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171.
[reaction: see text] An expedient solid-phase synthetic approach to secondary and tertiary amines was developed. The protocol employs conversion of resin-bound amino alcohols to the corresponding iodides, followed by iodide displacement with primary or secondary amines or with unprotected amino alcohols. This two-step procedure, affording products in good to excellent yields, is suitable for solid-phase synthesis of polyamines. 相似文献
172.
Tsybin YO Witt M Baykut G Håkansson P 《Rapid communications in mass spectrometry : RCM》2004,18(14):1607-1613
Electron capture dissociation (ECD) of polypeptide cations was obtained with pencil and hollow electron beams for both sidekick and gas-assisted dynamic ion trapping (GADT) using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) with an electrostatic ion transfer line. Increasing the number of trapped ions by multiple ICR trap loads using GADT improved the ECD sensitivity in comparison with sidekick ion trapping and ECD efficiency in comparison with single ion trap load by GADT. Furthermore, enhanced sensitivity made it possible to observe ECD in a wide range of electron energies (0-50 eV). The degree, rate and fragmentation characteristics of ECD FTICR-MS were investigated as functions of electron energy, electron irradiation time, electron flux and ion trapping parameters for this broad energy range. The results obtained show that the rate of ECD is higher for more energetic (>1 eV) electrons. Long electron irradiation time with energetic electrons reduces average fragment ion mass and decreases efficiency of formation of c- and z-type ions. The obtained dependencies suggest that the average fragment ion mass and the ECD efficiency are functions of the total fluence of the electron beam (electron energy multiplied by irradiation time). The measured electron energy distributions in low-energy ECD and hot ECD regimes are about 1 eV at full width half maximum in employed experimental configurations. 相似文献
173.
Matthias Weil Franz Werner Frank Kubel 《Monatshefte für Chemie / Chemical Monthly》2002,133(3):267-275
Summary. Single crystals of MgAl2F8(H2O)2 have been obtained under hydrothermal conditions (250°C, 14 d) from a starting mixture of AlF3 and MgAlF5(H2O)2 in a 5% (w/w) HF solution. The crystal structure has been determined and refined from single crystal data (Fmmm (#69), Z = 4, a = 7.2691(7), b = 7.0954(16), c = 12.452(2) ?, 281 structure factors, 27 parameters, R(F
2 > 2σ (F
2)) = 0.0282, wR(F
2 all) = 0.0885). The obtained crystals were systematically twinned according to (010/100/001) as twinning matrix, reflecting
the pseudo-tetragonal metric. The crystal structure is composed of perowskite-type layers built of corner sharing AlF6 octahedra with an overall composition of AlF4
− which are connected via common fluorine atoms of [MgF4/2(H2O)2/1] octahedra. Group-subgroup relations of MgAl2F8(H2O)2 to WO3(H2O)0.33 and to other M(II)M(III)2 F8(H2O)2 structures are briefly discussed. Above 570°C, MgAl2F8(H2O)2 decomposes under elimination of water into α-AlF3, β-AlF3, and MgF2.
Received October 29, 2001. Accepted (revised) December 6, 2001 相似文献
174.
Reverse micelles currently gain increasing interest in chemical technology. They also become important in biomolecular NMR due to their ability to host biomolecules such as proteins. In the present paper, a procedure for the preparation of high-pressure NMR samples containing reverse micelles dissolved in supercritical xenon is presented. These reverse micelles are formed by sodium bis(2-ethylhexyl) sulfosuccinate (AOT). For the first time, NMR spectroscopy could be applied to reverse micelles in supercritical xenon. The AOT/H(2)O/Xe system was studied as a function of experimental parameters such as xenon pressure, water content, and salt concentration. Optimum conditions for reverse micelle formation in supercritical xenon could be determined. It is, furthermore, demonstrated that biomolecules such as amino acids and proteins can be incorporated into the reverse micelles dissolved in supercritical xenon. 相似文献
175.
