首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 32 毫秒
1.
The thermodenaturation behavior of Bacillus subtilis α‐amylase on some chromatographic media was studied by determining their adsorption parameters with frontal analysis. The experimental results show that on a RP‐C18 reversed‐phase medium, a Chelating Sepharose Fast‐Flow chelated by Zn2+ affinity medium and a WCX‐1 cation‐exchange medium, a stable conformation of α‐amylase molecule separately exists below or over 30 °C; while on a PEG‐400 hydrophobic medium and a modified PEG‐400 medium, a stable conformation of α‐amylase molecule separately exists below 40 and 30 °C, and when the experimental temperatures are separately over 40 and 30 °C, a drastically conformational change of α‐amylase molecules can continuously take place. And by combining the intrinsic fluorescence emission spectrum and thermal inactivation profile of α‐amylase in free solution and on the PEG‐400 and modified PEG‐400 hydrophobic media, it can be concluded that in liquid chromatographic procedure, chromatographic media can induce the conformational change of α‐amylase molecules and promote their thermodenaturation; and in hydrophobic interaction chromatography, the higher the hydrophobicity of chromatographic medium, the lower the conformational change temperature of α‐amylase molecules on the chromatographic medium.  相似文献   

2.
通过测定不同温度范围的热力学平衡常数、焓变、熵变、自由能变和补偿温度,研究了枯草杆菌α-淀粉酶在几种色谱介质上的热力学和超热力学。结果表明,在RP-C18反相介质、Zn2+螯合的Sepharose fast-flow亲和介质和WCX-1阳离子交换介质上,当温度分别在13-30和30-50℃范围时,它们的lnKSL分别随绝对温度的倒数线性变化;而在PEG-400和修饰的PEG-400疏水色谱介质上,当温度分别在13-40和13-30℃范围时,它们的lnKSL分别随绝对温度的倒数线性减小,但当温度分别高于40℃和30℃时,它们则随绝对温度的倒数剧烈减小。通过研究不同温度范围的焓变、熵变、自由能变和α-淀粉酶构象变化之间的关系,发现在RP-C18反相和Zn2+螯合的Sepharose fast-flow亲和介质上在30- 50 ℃温度范围内,在WCX-1阳离子交换介质上在13-30 ℃温度范围内,α-淀粉酶的吸附过程由焓变和熵变共同所支配,而在Zn2+螯合的Sepharose fast-flow亲和介质上在13- 30 ℃温度范围内,在WCX-1阳离子交换介质上在30-50 ℃温度范围和在PEG-400 和修饰的PEG-400疏水色谱介质上在13-65 ℃温度范围时,α-淀粉酶的吸附过程仅仅由熵变所控制。最后,通过α-淀粉酶在这些色谱体系中的补偿温度进一步发现,它们的焓变仅仅只能通过它们构象变化所引起的熵变所补偿。  相似文献   

3.
Adsorption of p-Cresol and p-Nitrophenol by untreated activated carbon in single and multisolute solutions was carried out at 301 K and at controlled pH conditions. In acidic conditions, well below the pK a of both solutes, it was observed that the adsorbate solubility and the electron density of aromatic rings influenced the extent of adsorption by affecting the extent of London dispersion forces. The fitted parameters obtained from single-solute Langmuir equation show that Q max and the adsorption affinity of carbon for the compound with low pK a decrease more significantly. In higher solution pH conditions, on the other hand, it was found that electrostatic forces played a significant role on the extent of adsorption. The presence of another compound decreases Q max and the adsorption affinity of carbon for the principal compound. The effect of pH, on the carbon surface and on the solute molecules, must be considered. Adsorption of the solute at higher pH values was found to be dependent on the concentration of anionic form of the solute. The isotherm data were fitted to the Langmuir isotherm equation for both single and double solute solutions.  相似文献   

