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21.
A convenient and efficient method for the cleavage of 1,3-oxazolidin-5-ones and 1,3-oxazolidin-2-ones utilising potassium trimethylsilanolate in tetrahydrofuran is described. The benzyloxycarbonyl-protecting group is readily removed under the reaction conditions, whereas the N-benzoyl group is stable. A synthesis of (R)-salmeterol exploiting the 2-oxazolidinone ring as a protecting group for the ethanolamine moiety is also described. 相似文献
22.
[reaction: see text] A regioselective method for the preparation of 1,5-trisubstituted 1H-1,2,3-triazoles via a 1,3-dipolar cycloaddition of 1-trimethylsilylacetylenes with organoazides is described. Immobilization of the azide on REM resin and subsequent cycloaddition afforded a 2 x 2 x 4 x 3 membered 1,5-disubstituted 1H-1,2,3-triazole library with an average purified yield of 68%. 相似文献
23.
The rate constants at which oxidizing and reducing radicals react with the dinuclear iron(III) complex Fe2O(ttha)2− were measured in neutral aqueous solution. The rate constants for reduction of the complex by ·CO2.− CH3.CHOH and O2.− were found to be comparable with rate constants previously measured in mononuclear iron(III) polyaminocarboxylate systems. Fe2O(ttha)2− reacts slowly with O2.− (k8 = (1.2 ± 0.2) × 104 dm3 mol−1 s−1) and, hence, is a relatively poor catalyst for the dismutation of superoxide radical. The hydrated electron reduces the complex at a diffusion-controlled rate in a process which consumes one proton: eaq− + Fe2O(ttha)2− → Fe2III,IIO(ttha)3− The reduction by carbon-centered radicals produces a (III,II) mixed-valence complex with an absorption spectrum different from that of the Fe2(II,III) species produced from reduction by the hydrated electron. The oxidizing radicals .OH and ·CO3− appear to act as reductants of the complex via ligand oxidation rather than by oxidation of the Fe2IIIO core to Fe2III,IVO. In the former case ligand attack appears to occur mainly at the methylene carbon of a glycinate group. The decarboxylation product, CO2, was detected by its aquation reaction in the presence of a pH sensitive dye, bromthymol blue. 相似文献
24.
Goodman D Kizhakkedathu JN Brooks DE 《Langmuir : the ACS journal of surfaces and colloids》2004,20(15):6238-6245
The accuracy of the molecular weights Mn and polydispersities of polymer brushes, determined by stretching the grafted chains using atomic force microscopy (AFM) and measuring the contour length distribution, was evaluated as a function of grafting density sigma. Poly(N,N-dimethylacrylamide) brushes were prepared by surface initiated atom transfer radical polymerization on latex particles with sigma ranging between 0.17 and 0.0059 chains/nm2 and constant Mn. The polymer, which could be cleaved from the grafting surface by hydrolysis and characterized by gel permeation chromatography (GPC), had a Mn of 30,600 and polydispersity (PDI) of 1.35. The Mn determined by the AFM technique for the higher density brushes agreed quite well with the GPC results but was significantly underestimated for the lower sigma. At high grafting density in good solvent, the extended structure of the brush increases the probability of forming segment-tip contacts located at the chain end. When the distance between chains approached twice the radius of gyration of the polymer, the transition from brush to mushroom structure presumably enabled the formation of a larger number of segment-tip contacts having separations smaller than the contour length, which explains the discrepancy between the two methods at low sigma. The PDI was typically higher than that obtained by GPC, suggesting that sampling of chains with above average contour length occurs at a frequency that is greater than their spatial distribution. 相似文献
25.
Diane C. Rawlings Ernest R. Davidson Martin Gouterman 《International journal of quantum chemistry》1984,26(2):237-250
A new minimum basis set was developed for use in computing excitation energies of large molecules. It is particularly suited to calculating ionization potentials and Rydberg transitions. Pyrrole excitation energies and oscillator strengths calculated with this basis set are compared to larger basis set ab initio and semiempirical results. The 6-eV band in the experimental spectrum is predicted to be the result of three Rydberg absorptions, with no underlying (π, π*) absorption. The calculations also provide an explanation for the observed N? H stretch in the 6-eV region. 相似文献
26.
