共查询到20条相似文献,搜索用时 171 毫秒
1.
Takiue T Murakami D Tamura T Sakamoto H Matsubara H Aratono M 《The journal of physical chemistry. B》2005,109(29):14154-14159
The interfacial tensions (gamma) of the hexane solutions of 1H,1H-perfluorononanol (FDFC9OH) and its omega-hydrogenated analogue 1H,1H,9H-perfluorononanol (HDFC9OH) against water were measured as a function of temperature and concentration under atmospheric pressure in order to know the effect of omega-dipoles on the adsorption behavior of fluorononanols. The interfacial pressure (pi) versus mean area per adsorbed molecule (A) curves consist of two discontinuous changes among three different states: the gaseous, expanded, and condensed states. The A values at given pi in the gaseous and expanded states are larger for HDFC9OH than for FDFC9OH. The changes in partial molar entropy (s1(H) - s1(O)) and energy (u1(H) - u1(O)) of adsorption were evaluated. Their values are negative, and therefore, the alcohols have a smaller entropy and energy at the interface than in the bulk solution. Furthermore, the u1(H) - u1(O) value is more negative for HDFC9OH than for FDFC9OH in the expanded state and also in the condensed film just above the expanded-condensed phase transition point. This seems to be due to the following: (1) HDFC9OH may tilt from interface normal for omega-dipoles to interact effectively with water molecules in the interfacial region and to reduce their own repulsive interaction between neighbors arranging parallel in the adsorbed film. This leads to a lower value for HDFC9OH than for FDFC9OH. (2) The contact of omega-dipoles with hexane molecules in the bulk solution is energetically unfavorable, and thus, the u1(O) value of HDFC9OH is expected to be larger than that of FDFC9OH. 相似文献
2.
Murakami D Takata Y Matsubara H Aratono M Takiue T 《The journal of physical chemistry. B》2005,109(47):22366-22370
The interfacial tension of the hexane solution of 1H,1H-perfluorononanol (FDFC9OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC9OH), against water was measured as a function of the total molality and composition of the mixture at 298.15 K under atmospheric pressure. The existence of omega-dipole in HDFC9OH makes the interfacial density larger in the gaseous and expanded states and smaller in the condensed state compared to FDFC9OH. The phase diagram of adsorption (PDA) was constructed, and the excess Gibbs energy of adsorption (gH,E) was calculated at each state in order to discuss quantitatively the miscibility of FDFC9OH and HDFC9OH in the adsorbed film. We found that the gH,E value is negative in the gaseous state, while it is positive and increases with decreasing interfacial tension in the condensed state. These results are explained mainly by the balance of two effects induced by mixing of two alcohols: (1) Reduction of repulsive interaction between omega-dipoles aligning parallel in the adsorbed film because of the increase in mean distance between HDFC9OH molecules. (2) The loss of effective dispersion interaction between hydrophobic chains due to the fact that the oblique orientation of HDFC9OH molecules at the interface is mixed with the perpendicular one of FDFC9OH. We concluded that the factor (2) is negligible compared to the factor (1) in the gaseous and expanded films and exceeds the factor (1) in the condensed film, in which molecules are closely packed. 相似文献
3.
K. Shibata T. Matsuda R. Fujimoto H. Matsubara T. Takiue M. Aratono 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):443-448
The surface tension of the aqueous solution of the binary mixture of 1H,1H-heptafluoro-1-butanol (FC4OH) and dodecyltrimethylammonium bromide (DTAB) was measured as a function of the total molality of the mixture and the composition (mole fraction in the surfactant mixture) of DTAB at 298.15 K under atmospheric pressure to examine the phase behavior in the adsorbed film. The results of the surface tension measurement were analyzed by the thermodynamic procedure proposed by us and the composition of the mixed adsorbed film in equilibrium with their bulk solution was calculated. Three different phases of the adsorbed film appeared by a subtle balance between the attractive interaction of the polar head groups and weak dispersion interaction of the hydrophobic chains. In the low-concentration regime, FC4OH molecules and DTAB molecules form a gaseous film and mix attractively in the whole composition by the long-range ion–dipole attraction between hydrophilic groups. The effect of the attractive dispersion interaction between CH and CF chains became more influential in the expanded film within a restricted composition region, where it should be noted that the interaction between CH and CF is weaker than that between CH chains or between CF chains alone. Furthermore, the adsorbed films at two specific compositions are stabilized by the stoichiometric arrangements of the molecules, which help ion–dipole attraction, in them. 相似文献
4.