Microcolumns with self-assembled particle frits for proteomics 总被引:1,自引:0,他引:1
LC-MS-MS experiments in proteomics are usually performed with packed microcolumns employing frits or outlets smaller than the particle diameter to retain the packing material. We have developed packed microcolumns using self-assembled particles (SAPs) as frits that are smaller than the size of the outlet. A five to one ratio of outlet size to particle diameter appears to be the upper maximum. In these situations the particles assembled into an arch over the outlet like the stones in a stone bridge. When 3 microm particles were packed into a tapered column with an 8 microm outlet, two particles bridged the outlet with 0.3 pl dead volume and perfect success rate. In peptide analysis by LC-MS, the peak width at half height was normally less than 6 s, compared to 12 s without SAPs. The LC-MS-MS system provided 37% sequence coverage (21 matched peptides) for a tryptically-digested sample of 10 fmol bovine serum albumin. We also describe application of the SAP principle to make disposable pipette tip columns with short pieces of fused-silica capillary as the outlet. 相似文献
176.
树脂填充EVAL纤维吸附剂的制备及其吸附性能表征 总被引:3,自引:0,他引:3
采用具有亲水性的乙烯-乙烯醇共聚物(EVAL)作为纤维吸附剂基质材料,粉末型Lewatit阳离子交换树脂CNP80ws为功能材料,采用可控相分离方法,制备了不同表面形态结构的树脂填充EVAL吸附剂.当使用外部液体调控相分离过程时,在纤维的表面形成了粗糙的开孔结构,并且随树脂的填充量提高纤维表面的粗糙度与开孔度有所提高.研究结果表明:树脂填充EVAL纤维吸附剂具有较大的吸附容量与较高的脱附率,其吸附容量不低于53.9mg BSA/g吸附剂(树脂填充量50%). 相似文献
177.
Matthias Treu Christian Hametner Johannes Frohlich Ulrich Jordis Kurt Mereiter 《Journal of heterocyclic chemistry》2002,39(6):1283-1288
The synthesis of a novel unnatural carbocyclic analog of the acetylcholine esterase inhibitor galanthamine with a K3[Fe(CN)6] promoted oxidative tandem cyclization as the key step is reported. 相似文献
178.
(?)-β-Caryophyllene (1) adopts three conformations in solution: αα(48%), βα(28%), and ββ(24%). The conformations were identified by an analysis of the 13C- and 1H-NMR spectra at ?87.2 and ?153.8° in connection with APT, HETCOR, and COSY spectra, and subsequent NOESY experiments. The activation parameters of the conversion αα → βα were determined from a bandshape analysis of exchange-broadened 13C-NMR spectra of 8-[methylene-13C]- 1 to give ΔH≠ = 5.9 ± 0.3 kcal/mol, ΔS? = ?8.1 ± 1.8 cal/mol. · K. and ΔG = ?8.3 ± 0.8 kcal/mol. The observed population ratio of the different conformers is best described by MM3. 相似文献
179.
180.
Jonathan Pansieri Igor A. Iashchishyn Hussein Fakhouri Lucija Ostoji Mantas Malisauskas Greta Musteikyte Vytautas Smirnovas Matthias M. Schneider Tom Scheidt Catherine K. Xu Georg Meisl Tuomas P. J. Knowles Ehud Gazit Rodolphe Antoine Ludmilla A. Morozova-Roche 《Chemical science》2020,11(27):7031
The mechanism of amyloid co-aggregation and its nucleation process are not fully understood in spite of extensive studies. Deciphering the interactions between proinflammatory S100A9 protein and Aβ42 peptide in Alzheimer''s disease is fundamental since inflammation plays a central role in the disease onset. Here we use innovative charge detection mass spectrometry (CDMS) together with biophysical techniques to provide mechanistic insight into the co-aggregation process and differentiate amyloid complexes at a single particle level. Combination of mass and charge distributions of amyloids together with reconstruction of the differences between them and detailed microscopy reveals that co-aggregation involves templating of S100A9 fibrils on the surface of Aβ42 amyloids. Kinetic analysis further corroborates that the surfaces available for the Aβ42 secondary nucleation are diminished due to the coating by S100A9 amyloids, while the binding of S100A9 to Aβ42 fibrils is validated by a microfluidic assay. We demonstrate that synergy between CDMS, microscopy, kinetic and microfluidic analyses opens new directions in interdisciplinary research.Templating mechanism of S100A9 amyloids on Aβ fibrillar surfaces during amyloid co-aggregation process was revealed by synergy of biophysical methods including charge detection mass spectrometry, microscopy, kinetic and microfluidic analyses. 相似文献