4.
Highly ordered mesoporous three‐dimensional Ia3d silica (KIT‐6) with different pore diameters has been synthesized by using pluronic P123 as surfactant template and n‐butanol as cosolvent at different synthesis temperatures in a highly acidic medium. The materials were characterized by XRD and N2 adsorption. The synthesis temperature plays a significant role in controlling the pore diameter, surface area, and pore volume of the materials. The material prepared at 150 °C, KIT‐6‐150, has a large pore diameter (11.3 nm) and a high specific pore volume (1.53 cm3 g?1). We also demonstrate immobilization of lysozyme, which is a stable and hard protein, on KIT‐6 materials with different pore diameters. The amount of lysozyme adsorbed on large‐pore KIT‐6 is extremely large (57.2 μmol g?1) and is much higher than that observed for mesoporous silicas MCM‐41, SBA‐15, and KIT‐5, mesoporous carbons, and carbon nanocages. The effect of various parameters such as buffer concentration, adsorption temperature, concentration of the lysozyme, and the textural parameter of the adsorbent on the lysozyme adsorption capacity of KIT‐6 was studied. The amount adsorbed mainly depends on solution pH, ionic strength, adsorption temperature, and pore volume and pore diameter of the adsorbent. The mechanism of adsorption on KIT‐6 under different adsorption conditions is discussed. In addition, the structural stability of lysozyme molecules and the KIT‐6 adsorbent before and after adsorption were investigated by XRD, nitrogen adsorption, and FTIR spectroscopy.  相似文献   

5.
New insights into pseudo-second-order kinetic equation for adsorption   总被引:1,自引:0,他引:1  
This study looked into the theoretical basis of the most commonly used pseudo-second-order kinetic equation for adsorption. It was demonstrated that the pseudo-second-order kinetic equation for adsorption indeed is in line with the universal rate law for a chemical reaction, while the same principle can also be applied to the pseudo-first-order kinetic equation for adsorption. This in turn offers a theoretical basis for the pseudo-second-order equation. If the second-order equation is applicable, the rate of adsorption was found to be subject to a second-order rate law with respect to the availability of adsorption sites on the surface of adsorbent rather than adsorbate concentration in bulk solution as proposed in the literature. Based on the rate law for the second-order adsorption process, the original complex second-order kinetic equation can be transformed to a simple hyperbolic form with clearly defined mathematical structure: Qt = Qe(t/t + tr) in which tr is relaxation time representing time required for adsorption to reach half-saturation state of adsorbent under given experimental conditions, i.e., Qt = 0.5Qe.  相似文献   

6.
The objective of this study was to qualitatively and quantitatively evaluate bovine lactoferrin (bLf) and its stability using a rapid RP‐HPLC method. bLf could be rapidly detected within 20 min and quantitated at levels down to 5 µg/mL, and the equation of linearity was y = 86.10x + 178.31 with the correlation coefficient (r2) 0.9997. Quantitative data obtained in the present study proved the improved RP‐HPLC method to be a sensitive and accurate analytical tool for bLf determination. The proteolytic cleavage of bLf in simulated human gastrointestinal fluids was further analyzed by RP‐HPLC, and found to follow pseudo‐first‐order kinetics. The typical equation obtained by pepsin was log10 [At]/[A0] = ?0.03x (r2 = 0.85), and log10 [At]/[A0] = ?0.01x (r2 = 0.81) for trypsin and chymotrypsin combination. Pepsinolysis of bLf in simulated gastric fluid was relatively fast with the half‐life t1/2 23.1 min. The digestion of bLf in simulated intestinal fluid was slower with about a 3‐fold increase in half‐life (69.3 min). After the complete proteolysis of bLf, small cleaved peptide fragments were fully separated and identified by RP‐HPLC. The proteolytic study indicated that this validated RP‐HPLC was able to evaluate bLf stability though monitoring the derivatization products. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

7.
IntroductionManyfactors ,includingTraube’srule ,temperature ,solubilityofsolute ,inorganicsalt,thestructureofadsor bentandthenatureandconcentrationofthesolvent,affectsoluteadsorptioninaliquid solidsystem .1Amongthemsolventeffectsareofsignificance .Dispersionsofsilicaarestabilizedbyethanol.Itisreportedthatsolventfilmthick nessisgreatestinmixturesof 5 0percentethanolwithwa ter.2 TherepulsionbetweendispersedparticlesisabovetheeffectsfromthedoublelayerandvanderWaalsforces3andisattributedtostruc…  相似文献   