Leitch JJ Collins J Friedrich AK Stimming U Dutcher JR Lipkowski J 《Langmuir : the ACS journal of surfaces and colloids》2012,28(5):2455-2464
Quantitative subtractively normalized interfacial Fourier transform infrared reflection spectroscopy (SNIFTIRS) was used to determine the conformation and orientation of sodium dodecyl sulfate (SDS) molecules adsorbed at the single crystal Au(111) surface. The SDS molecules form a hemimicellar/hemicylindrical (phase I) structure for the range of potentials between -200 ≤ E < 450 mV and condensed (phase II) film for electrode potentials ≥500 mV vs Ag/AgCl. The SNIFTIRS measurements indicate that the alkyl chains within the two adsorbed states of SDS film are in the liquid-crystalline state rather than the gel state. However, the sulfate headgroup is in an oriented state in phase I and is disordered in phase II. The newly acquired SNIFTIR spectroscopy measurements were coupled with previous electrochemical, atomic force microscopy, and neutron reflectivity data to improve the current existing models of the SDS film adsorbed on the Au(111) surface. The IR data support the existence of a hemicylindrical film for SDS molecules adsorbed at the Au(111) surface in phase I and suggest that the structure of the condensed film in phase II can be more accurately modeled by a disordered bilayer. 相似文献
5.
The interfacial tension of aqueous dodecyltrimethylammonium chloride (DTAC) solution/hexane interface has been measured as a function of pressure at concentrations around the critical micelle concentration (CMC). The derivative of the interfacial tension with respect to pressure has been observed to change abruptly at the CMC as in the case of aqueous dodecylammonium chloride (DAC) solution-hexane system studied already. The volume changes associated with the adsorption of DTAC from its monomeric and micellar states have been calculated. The results have indicated that the micelle formation of surfactant is treated like the appearance of a new macroscopic phase in the system. It has also been concluded that the micelle solubilizing hexane bears resemblance to the adsorbed film in terms of the volume. The difference in the pressure dependence of the volume of micelle formation
MW between DTAC and DAC has been attributed to a larger polar group of DTAC. The fact that the value of
MW is larger than that estimated from the conductivity data has been explained by the solubilization of hexane into the micelle. 相似文献
6.
Guennoun Z Couturier-Tamburelli I Piétri N Aycard JP 《The journal of physical chemistry. B》2005,109(8):3437-3441
Dicyanoacetylene adsorbed on amorphous ice water at 10 K presents an interaction with the dangling H site and induces a s(4) adsorption site formation due to the restructuring of the ice bulk. Warming up the sample provokes the dicyanoacetylene desorption from the H(2)O ice film, which could be due to the beginning of the ice crystallization process. The desorption activation energy measured by temperature-programmed desorption (E(d) = 42 +/- 5 kJ x mol(-1)) is in good agreement with that calculated (E(d) = 46 kJ x mol(-1)) and gives evidence of a hydrogen-bonded adsorbed state on amorphous ice films. 相似文献
7.
Takajo Y Matsuki H Kaneshina S Aratono M Yamanaka M 《Colloids and surfaces. B, Biointerfaces》2007,59(1):52-58
The miscibility and interaction of 1-hexanol (C6OH) and 1-heptanol (C7OH) with 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) in the adsorbed films and micelles were investigated by measuring the surface tension of aqueous C6OH-DHPC and aqueous C7OH-DHPC solutions. The surface density, the mean molecular area, the composition of the adsorbed film, and the excess Gibbs energy of adsorption g(H,E), were estimated. Further, the critical micelle concentration of the mixtures was determined from the surface tension versus molality curves; the micellar composition was calculated. The miscibility of the 1-alkanols and DHPC molecules in the adsorbed film and micelles was examined using the phase diagram of adsorption (PDA) and that of micellization (PDM). The PDA and the composition dependence of g(H,E) indicated the non-ideal mixing of the 1-alkanols and DHPC molecules due to the attractive interaction between the molecules in the adsorbed film, while the PDM indicated that the 1-alkanol molecules were not incorporated in the micelles within DHPC rich region. The dependence of the mean molecular area of the mixtures on the surface composition suggested that the packing property of the adsorbed film depends on the chain length of 1-alkanol: C6OH expands the DHPC adsorbed film more than C7OH. 相似文献
8.
