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141.
Jaime Muñoz-Flores Alberto Herrera-Gomez 《Journal of Electron Spectroscopy and Related Phenomena》2012,184(11-12):533-541
Peak-fitting of X-ray photoelectron spectroscopy (XPS) data can be very sensitive to noise when the difference on the binding energy among the peaks is smaller than the width of the peaks. This sensitivity depends on the fitting algorithm. Angle-resolved XPS (ARXPS) analysis offers the opportunity of employing the combined information contained in the data at the various angles to reduce the sensitivity to noise. The assumption of shared peak parameters (center and width) among the spectra for the different angles, and how it is introduced into the analysis, plays a basic role. Sequential fitting is the usual practice in ARXPS data peak-fitting. It consist on first estimating the center and width of the peaks from the data acquired at one of the angles, and then using those parameters as a starting approximation for fitting the data for each of the rest of the angles. An improvement of this method consists of averaging the centers and widths of the peaks obtained at the different angles, and then employing these values to assess the areas of the peaks for each angle. Another strategy for using the combined information is by assessing the peak parameters from the sum of the experimental data. The complete use of the combined information contained in the data-set is optimized by the simultaneous fitting method. It consists of the assessment of the center and width of the peaks by fitting the data at all the angles simultaneously. Computer-generated data was employed to compare the sensitivity with respect to noise between the sequential, averaged-sequential, sum, and simultaneous fitting methods. It is shown that the latter is significantly more robust and could provide reliable results even for noisy data and small peak separation. The fundamentals for the robustness of the simultaneous method are discussed, as well as the possibility of fitting many parameters at the same time. As an added feature of ARXPS, it was found that the estimation of the error intervals on the peak parameters is done remarkably more precisely by employing XPS data at various angles. 相似文献
142.
Zongxia Guo Yubao Song Ruiying Gong Youbing Mu Yi Jiang Ming Li 《Supramolecular chemistry》2013,25(5-6):383-391
Biomolecule-directed self-assembly of π-conjugated oligomers has attracted great attention in the past decade. In this contribution, two conjugates composed of quaterthiophene and tetrapeptide (Gly-Val-Gly-Val) were synthesised, namely peptide–thiophene–peptide (PTP) and thiophene–peptide–thiophene (TPT), to investigate the influence of peptide content ratio and its location in the molecular structures on the nanostructures and properties of the assemblies. Both conjugates formed organogels consisting of left-handed twisted nanostructures; however, anti-parallel β-sheets were observed in PTP while parallel β-sheets were obtained for TPT, although in both cases oligothiophenes adopted an H-like stacking mode. Obvious solvent-induced supramolecular chirality inversion from the oligothiophene segment was observed for PTP while such phenomenon was not clear for TPT. PTP and TPT gels also showed different stabilities towards temperature increase, as evidenced by variable-temperature circular dichroism study. From the data, it is suggested that the rational design of the location and ratio of peptide plays a key role in constructing materials with determined properties based on peptide–thiophene conjugates. 相似文献
143.
C. Lavilla A. Alla A. Martínez de Ilarduya E. Benito M.G. García‐Martín J.A. Galbis S. Muñoz‐Guerra 《Journal of polymer science. Part A, Polymer chemistry》2012,50(16):3393-3406
Random poly(hexamethylene terephthalate‐co‐galactarate)s and poly(dodecamethylene terephthalate‐co‐galactarate)s copolyesters covering the whole range of compositions were obtained with weight‐average molecular weights of ~30,000–50,000 g mol?1 by melt polycondensation. They were thermally stable above 300 °C, and displayed Tg in the +20 to ?20 °C range with values steadily decreasing with the content in galactarate units. All the copolyesters were semicrystalline with Tm between 50 and 150 °C and those made from dodecanediol were able to crystallize from the melt at a crystallization rate depending on composition. Copolyesters containing up to 50% of galactaric units retained the crystal structure of their respective polyterephthalate homopolyesters, whereas they adopted the structure of the respective polygalactarates when the content in Galx units reached 70%. Stress‐strain essays revealed decay in the mechanical parameters as the aromatic units were replaced by Galx. Incubation in aqueous buffer revealed that hydrolysis of the polyesters were largely enhanced by copolymerization and evidenced the capacity of the Galx unit for making aromatic polyesters susceptible to biodegradation. A detailed NMR analysis complemented by SEM observations indicated that hydrolysis took place by preferred splitting of galactarate ester bonds with releasing of alkanediol and Galx‐diacid. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
144.
145.
Bert C. Lynn Jesus V. Mallén Servando Muñoz Minsook Kim George W. Gokel 《Supramolecular chemistry》2013,25(3-4):195-197
Abstract Bola-amphiphiles having two aza-18-crown-6 ether rings attached by a covalent spacer (O—O) and an analogous tris (macrocycle) (O—O—O) have been prepared and their cation complexation behavior has been assessed by fast atom bombardment and collisionally activated dissociation tandem mass spectrometry; the key finding is that two cations may simultaneously be complexed by a two- or three-crown system and that this complexation may also involve an anion. 相似文献
146.
Abstract: Titanium tetrachloride was reduced by zinc powder in THF to produce low-valent titanium which reacted with 4,4-dicyano-1,3-diaryl-1-buanone to give the derivatives of 1-amino-2-cyanocyclopentene. 相似文献
147.
148.
Two new 4‐hydroxyisoflavanes, cordifoliflavanes A and B (1 and 2), were isolated from the roots of Codonopsis cordifolioidea. Their structures were elucidated by spectroscopic methods, including extensive 1D‐ and 2D‐NMR techniques. Compounds 1 and 2 were tested for their anti‐HIV‐1 activities and anti‐tobacco mosaic virus activities. The results showed that compounds 1 and 2 have modest anti‐HIV‐1 activities and anti‐tobacco mosaic virus activities, respectively. 相似文献
149.
Ren Y Acuña UM Jiménez F García R Mejía M Chai H Gallucci JC Farnsworth NR Soejarto DD Carcache de Blanco EJ Kinghorn AD 《Tetrahedron》2012,68(12):2671-2678
Six new (1-6) and eight known germacranolide-type sesquiterpene lactones, along with several known phenylpropanol coumarates and methylated flavonoids, were isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. The new compounds were identified by analysis of their spectroscopic data, with the molecular structure of 3 being established by single-crystal X-ray diffraction. The absolute configurations of the sesquiterpene lactones isolated were determined from their CD and NOESY NMR spectra, together with the analysis of Mosher ester reactions. Bioassay screening results showed the majority of the sesquiterpene lactones isolated (1-13) to be highly cytotoxic toward the HT-29 human colon cancer cell line, with the most potent compound being 15-deoxygoyazensolide (10, IC(50), 0.26 μM). In addition, several of the sesquiterpene lactones exhibited NF-κB (p65) inhibitory activity. 相似文献
150.