Capillary viscometry was used to determine the kinematic viscosity of the binary systems composed of N-methylpyrrolidone + monoethanolamine and N-methylpyrrolidone + diethanolamine throughout the concentration range, at eight different temperatures in the range 303.15–373.15 K. Pure component values of viscosity were also determined in the temperature range 303.15–423.15 K. Using a rolling ball viscometer the absolute viscosity was obtained for the binary systems composed of tetramethylene sulfone (sulfolane) + monoethanolamine and tetramethylene sulfone + diethanolamine, throughout the concentration range, at three different temperatures in the range 303.15–373.15 K. Density results were obtained using a vibrating-tube densimeter for the four pure components and the four binary systems studied, in the same temperature range and the whole concentration range for the binary systems as the viscosity measurements.
The experimental viscosity results for the four pure solvents cover a broader temperature range than previously reported by other workers. The experimental results of viscosity for both pure and binary systems show a decrease with increasing temperature as expected. In the case of the binary systems the change of viscosity with concentration for the two sets of mixtures with N-methylpyrrolidone is very large in the range of 303.15–353.15 K, whereas it is small in the range 363.15–373.15 K. The observed behaviour of the change of viscosity with concentration for sulfolane with monoethanolamine is different from that shown by sulfolane with diethanolamine, at 303.15 and 323.15 K; the first system shows a minimum viscosity point in the sulfolane-rich region whereas at 373.15 K it shows values of viscosity greater than that of the pure components in the whole range of concentration; and the second system shows large variations of viscosity at low sulfolane concentration, at 303.15 and 323.15 K; whereas at 373.15 K the viscosity values change smoothly between those for the two pure components.
From the density results, molar excess volumes were derived, which were correlated using the Redlich–Kister equation; the final expression includes the functionality with both concentration and temperature. 相似文献
The development of gate-like systems able to perform certain programmed functions is an interesting way of taking chemistry to the frontiers of nanoscience. In relation to this field, we report a complete study of the behavior of a pH-driven and anion-controlled nano-supramolecular gate-like ensemble obtained by anchoring suitable polyamines on the pore outlets of mesoporous materials of the type MCM-41 (solid N3-S). The release of an entrapped dye (Ru(bipy)3(2+)) from the pore voids into the bulk solution allows us to study the gating effect. A pH-driven open/close mechanism was observed that arises from the hydrogen-bonding interaction between amines at neutral pH (open gate) and Coulombic repulsions at acidic pH between closely located polyammoniums at the pore openings (closed gate). Molecular dynamics simulations using force field methods have been carried out to explain the pH-driven open/close mechanism. For this purpose, a mesoporous silica structure was constructed, taking as base the (111) plane of the beta-crystoballite structure on which large hexagonal nanopores and anchored polyamines were included. From these calculations, it was observed how completely unprotonated amines display poor coverage of the pore (fully open gate), whereas completely protonated amines (simulating a pH 2 or lower) result in a clear reduction of the pore aperture, in agreement with the experimental results. In additional to the pH-driven protocol, opening/closing of the gate-like ensemble can also be modulated via an anion-controlled mechanism. This study was carried out by monitoring the dye released from the pore voids of the N3-S solid at a certain pH in the presence of a range of anions with different structural dimensions and charges, including chloride, sulfate, phosphate, and ATP (C(anion) = 1 x 10(-2) mol dm(-3)). The choice of a certain anionic guest results in a different gate-like ensemble behavior, ranging from basically no action (chloride) to complete (ATP) or partial pore blockage, depending on the pH (sulfate and phosphate). The remarkable anion-controllable response of the gate-like ensemble can be explained in terms of anion complex formation with the tethered polyamines. These experimental studies are also in agreement with computational simulations with fluoride, chloride, iodide, and dihydrogen phosphate anions. In the model, larger anions push the tethered polyamines toward the pore openings more efficiently, and therefore the pore aperture decreases. The studies also show that, for anions showing a strong tendency to form hydrogen-bonding networks (e.g., phosphate), complete pore blockage was observed at acidic pH. Finally, selectivity patterns have been discussed in terms of kinetic rates of the liberation of the Ru(bipy)3(2+) dye from the amine-functionalized dye-containing material N3-S. 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