《Colloids and surfaces. A, Physicochemical and engineering aspects》2007,292(1):36-41
The surface tension of the 1H,1H-heptafluoro-1-butanol (FC4OH)–dodecyltrimethylammonium chloride (DTAC) mixed aqueous solution was measured as a function of the total molality of the mixture and the composition of DTAC at 298.15 K under atmospheric pressure.The phase diagram of adsorption (PDA) that gives the composition relation between the aqueous solution and adsorbed film was constructed. It was suggested that the subtle balance between the attractive surfactant cation-OH dipole interaction and the weak dispersion interaction between C–H and C–F chains is crucial for the phase behavior. The phase diagram of adsorbed film (PDAF) showing the composition relation between the different state of adsorbed films demonstrated the phase behavior is significantly dependent on the degree of counter ion binding. Moreover, the possible surface structures at the azeotropes are suggested. 相似文献
9.
Cain N Van Bogaert J Gin DL Hammond SR Schwartz DK 《Langmuir : the ACS journal of surfaces and colloids》2007,23(2):482-487
The self-organization behavior of a wedge-shaped surfactant, disodium-3,4,5-tris(dodecyloxy)phenylmethylphosphonate, was studied in Langmuir monolayers (at the air-water interface), Langmuir-Blodgett (LB) monolayers and multilayers, and films adsorbed spontaneously from isooctane solution onto a mica substrate (self-assembled films). This compound forms an inverted hexagonal lyotropic liquid crystal phase in the bulk and in thick adsorbed films. Surface pressure isotherm and Brewster angle microscope (BAM) studies of Langmuir monolayers revealed three phases: gas (G), liquid expanded (LE), and liquid condensed (LC). The surface pressure-temperature phase diagram was determined in detail; a triple point was found at approximately 10 degrees C. Atomic force microscope (AFM) images of LB monolayers transferred from various regions of the phase diagram were consistent with the BAM images and indicated that the LE regions are approximately 0.5 nm thinner than the LC regions. AFM images were also obtained of self-assembled films after various adsorption times. For short adsorption times, when monolayer self-assembly was incomplete, the film topography indicated the coexistence of two distinct monolayer phases. The height difference between these two phases was again 0.5 nm, suggesting a correspondence with the LE/LC coexistence observed in the Langmuir monolayers. For longer immersion times, adsorbed multilayers assembled into highly organized periodic arrays of inverse cylindrical micelles. Similar periodic structures, with the same repeat distance of 4.5 nm, were also observed in three-layer LB films. However, the regions of organized periodic structure were much smaller and more poorly correlated in the LB multilayers than in the films adsorbed from solution. Collectively, these observations indicate a high degree of similarity between the molecular organization in Langmuir layers/LB films and adsorbed self-assembled films. In both cases, monolayers progress through an LE phase, into LE/LC coexistence, and finally into LC phase as surface density increases. Following the deposition of an additional bilayer, the film reorganizes to form an array of inverted cylindrical micelles. 相似文献
10.
It was possible to determine the maximum loading of salicylic acid adsorbed onto γ-alumina and kaolinite clay after exposure to salicylic acid dissolved in hexane by examination using diffuse reflectance infrared Fourier transform infrared spectroscopy (DRIFTS). The maximum surface loading of salicylic acid (which resisted washing with fresh hexane) on γ-alumina was four times that observed using water as a solvent (approximately 3.0 compared with 0.7 molecules/nm2). Washing the sample with water removed the organic which was in excess to the maximum level observed for samples prepared with aqueous solution. The spectra of samples prepared with a loading up to the maximum observed with aqueous solution showed no significant differences to those of samples where the organic had been adsorbed from hexane (with the same surface loading). New peaks were observed for loadings greater than 1 molecules/nm2, but the salicylic acid was still present as carboxylate (with no clear evidence for the carbonyl group). Salicylic acid adsorbed more readily to the surface of kaolinite from solution in hexane than from aqueous solution (up to maximum average loading of 2 molecules/nm2). Washing the samples with water removed the organic to a loading in the region of 0.2 molecules/nm2, independent of the initial loading. Salicylic acid was adsorbed onto kaolinite as the carboxylate. The findings indicate that uptake is mediated by a surface water layer even in the absence of bulk water. 相似文献
11.
