triazacyclononane (L) has been developed, and crystal structures of mononuclear complexes [M(LH)]3+ (M = Ru, Cu) are reported. In [M(LH)]3+ the azamacrocyclic N-atoms are non-coordinating to M, but have a very high affinity for a single proton trapped in the macrocyclic cavity. An analogous and potentially nonadentate ligand has been developed based on 9N3 with three N-pendent terpyCH2-arms. 相似文献
100.
Lewis Couchman Sarah L. Belsey Simon A. Handley Robert J. Flanagan 《Analytical and bioanalytical chemistry》2013,405(29):9455-9466
Therapeutic drug monitoring (TDM) requires timely results in order to be clinically helpful. Such assays, when carried out using mass spectrometry-based methods, typically involve a batched sample approach with multipoint calibration. Isotopic internal calibration offers the possibility of open-access mass spectrometric analysis with consequent shortening of turnaround times. We measured plasma clozapine and N-desmethylclozapine (norclozapine) concentrations in (1) external quality assessment (EQA) samples (N?=?22) and (2) patient samples (N?=?100) using liquid chromatography-tandem mass spectrometry with isotopic internal calibration (ICAL-LC-MS/MS). Analyte concentrations were calculated from graphs of the response of three internal calibrators (clozapine-D4, norclozapine-D8, and clozapine-D8) against concentration. Precision (% RSD) and accuracy (% nominal concentrations) for the ICAL-LC-MS/MS method were <5 % and 104–112 %, respectively for both analytes. There was excellent agreement with consensus mean and with ‘spiked’ values on analysis of the EQA samples (R 2?=?0.98 and 0.97, respectively, inclusive of clozapine and norclozapine results). In the patient samples, comparison against traditionally calibrated HPLC-UV and LC-MS/MS methods showed excellent agreement (R 2?=?0.97 or better) with small albeit significant mean differences (<0.041 and <0.042 mg/L for clozapine and norclozapine, respectively). These differences probably reflect discrepancies in the in-house preparation of calibrators and/or interference in the UV method. Internal calibration offers a novel and attractive alternative to traditionally calibrated batch analysis in analytical toxicology. The method described has been validated for use in the high-throughput TDM of clozapine and norclozapine, and allows for (1) same-day reporting of results and (2) significant cost savings. Figure
A typical internal calibration curve produced using three different isotopically-labelled analogues of clozapine and norclozapine (clozapine-D4, norclozapine-D8 and clozapine-D8) and interpolation of the clozapine and norclozapine concentrations from an extracted patient sample (calculated clozapine and norclozapine 0.47 and 0.31 mg/L, respectively) 相似文献