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141.
142.
143.
The present work is an attempt to assess racemization in stepwise solid-phase peptide synthesis at elevated temperatures (SPPS-ET), a high-speed approach in which peptide elongation occurs at 55-75 °C. This attempt was based on the notion that a high propensity for this side reaction would hamper employment of this alternative approach and would dampen interest in its further development. Simple peptide models were synthesized using customized protocols for classical SPPS or SPPS-ET. Systematic analyses of the resulting crude peptides by reversed-phase HPLC, ion-exchange HPLC, capillary electrophoresis and electrospray ionization mass spectrometry revealed low diastereomeric byproduct contents. These results indicate that, from the standpoint of racemization, classical SPPS and SPPS-ET protocols were equivalent. Therefore, further studies employing SPPS-ET protocols are justified. 相似文献
144.
《Surface and interface analysis : SIA》2003,35(12):1015-1017
Material surface properties of polymers, plastics, ceramics and textiles can be modified by atmospheric or low‐pressure glow discharge plasma. The aim of the present work is to study the surface modification of biaxially oriented polypropylene (BOPP) film in order to improve its hydrophilic and wetting properties. In this article we used low‐pressure, low‐temperature oxygen plasma for the surface treatment of BOPP. Scanning electron microscopy indicates that plasma treatment causes mainly physical changes by creating microcraters and roughness on the surface and increasing surface friction. Attenuated total reflectance infrared spectra show oxygen‐containing groups such as ? OH at 3513 cm?1 and C?O at 1695 cm?1. Microscopic investigations of water droplets on BOPP (treated, untreated) show that the interfacial adhesion of treated surfaces is increased. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
145.
Aggregated aromatic molecule--cyclodextrin-precipitant complexes exhibit long-lived phosphorescence at room temperature in water after the chemical binding of oxygen. The temperature dependences of the phosphorescence lifetimes of naphthalene-h8, naphthalene-de, and phenanthrene in the aggregates were measured. For example, the phosphorescence lifetimes of naphthalene-d8 aggregated with -cyclodextrin and cyclohexane are equal to 25.1, 17.6, and 6.8 s at 77, 276, and 347 K, respectively, and that of phenanthrene aggregated with isooctane and -cyclodextrin are 3.24, 3.06, and 1.26 s at 268, 274, and 335 K, respectively. The temperature dependences of the phosphorescence lifetimes at room temperature are determined by the rate constants of the radiative and nonradiative transitions from the triplet state of an aromatic molecule.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2225–2228, September, 1996. 相似文献
146.
The first molal hydrolysis quotient, Q1.1, of Mg2+ was measured potentiometrically from 1 to 250°C at ionic strengths of 0.11, 0.31, 1.01, and 5.0 mol-kg-1 in an aqueous NaCl medium using a hydrogen-electrode, concentration cell. Only hydrolysis of the first four percent of the
magnesium in solution could be followed before precipitation of brucite, Mg(OH)2(cr), occurred. The log Q1.1 values were fitted as a function of temperature and ionic strength using four adjustable parameters. The resulting constants
are compared with the limited existing low temperature data. At infinite dilution and 25°C the following quantities are reported:
logK
1.1 = -11.68±0.05, †Hso = 70.1±1.2 kJ-mol-1, †So = 11±4 J-K-1-mol-1, and †C
p
o
= 0 J-K-1-mor-1. At each ionic strength, including the values extrapolated to infinite dilution, the heat capacity change for the hydrolysis
reaction was zero,i.e., logQ
1.1 was found to be a linear function of the reciprocal temperature in Kelvin, at least over the measured range of l-250°C. The
hydrolysis constants at infinite dilution were modeled to 550°C and two kbar pressure with a function incorporating solvent
density using published results obtained at these extreme conditions. 相似文献
147.
The technique of temperature waves to measure the complex thermophysical characteristics of materials has been proposed. The relations for the moduli and arguments of these characteristics for the case of plane temperature waves have been calculated. The temperature dependences of the moduli and arguments of complex thermophysical characteristics of polyvinylacetate (PVAc) at different frequencies and also the temperature dependences of its vibrational and configurational heat capacities have been determined. It has been shown that the vibrational heat capacity of PVAc in the region of softening grows sharply and its configurational heat capacity goes through a peak. The segmental mobility has been found to affect the heat transfer in the polymer in an ambivalent way causing both a decrease and increase of thermal conductivity.
Zusammenfassung Zur Bestimmung der komplexen thermophysischen Eigenschaften von Stoffen wurde eine Temperaturwellentechnik vorgeschlagen. Für den Fall zweidimensionaler Temperatur-wellen wurden die Verhältnisse von Moduli und Argumenten dieser Eigenschaften berechnet. Die Temperaturabhängigkeit von Moduli und Argumenten der komplexen thermophysischen Eigen-schaften von Polyvinylacetat (PVAc) bei verschiedenen Frequenzen und auch die Temperatur-abhängigkeit seiner Vibrations- und Konfigurations-Wärmekapazitäten wurden bestimmt. Es wurde gezeigt, daß die Vibrations-Wärmekapazität von PVAc im Erweichungsbereich scharf zunimmt und die Konfigurations-Wärmekapazität durch einen Peak geht. Man fand, daß die Segment-Mobilität den Wärmetransport im Polymer auf eine ambivalente Weise beeinflußt, in dem die Wärmeleit-fähigkeit entweder gesenkt oder angehoben wird.相似文献
148.