F. Th. Hesselink 《Journal of colloid and interface science》1977,60(3):448-466
A theory has been developed for the adsorption of polyelectrolytes on charged interfaces from an aqueous salt solution. This adsorption is determined by the electrical charge density of the polyelectrolyte, the adsorption energy, the salt concentration, the molecular weight, solubility, flexibility, and concentration of polymer. The theory relates these parameters to the properties of the adsorbed polymer layer, i.e., the amount of polymer adsorbed, the fraction of the adsorbent interface covered, the fraction of the segments actually adsorbed on the interface versus the fraction of the segments in the dangling loops, the final surface charge density, and the thickness of the adsorbed layer. As polyelectrolyte adsorption should resemble nonionic polymer adsorption at high ionic strength of the solution or low charge density on the polymer, this work is an extension of the nonionic polymer adsorption theory to polyelectrolyte adsorption. The following effects are taken into account: (a) the conformational change upon adsorption of a coil in solution into a sequence of adsorbed trains interconnected by loops dangling in solution; (b) the interactions of the adsorbed trains with the interface and with each other; (c) the interaction of the dangling loops with the solvent; (d) the change in surface charge density of the adsorbent due to adsorption of charged trains and the accompanying changes in the electrical double layer which contains “small” ions as well as charged loops; (e) the (induced) dipole interaction of the adsorbed trains with the charged adsorbent interface. The theory is worked out for low potentials (Debye—Hückel approximation); in Appendix B an outline of a more complete treatment is given. The predicted adsorption isotherms have the experimentally observed high-affinity character. A relation between the adsorption energy, the surface charge density on the adsorbent, the degree of dissociation of the polymer, and the salt concentration predicts the conditions under which no adsorption will occur. For adsorbent and polymer carrying the same type of charge (both positive or both negative) the adsorption is predicted to decrease with increased charge density on polymer or adsorbent and to increase with salt concentration. If adsorbent and polymer carry different type charges, the adsorption as a function of the degree of dissociation, α, goes through a maximum at a relatively low value of α and, depending on the adsorption energy, an increase in the salt concentration can then increase or decrease the adsorption. At finite polymer concentration in solution the number of adsorbed segments and the fraction of the interface covered practically do not change with an increase in polymer concentration, whereas the total number of polymer molecules adsorbed increases slightly, as does the average fraction of segments in loops. The experimental results for polyelectrolyte adsorption have been reviewed in general and, as far as data are available, the predictions of the theory seem to follow the experimentally observed trends quite closely, except for the thickness of the adsorbed layer. This thickness is systematically overestimated by the theory and two reasons for this are given. The theoretical model implies a not too low ionic strength of the solution. Extrapolation of results to solutions of very low ionic strength is not warranted. 相似文献
12.
Pancera SM Gliemann H Schimmel T Petri DF 《The journal of physical chemistry. B》2006,110(6):2674-2680
The combination of in situ ellipsometry with atomic force microscopy in the liquid for the study of adsorption of creatine phosphokinase (CPK) onto silicon wafers was shown for the first time. The thickness, adsorbed amount, and topographic information of the adsorbed CPK layers were obtained under different pH conditions. The thickness values of adsorbed CPK layer determined by both techniques were in excellent agreement. At pH 4, CPK monomers present in solution adsorb, forming a very thin (approximately 0.8 nm) layer, indicating CPK unfolding. Upon increasing the pH to 6.8, the adsorbed layer is composed of a mixture of CPK dimers (native structure) and intermediates, increasing the film thickness (approximately 2.4 nm). At pH 9, CPK dimers form monolayers with the highest thickness (approximately 4.0 nm). The nature of interactions between CPK and Si wafers associated with the hydration force seems to control the degree of CPK unfolding upon adsorbing. The enzymatic activity of free CPK and of adsorbed CPK at pH 4, pH 6.8, and pH 9 was measured as a function of pH. In comparison to free CPK in solution, adsorbed CPK presented a shift of the optimal pH from 6.8 toward alkaline pH. 相似文献
13.
Fink K 《Physical chemistry chemical physics : PCCP》2006,8(13):1482-1489
Oxygen vacancies at the polar O terminated (0001) surface of ZnO are of particular interest, because they are discussed as active sites in the methanol synthesis. In general, the polar ZnO surfaces are stabilized by OH groups, therefore O vacancies can be generated by removing either O atoms or OH or H2O groups from the surface. These defects differ in the number of electrons in the vacancy and the number of OH groups in the neighborhood. In the present study, the electronic structure and the adsorption properties of four different types of oxygen vacancies have been investigated by means of embedded cluster calculations. We performed ab initio calculations on F+ like surface excitations for the different defect types and found that the transition energies are above the optical band-gap, while F+ centers in bulk ZnO show a characteristic optical excitation at 3.19 eV. Furthermore, we studied the adsorption of CO2 and CO at the different defect sites by DFT calculations. We found that CO2 dissociates at electron rich vacancies into CO and an O atom which remains in the vacancy. At the OH vacancy which contains an unpaired electron CO2 adsorbed in the form of CO2-, while it adsorbed as a linear neutral molecule at the H2O defect. CO adsorbed preferentially at the H2O defect and the OH defect, both with a binding energy of 0.3 eV. 相似文献
14.