8.
边六交  杨晓燕 《中国化学》2006,24(5):653-659
Based on three-state renaturation process of denatured proteins, an equation describing the effect of denaturant concentration on renaturation yield of denatured proteins was presented. By this equation, two parameters n(m1 -m2) and Ka can be obtained. The former indicates the difference in the number of denaturant molecules between the renaturation process of n number of refolding intermediates from refolding intermediate state to native state and their aggregate process from refolding intermediate state to aggregate state, the latter denotes the apparent aggregate equilibrium constant for protein molecules aggregated from native state to aggregate state, and from them, the characteristics of the renaturation process of denatured proteins in denaturant solution can be identified. This equation was tested by the renaturation processes of denatured egg white lysozyme in guanidine hydrochloride and urea solutions, with the results to show that when guanidine hydrochloride and urea concentrations were separately higher than 1.25 and 3.00 mol/L or separately lower than 1.00 and 3.00 mol/L, the refolding intermediates of egg white lysozymes were more easily aggregated to aggregate state or more easily renatured to native state, respectively. Under different initial total egg white lysozyme concentrations in urea solution, the refolding egg white lysozyme intermediates could be deduced to have a tendency to form a bimolecular intermediate aggregate, and this inference was further confirmed by their nonreducing SDS-PAGE and size exclusion chromatography.  相似文献   

9.
Alkyl chains are common structural units, for example in lipids, and their 1H NMR spectral parameters offer valuable information about their conformational behavior in solvent environment. Even the spectra of short n‐alkanes are complex, which is obviously a reason why their accurate spectral analyses have not been reported before. The present study reports the quantum mechanical analysis of 1H NMR spectra of n‐butane, n‐pentane, n‐hexane, and n‐heptane. The spectral parameters were used to characterize the conformational behavior of n‐alkanes. The temperature dependence analysis of coupling constants suggests that the enthalpy difference between the gauche (g) and trans (t) conformations (ΔHg) of n‐butane in chloroform is 2.55–2.85 kJ mol?1. The difference between the trans–gauche (tg) and all‐trans (tt) conformers of n‐pentane (ΔHtg) seems to be 0.1–0.2 kJ mol?1 higher. The coupling constant information shows that the tn conformations become more favored with longer chains, although not only for energetic reasons but also partly because the g+g arrangements become sterically unfavorable, which decreases the number of favorable gn‐type conformations. The analysis of the 1H NMR spectra of n‐pentane and n‐hexane in solvents representing different chemical environments indicates that polar and spherical dimethyl sulfoxide favors clearly the g conformations, whereas n‐hexane‐d14 favors slightly the extended tn conformation. In addition to the intrinsic scientific importance for NMR spectral parameter prediction and molecular modeling in solution, the results provide some insights to behavior of hydrocarbon chains and their spectra in different chemical environments. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

10.
Ninety‐six acidic phosphorus‐containing molecules with pKa 1.88 to 6.26 were collected and divided into training and test sets by random sampling. Structural parameters were obtained by density functional theory calculation of the molecules. The relationship between the experimental pKa values and structural parameters was obtained by multiple linear regression fitting for the training set, and tested with the test set; the R2 values were 0.974 and 0.966 for the training and test sets, respectively. This regression equation, which quantitatively describes the influence of structural parameters on pKa, and can be used to predict pKa values of similar structures, is significant for the design of new acidic phosphorus‐containing extractants. © 2016 Wiley Periodicals, Inc.  相似文献   

11.
Adsorption equilibria of nitrogen and methane on microporous ( < 2 nm) activated carbon were measured for a wide temperature range (103‐298 K) spanning the critical region. Information relating to Henry constants, the isosteric heat of adsorption, and the amount of limiting adsorption were evaluated. All isotherms show type‐I features for both sub‐ and supercritical temperatures. A new isotherm equation and a consideration for the importance of the effect of the adsorbed phase volume allow this kind of isotherms to be modeled satisfactorily. The model parameter of the saturated amount of absolute adsorption (n0t) equals the limiting adsorption amount (nitm), leaving the physical meaning of the latter clarified, and the exponent parameter (q) proves to be an appropriate index of surface heterogeneity.  相似文献   