Young Gun Ko Ung Su Choi Yong Sung Park Je Wan Woo 《Journal of polymer science. Part A, Polymer chemistry》2004,42(8):2010-2018
The role of hydrogen bonding in the chemistry of transition‐metal complexes remains a topic of intense scientific and technological interest. Poly(acrylo‐amidino diethylenediamine) was synthesized to study the effects of hydrogen bonding on complexes at different pHs. The polymer was synthesized through the coupling of diethylene triamine with polyacrylonitrile fiber in the presence of AlCl3 · 6H2O addition. The adsorption capacity of this polymer was 11.4 mequiv/g. The ions used for the adsorption test were CrO, PO, Cu2+, Ni2+, Fe2+, and Ag+. All experiments were confirmed with Fourier transform infrared. In the study of anion adsorption, at low pHs, only ionic bonds existed, whereas at high pHs, no bonds existed. However, in the middle pH region, both ionic bonds and hydrogen bonds formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion or phosphate ion. When poly(acrylo‐amidino diethylenediamine) and metal ions (Cu2+, Ni2+, Fe2+, and Ag+) formed complexes, a hydrogen‐bonding effect was not observed with Fourier transform infrared. The quantity of metal ions adsorbed onto poly(acrylo‐amidino diethylenediamine) followed the order Ag+ > Cu2+ > Fe2+ > Ni2+. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2010–2018, 2004 相似文献
27.
Medicinal plants have been explored therapeutically in traditional medicines and are a valuable source for drug discovery. Insufficient knowledge about the molecular mechanism of these medicinal plants limits the scope of their application and hinders the effort to design new drugs using the therapeutic principles of herbal medicines. This problem can be partially alleviated if efficient methods for rapid identification of protein targets of herbal ingredients can be introduced. Efforts have been directed at developing efficient computer methods for facilitating target identification. Various methods being explored or under investigation are reviewed here. So far, one computer method, INVDOCK, has been specifically used for automated drug target identification. Its usefulness in the identification of therapeutic targets of medicinal herbal ingredients as well as synthetic chemicals is reviewed. The majority of INVDOCK identified therapeutic targets of several well-known medicinal herbal ingredients have been found to be confirmed or implicated by experiments, which suggests the potential of in silico methods in facilitating the study of molecular mechanism of medicinal plants. 相似文献
28.
Supplier-customer interaction in quality control 总被引:5,自引:0,他引:5
Diane J. Reyniers 《Annals of Operations Research》1992,34(1):307-330
We develop a game theoretic model of joint quality control in a single sourcing environment which integrates supplier and customer decisions. In this model, both parties behave strategically and take each other's incentives into account when deciding on their respective sampling plans. The specific sampling plans considered are of the single sample fraction defective with rectifying inspection type. A method to find the optimal sampling plans for both supplier and customer in two different informational setups is constructed. The resulting models lead to examination of Stackelberg and Nash equilibria. Numerical examples of such equilibria are presented, indicating how optimal strategies depend on the parameters of the problem. 相似文献
29.
A polyacrylonitrile (PAN) fiber was adopted for the backbone of a chelate polymer and poly(acrylo‐amidino ethylene amine) (PAEA) was prepared through a one‐step reaction between the PAN fiber and ethylenediamine (EDA). The maximum removal capacity and degree of substitution were 7.8 meq per gram of dried PAEA and 98%, respectively. The PAEA was tested as an adsorbent in single and two‐component metal aqueous solutions under changing pH. The Cu2+ ion accomplished maximum adsorption amount at pH 3 and the order of maximum adsorbed amounts on PAEA is Cu2+ > Ag+ > Zn2+ > Ni2+ > Pb2+ in molar basis. FT‐IR spectroscopy was employed to characterize the chemical bonding in metal aqueous solutions and surface morphology was examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
30.
Hydroxylamine and some of its O -substituted derivatives ( 2 ) have been used as the amine component in Mannich reactions with 2,4,6-triaminopyrimidine ( 1 ). The resulting 6-substituted tetrahydropyrimido[4,5-d]-pyrimidines ( 3 ) contain an N-0 bond linking the substituent to the ring. These results extend the utility of this modified Mannich reaction to otherwise inaccessible substituents. Reaction conditions, spectral data and certain limitations of the reaction are discussed. 相似文献