The adsorption of berberine and canadine was measured by a.c. polarography. For berberine three different superficial structures were observed: the ions lying flat, the mixed layer of flat and perpendicular ions and the condensed film of perpendicular ions which incorporates anions of the supporting electrolyte. The boundaries between these structures are diffuse. The condensation is an instantaneous nucleation and two-dimensional film growth process. The adsorption of canadine is similar, but its condensed film is very stable and the exchange rate between the adsorbed canadine and the dissolved berberinium ions is very low. Different structures of the adsorbed berberine result in different faradaic square-wave responses. 相似文献
15.
Richard T Mercury L Poulet F d'Hendecourt L 《Journal of colloid and interface science》2006,304(1):125-136
We present experimental data acquired by diffuse reflectance infrared spectroscopy in the mid-IR (4000-400 cm(-1)), on micrometric-sized mineral grain powders. The spectral evolution of the OH-stretching band is followed when the adsorbed water film is thinned under dry conditions, from high to low hydration states. The IR bands are found to be characteristic of the degree of adsorption/confinement of the liquid water. The OH-stretching band is shifted toward shorter wavenumbers than in bulk water, showing that a significant portion of adsorbed water has a higher intermolecular bonding energy. Complementary treatment of the kinetics of water desorption, varying with the surface forces in the water film, confirms the relationships of these bands with the constrained water state. We distinguish different water types obeying liquid-liquid interactions (free and capillary water) or dominated by solid-water interactions (confined and adsorbed water). Part of this study is devoted to mesoporous silica MCM-41, of interest due to the restricted geometries of its mesopores (4.7 nm) favouring the confined water state. The methodology allows us to distinguish bulk and adsorbed/confined water, using spectral analysis coupled with an understanding of the dynamic behaviour of the desorption process. 相似文献
16.
Engelhardt K Rumpel A Walter J Dombrowski J Kulozik U Braunschweig B Peukert W 《Langmuir : the ACS journal of surfaces and colloids》2012,28(20):7780-7787
The surface chemistry of ions, water molecules, and proteins as well as their ability to form stable networks in foams can influence and control macroscopic properties such as taste and texture of dairy products considerably. Despite the significant relevance of protein adsorption at liquid interfaces, a molecular level understanding on the arrangement of proteins at interfaces and their interactions has been elusive. Therefore, we have addressed the adsorption of the model protein bovine serum albumin (BSA) at the air-water interface with vibrational sum-frequency generation (SFG) and ellipsometry. SFG provides specific information on the composition and average orientation of molecules at interfaces, while complementary information on the thickness of the adsorbed layer can be obtained with ellipsometry. Adsorption of charged BSA proteins at the water surface leads to an electrified interface, pH dependent charging, and electric field-induced polar ordering of interfacial H(2)O and BSA. Varying the bulk pH of protein solutions changes the intensities of the protein related vibrational bands substantially, while dramatic changes in vibrational bands of interfacial H(2)O are simultaneously observed. These observations have allowed us to determine the isoelectric point of BSA directly at the electrolyte-air interface for the first time. BSA covered air-water interfaces with a pH near the isoelectric point form an amorphous network of possibly agglomerated BSA proteins. Finally, we provide a direct correlation of the molecular structure of BSA interfaces with foam stability and new information on the link between microscopic properties of BSA at water surfaces and macroscopic properties such as the stability of protein foams. 相似文献
17.
Benoit Coasne Anne Galarneau Francesco Di Renzo Roland J. M. Pellenq 《Adsorption》2008,14(2-3):215-221
This paper reports Monte Carlo simulations of the adsorption or intrusion in cylindrical silica nanopores. All the pores are
opened at both ends towards an external bulk reservoir, so that they mimic real materials for which the confined fluid is
always in contact with the external phase. This realistic model allows us to discuss the nature of the filling and emptying
mechanisms. The adsorption corresponds to the metastable nucleation of the liquid phase, starting from a partially filled
pore (a molecular thick film adsorbed at the pore surface). On the other hand, the desorption occurs through the displacement
at equilibrium of a gas/liquid hemispherical interface (concave meniscus) along the pore axis. The intrusion of the non-wetting
fluid proceeds through the invasion in the pore of the liquid/gas interface (convex meniscus), while the extrusion consists
of the nucleation of the gas phase within the pore. In the case of adsorption, our simulation data are used to discuss the
validity of the modified Kelvin equation (which is corrected for both the film adsorbed at the pore surface and the curvature
effect on the gas/liquid surface tension). 相似文献
18.
