An accurate estimation of pKa values in methanol-water binary mixtures is very important for several separation techniques such as liquid chromatography and capillary electrophoresis that use these solvent mixtures. In this study, the pKa values of 11 polyphenolic acids have been determined in methanol-water binary mixtures (10%, 20% and 30% (v/v)) by potentiometry, liquid chromatography (LC) and LC-DAD methodology.The results show a similar trend for the pKa values of all the studied compounds, as they increase with increasing concentration of organic modifier, which allows a linear relationship between pKa values and mole fraction of methanol to be obtained. The pKa values obtained in aqueous medium have been compared with those given in the literature, and also with the values predicted by the SPARC on-line pKa calculator. The data obtained have been used to test the feasibility of an estimation of dissociation constants in a methanol-water medium from the relationship between pKa values and the organic cosolvent fraction in the mixtures. 相似文献
The structural study of two (C30H48O2) pentacyclic triterpene (PCTT) isomers is presented. These terpenes, known as 30-hydroxy-lup-20(29)-en-3-one (1) and (11α)-11-hydroxy-lup-20(29)-en-3-one (2), were isolated from Maytenus imbricata Mart. Ex Reissek (Celastraceae). The molecular structure of 1 and 2 differs in the position of the hydroxyl group. Both compounds crystallize in non-centrosymmetric space groups with two molecules in the asymmetric unit. The crystal structure of 1 shows a triclinic P1 space group (a = 9.5518(1) ?, b = 9.7083(1) ?, c = 14.4696(2) ?, α = 93.832(1)°, β = 102.833(1)°, and γ = 103.307(1)°), while compound 2 crystallizes in a monoclinic P21 one (a = 13.4439(16) ?, b = 14.4463(14) ?, c = 13.5224(9) ? and β = 99.703(8)°). The two molecules independent by symmetry of 1 differ slightly due to the presence of static disorder in oxygen atoms. In addition, the intermolecular geometries of 1 and 2 were analysed, and in each isomer the crystal packing is stabilized by O-H…O intermolecular hydrogen bonds and van der Waals forces. 相似文献
A simple synthesis of 3-iodothiophenes was demonstrated using a wide range of (Z)-thioenynes. The key step in the iodocyclofunctionalization was the selective reduction of the triple bond in (Z)-thioenynes by the addition of iodine as an electrophilic agent. The 3-iodothiophenes were obtained in good to excellent yields of 61–92%. The 3-iodothiophenes were used as substrates in Sonogashira cross-coupling reactions to obtain thiophene acetylenes. 相似文献
The environmental impacts associated with the exploitation and transformation of fossil resources aggravate the planet's situation in terms of climate change. Due to this, this paper studies an alternative use of mineral coal as a precursor to obtaining new materials with different properties to the starting coals. The thermal degradation of two Colombian semi-anthracites is analyzed through the thermogravimetry (TG) technique coupled to a Fourier transform infrared spectroscopy (FTIR) equipment from room temperature (25 °C) to 900 °C, at a heating rate of 10 K min?1 in an inert atmosphere. The catalytic effect of the addition of silicon to these samples before being subjected to a carbonization process is evaluated during this process. The results indicated that the primary reaction occurs in the temperature range between 400 and 680 °C, where the highest mass loss rate was observed. At the end of the heating process, the TG profile of the samples with silicon addition showed losses between 14.33 and 18.82% in mass, these values being slightly higher compared to the starting and demineralized samples. The release of water, light gases such as CO2, CH4, and species such as toluene, phenol and formic acid was identified in most of the samples. The presence of silica seems to favor the release of all these species, being more evident in one of the semi-anthracites studied. According to the results obtained, it is proved that the presence of silicon in samples subjected to carbonization processes has a catalytic effect that improves some characteristics of the new materials obtained, thus contributing to the use of carbon to get new materials.
Journal of Solid State Electrochemistry - Polyaniline was electrosynthesized using three voltammetric cycles on carbon fiber felts annealed at 1400, 1600, 2000, and 2300 K. Felts and... 相似文献
Most of the pharmaceutical products are formulated as solid dosage form, which may present drug–excipient interactions that lead to changes in the chemical nature of the drug, such as solubility and bioavailability and may compromise its safety and effectiveness. Differential scanning calorimetry (DSC) is a widely used method for the rapid evaluation of the drug-excipient compatibility and the stability of the mixture formed; however, there is no consensus on the preparation methods of the drug–excipient mixtures. The aim of this study was to investigate the influence of the mixing method on the drug–excipient compatibility studies by means of DSC analysis, using tenofovir disoproxil fumarate as a drug model. Statistical analysis revealed significant differences in the heat of fusion of the drug in the mixtures prepared by several mixing methods. Vortex Mixer with a Pop-Off Cup used for 3 min proved to be very satisfactory for these studies. A polymorphic transition was observed in the mixture prepared with the mortar and pestle. Therefore, this method should be avoided since it may induce errors in the interpretation of DSC results. In this way, the mixing method used to prepare a mixture for studies of interactions between the API and the excipients in a pharmaceutical formulation has a great influence on the results and it must be chosen carefully. 相似文献
In 2010 we presented an update of the nuclear quadrupole moments (Q) for the Cd and Zn isotopes, based essentially on straightforward density functional (DF) calculations (H. Haas and J.G. Correia, Hyperfine Interact 198, 133–137 (2010)). It has been apparent for some years that the standard DF procedure obviously fails, however, to reproduce the known electric-field gradient (EFG) for various systems, typical cases being Cu2O, As and Sb, and the solid halogens. Recently a cure for this deficiency has been found in the hybrid DF technique. This method is now applied to solid Cd and Zn, and the resultant quadrupole moments are about 15 % smaller than in our earlier report. Also nuclear systematics, using the recently revised values of Q for the long-lived 11/2 isomers in111Cd to129Cd, together with earlier PAD data for107,109Cd, leads to the same conclusion. In addition, EFG calculations for the cadmium dimethyl molecule further support the new values: Q(111Cd, 5/2+) = .683(20) b, Q(67Zn, gs) = .132(5) b. This implies, that the value for the atomic EFG in the \(^{3}\textit {P}_{1}\) state of Zn must be revised, as it has been for Cd. 相似文献
Wireless Networks - Since the introduction of the original IEEE 802.11 medium access mechanism, the definition of the multicast access mechanism has been the subject of numerous amendments and... 相似文献
Different matrices and sample-matrix preparation procedures have been tested in order to study their influence on the matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra of intact glycoproteins, which present different degrees of glycosylation (human transferrin; bovine fetuin; bovine alpha(1)-acid-glycoprotein; recombinant human erythropoietin; and the novel erythropoiesis stimulating protein). Using sinapinic acid (SA) and the fast evaporation method, the studied glycoproteins became susceptible to fragmentation at any laser intensity, suggesting that this 'hot' matrix is unsuitable for a reliable molecular mass determination of glycosylated compounds. In contrast, 2,5-dihydroxybenzoic acid (DHB) and 6-aza-2-thiothymine (ATT), with an adequate sample-matrix preparation, provided improved results. Samples containing DHB after crystallization by vacuum drying demonstrated the best performance because the labile functional groups from the glycoforms were apparently fragmented to a lower extent. The average molecular masses obtained using this methodology were in all cases a better estimation than those values reported in the literature. The results were reproducible, and sensitivity was similar to that obtained with SA and the fast evaporation method. These excellent results suggest that this MALDI-TOF-MS methodology could be useful for an improved determination of the average molecular mass values of microheterogeneous compounds such as glycoproteins, glycosylated compounds or, in general, molecular mass values of molecules with similar labile functional groups. 相似文献