Binal N. Shah 《Thermochimica Acta》2006,443(1):78-86
Protein crystals are usually grown in multi-component aqueous solutions containing salts, buffers and other additives. To measure the X-ray diffraction data of the crystal, crystals are rapidly lowered to cryogenic temperatures. On flash cooling, ice frequently forms affecting the integrity of the sample. In order to eliminate this effect, substances called cryoprotectants are added to produce a glassy (vitrified) state rather than ice. Heretofore, the quantity of cryoprotectant needed to vitrify the sample has largely been established by trial and error. In this study, differential scanning calorimetry (DSC) was used to measure the melting (Tm), devitrification (Td) and glass transition (Tg) temperatures of solutions with a range of compositions typical of those used for growing protein crystals, with the addition of glycerol as cryoprotectant. The addition of cryoprotectant raises the Tg and lowers the Tm of bulk solution thereby decreasing the cooling rates required for vitrification of protein crystals. The theoretical Tg value was calculated using the apparent volume fraction using the Miller/Fox equation extended for multi-component systems. The experimental values of Tg were within approximately ±4% of that predicted by the model. Thus, the use of the model holds the promise of a rational method for the theoretical determination of the composition of cryoprotectant requirement of protein crystallization solutions. 相似文献
149.
Polystyrenes with different concentrations of side groups with cyano groups were prepared and complex dielectric constants were measured in the range of the glass transition temperature and the frequency range of 10–2–107 Hz.The GPC and DSC measurements showed that the molecular weight of these polystyrenes was about 10500 g/mole and the glass transition temperatures were 89.5°C for all samples.The dielectric relaxation spectra obtained for the side group polystyrene labels and also the chain-end polystyrene labels prepared before [9] were analyzed to find out the degree of coupling of the chain-end and side-group labels with the cooperative reorientation of the polymeric matrix. The analysis of the spectra was carried out using the analysis method developed by Mansour and Stoll [6].The results obtained showed that both end- and side-group labels are strongly coupled with the segmental reorientation and relax with relaxation times longer than that of the segments.The value of logf
m = (logf
m(label)) – logf
m(matrix)) was obtained from the recently designed comparison diagram suggested by Mansour and Stoll [6, 14]. The value of logf
m depends on the label length in the case of chain-end labels.It was surprising to find that the side groups relax slower than the segments by only 0.9 decades. These results obtained implied that the label relaxes through a multistep relaxation mechanism of the side and end groups and not through a diffusion mechanism of the whole chain. In addition, the effective lengths of the relaxing units were determined using the empirical equation obtained before in the case of rodlike molecules in polyisoprene [7]. 相似文献
150.
We have studied the electrocatalytic activity of RuO2-PVC film electrodes, fabricated using RuO2 powders prepared at five different temperatures, viz., 300, 400, 500, 600 and 700°C, for the oxidation of glucose in high alkaline media, 1 to 3 M NaOH. The RuO2-PVC film electrodes have been first characterized in 1 to 3 M NaOH solution by cyclic voltammetry (CV) and rotating disc electrode (RDE) techniques in a wide potential range −1,100 to 450 mV (SCE), and three redox pairs representing Ru(IV)/Ru(III), Ru(VI)/Ru(IV) and Ru(VII)/Ru(VI) transitions have been identified. The voltammetric peaks at low sweep rates have been analyzed using surface activity theory formulated for interacting electroactive adsorption sites, and interaction terms have been evaluated. The total voltammetric surface charges have been analyzed as per Trassatti’s formalism with respect to their dependence on potential sweep rate, and charges associated with less accessible and more accessible surface sites have been calculated. For glucose oxidation, the results have indicated that RuO2 (700°C)-PVC electrode shows two oxidation peaks in contrast to RuO2 (300°C)-PVC electrode. Also, RuO2 (700°C)-PVC electrode exhibits higher intrinsic electrocatalytic activity than the 300°C electrode, although the former possesses lower electrochemically active surface area. Additionally, kinetic analyses made from RDE results with reference to Michealis–Menten (MM) enzyme catalysis has shown that RuO2 (700°C) electrode possesses extended glucose-sensing range in terms of MM kinetic constant, K
M
, compared to other electrodes. Possible reasons for such differences in the behavior of the electrodes of different temperatures towards glucose oxidation are identified from studies on oxidation of glucose in solutions of different pH, oxidation of different glucose derivatives, and also from physicochemical results from BET, XRD, SEM, DTGA, XPS analysis of RuO2 powder samples. 相似文献