Thiocoraline is a potent antitumor agent isolated from the marine organism Micromonospora sp. This symmetric bicyclic depsipeptide binds the minor groove of DNA. Here we report two solid-phase strategies for the syntheses of azathiocoraline and its analogues. The thioester linkage was replaced by an amide bond to improve the compound's pharmacokinetic properties. The first strategy is based on a convergent (4+4) approach, whilst the second is a stepwise synthesis, cyclizations in both approaches occurring on the solid support. These two strategies were designed to overcome problems caused by the presence of consecutive noncommercial N-methyl amino acids, to avoid epimerization during cyclization and/or fragment condensation, and to form the disulfide bridge under solid-phase conditions. The heterocyclic moiety was added in the last step of the synthesis to assist the preparation of libraries of new compounds with potential therapeutic applications. 相似文献
Capillary electrophoresis electrospray–mass spectrometry was used to detect and characterize the great variety of O- and N-glycopeptide glycoforms of recombinant human erythropoietin (rhEPO) using an orthogonal accelerating time-of-flight mass spectrometer to obtain their exact molecular masses (CE–TOF-MS). rhEPO was digested with trypsin and Glu-C and analyzed by CE–TOF-MS to detect O126, N83, N24–N38 and N24 and N38 glycopeptide glycoforms, respectively. Neuraminidase was first used to enhance the detection of the glycopeptides and detect all possible glycoforms contained in each glycosylation site. O126 and N83 glycopeptides were extensively characterized. Twelve sialoforms corresponding to 5 different glycoforms were detected in N83, and for the first time, a sulfated sialoform of this glycopeptide was also detected. In the case of O126, different sialoforms with different types of sialic acids (Neu5Gc and Neu5Ac) were detected and an estimation of the relative percentage of Neu5Gc versus Neu5Ac was also carried out for this glycopeptide. N24 and N38 glycosylation sites were also characterized by CE–TOF-MS after Glu-C digestion and these results permitted to rule out some glycan combinations for N24–N38 glycopeptide glycoforms. This study provided a reliable glycopeptide map of rhEPO and may be regarded as an excellent starting point to analyze rhEPO glycopeptides in biological fluids and detect the use of this hormone in sports. 相似文献
A (k;r)-arc
$\cal K$ is a set of k points of a projective plane PG(2, q) such that some r, but no
r +1 of them, are collinear. The maximum size of a
(k; r)-arc in PG(2,
q) is denoted by mr (2, q). In this paper a (35; 4)-arc, seven (48; 5)-arcs, a (63; 6)-arc and two (117; 10)-arcs in PG(2, 13) are given. Some were found by means of computer search, whereas the example of a (63; 6)-arc was found by adding points to those of a sextic curve $\cal C$ that was not complete as a (54; 6)-arc. All these arcs are new and improve the lower bounds for mr (2, 13) given in [10, Table 5.4]. The last section concerns the nonexistence of (40; 4)-arcs in PG(2, 13). 相似文献
Adsorption of hydrogen on the ordered FePd face centered tetragonal alloy is investigated using a tight binding theoretical method. The changes in the electronic structure and bonding in the (100), (110) and (111) surfaces are analyzed. A simplified model for H diffusion to the bulk is also developed. The H-surface bond is achieved at the expense of the metal-metal bond being the Pd-Pd the more affected in the (100) and (110) cases. 相似文献
Summary The potential use of the activating effect of Pb(II) on the Mn(II)-catalysed oxidation of Tiron by hydrogen peroxide in the presence of 1,10-phenanthroline for the simultaneous determination of the two metals was investigated. The results obtained allowed the development of a new kinetic photometric method for the simultaneous determination of Pb(II) and Mn(II). The catalysed reaction was monitored by the initial rate method, which was applied to absorbance-time curves. Different Mn(II) concentrations were used to construct calibration graphs by plotting the slopes of the photometric curves obtained against the Mn(II) concentration at each Pb(II) concentration assayed. A new calibration graph was obtained in terms of the Pb(II) concentration from the slopes of such graphs. By applying the standard-addition method to the sample to be assayed a third graph was obtained, the slope and intercept of which provided the analytical concentration of Pb(II) and Mn(II), respectively. The optimized values of the different variables involved were used to determine Mn(II) and Pb(II) over the concentration ranges 1–5 and 200–800 ng/ml, respectively. 相似文献
Summary A new method for the simultaneous kinetic thermometric determination of V(V) and W(VI) traces based on the inhibitory effect of the latter ion on the catalytic action of the former on the oxidation of thiosulphate ion by hydrogen peroxide was developed. A universal mathematical model for the kinetics of the process which includes the catalytic and inhibitory effects of the species involved and relies on the standard-addition and Newton-Gauss methods facilitates the determination. The applicability ranges of the proposed method are 0.1–0.8 ppm V(V) and 1–14 ppm W(VI). The method is subject to few interferences, of which those from Fe(III) and Mo(VI), which also catalyse the analytical reaction, are the most serious. 相似文献