Abraham RJ Byrne JJ Griffiths L Koniotou R 《Magnetic resonance in chemistry : MRC》2005,43(8):611-624
The (1)H NMR spectra of a number of alcohols, diols and inositols are reported and assigned in CDCl(3), D(2)O and DMSO-d(6) (henceforth DMSO) solutions. These data were used to investigate the effects of the OH group on the (1)H chemical shifts in these molecules and also the effect of changing the solvent. Inspection of the (1)H chemical shifts of those alcohols which were soluble in both CDCl(3) and D(2)O shows that there is no difference in the chemical shifts in the two solvents, provided that the molecules exist in the same conformation in the two solvents. In contrast, DMSO gives rise to significant and specific solvation shifts. The (1)H chemical shifts of these compounds in the three solvents were analysed using the CHARGE model. This model incorporates the electric field, magnetic anisotropy and steric effects of the functional group for long-range protons together with functions for the calculation of the two- and three-bond effects. The long-range effect of the OH group was quantitatively explained without the inclusion of either the C--O bond anisotropy or the C--OH electric field. Differential beta and gamma effects for the 1,2-diol group needed to be included to obtain accurate chemical shift predictions. For DMSO solution the differential solvent shifts were calculated in CHARGE on the basis of a similar model, incorporating two-bond, three-bond and long-range effects. The analyses of the (1)H spectra of the inositols and their derivatives in D(2)O and DMSO solution also gave the ring (1)H,(1)H coupling constants and for DMSO solution the CH--OH couplings and OH chemical shifts. The (1)H,(1)H coupling constants were calculated in the CHARGE program by an extension of the cos(2)phi equation to include the orientation effects of electronegative atoms and the CH--OH couplings by a simple cos(2)phi equation. Comparison of the observed and calculated couplings confirmed the proposed conformations of myo-inositol, chiro-inositol, quebrachitol and allo-inositol. The OH chemical shifts were also calculated in the CHARGE program. Comparison of the observed and calculated OH chemical shifts and CH.OH couplings suggested the existence of intramolecular hydrogen bonding in a myo-inositol derivative. 相似文献
19.
Perriman AW Henderson MJ Evenhuis CR McGillivray DJ White JW 《The journal of physical chemistry. B》2008,112(31):9532-9539
We report observations of the changes in the surface structure of lysozyme adsorbed at the air-water interface produced by the chemical denaturant guanidinium chloride. A primary result is the durability of the adsorbed surface layer to denaturation, as compared to the molecule in the bulk solution. Data on the surface film were obtained from X-ray and neutron reflectivity measurements and modeled simultaneously. The behavior of lysozyme in G.HCl solutions was determined by small-angle X-ray scattering. For the air-water interface, determination of the adsorbed protein layer dimensions shows that at low to moderate denaturant concentrations (up to 2 mol L(-1)), there is no significant distortion of the protein's tertiary structure at the interface, as changes in the orientation of the protein are sufficient to model data. At higher denaturant concentrations, time-dependent multilayer formation occurred, indicating molecular aggregation at the surface. Methodologies to predict the protein orientation at the interface, based on amino acid residues' surface affinities and charge, were critiqued and validated against our experimental data. 相似文献
20.
SHANG Yan-mei LI Jing SONG Zhi-guang LI Ye-zhi HUANG Hua-min 《高等学校化学研究》2007,23(4):430-432
A series of esters of R-tetrahydrothiazo-2-thione-4-carboxylic acid[R-TTCA] was synthesized by direct esterification of R-TTCA with alcohols(CH3OH,C2H5OH,n-C3H7OH,i-C3H7OH,n-C4H9OH,sec-C4H9OH)in the presence of TiCl4 as the catalyst at room temperature without using any other solvent or dehydrant in high yields,91.6%-99.1% for primary alcohols and 55%- 80% for secondary alcohols.The catalyst has a strong chemoselective activity for the esterification of primary alcohols with R-TTCA in the presence of secondary alcohols.Owing to high yield,high chemoselectivity,and mild conditions used,this is an efficient method for the esterification of primary alcohols with R-TTCA. 相似文献