12.
Three isostructural lanthanide‐based two‐ dimensional coordination polymers (CPs) {[Ln2(L)3(H2O)2]n ? 2n CH3OH) ? 2n H2O} (Ln=Gd3+ ( 1 ), Tb3+ ( 2 ), Dy3+ ( 3 ); H2L=cyclobutane‐1,1‐dicarboxylic acid) were synthesized by using a low molecular weight dicarboxylate ligand and characterized. Single‐crystal structure analysis showed that in complexes 1 – 3 lanthanide centers are connected by μ3‐bridging cyclobutanedicarboxylate ligands along the c axis to form a rod‐shaped infinite 1D coordination chain, which is further linked with nearby chains by μ4‐connected cyclobutanedicarboxylate ligands to form 2D CPs in the bc plane. Viewing the packing of the complexes down the b axis reveals that the lattice methanol molecules are located in the interlayer space between the adjacent 2D layers and form H‐bonds with lattice and coordinated water molecules to form 1D chains. Magnetic properties of complexes 1 – 3 were thoroughly investigated. Complex 1 exhibits dominant ferromagnetic interaction between two nearby gadolinium centers and also acts as a cryogenic magnetic refrigerant having a significant magnetic entropy change of ?ΔSm=32.8 J kg?1 K?1 for ΔH=7 T at 4 K (calculated from isothermal magnetization data). Complex 3 shows slow relaxation of magnetization below 10 K. Impedance analysis revealed that the complexes show humidity‐dependent proton conductivity (σ=1.5×10?5 S cm?1 for 1 , σ=2.07×10?4 S cm?1 for 2 , and σ=1.1×10?3 S cm?1 for 3 ) at elevated temperature (>75 °C). They retain the conductivity for up to 10 h at high temperature and high humidity. Furthermore, the proton conductivity results were correlated with the number of water molecules from the water‐vapor adsorption measurements. Water‐vapor adsorption studies showed hysteretic and two‐step water vapor adsorption (182000 μL g?1 for 1 , 184000 μL g?1 for 2 , and 1874000 μL g?1 for 3 ) in the experimental pressure range. Simulation of water‐vapor adsorption by the Monte Carlo method (for 1 ) confirmed the high density of adsorbed water molecules, preferentially in the interlayer space between the 2D layers.  相似文献   

13.
Abstract

In solution, solute molecules B are coupled by attractive forces between them and all other molecules present; and these other molecules enhance the tension in the coupling force between solute molecules an amount πB, the osmotic pressure of the solution solute. Two equilibria determine the n o B moles of pure solute which dissolve in n 10 A moles of pure liquid solvent. If at T the solute is solid and in excess, then 1) the n B lsat moles of B in the nl A moles of A in a solution saturated with B are in thermodynamic equilibrium with the solid solute at the same T and p and 2) the n B lsat moles of B and nl A moles of A may also be in chemical equilibrium with the moles of new molecular or ionic species formed in the solution. Solute molecules dissolve until the chemical potential of the solution solute, pl B(T p, xB lsat), equals the chemical potential of pure solid solute at the same T and p, μ B so(T, p). When the solution is saturated with B and the mole fraction of B is xB lsat = n B lsat/σj n 1 j, then the vapor pressures of the solid solute at T and p, the solution solute at T and p, and the pure undercooled liquid solute at T and p-π B lsat are identical. If at T the n B lo moles of pure solute and the nl A moles of pure solvent are liquids, then if molecules of B are allowed to dissolve in A while molecules of A are dissolved in B, the resulting solutions may 1) contain only molecules of A and B or 2) contain A and B which also react to form other ionic and molecular species. The two solutions may be identical or they may differ. In all cases, however, the mole ratio of nl Bnl A in both solutions must be identical.  相似文献   

14.
In previous paper a new adsorption isotherm which relates the amount of solute absorbed to the solvent concentration is pro-posed and simplified, and it only can be used at lower solute concentration. In this article the scope of the new adsorption isotherm is extended and the expressions with three and four parameters are obtained. The equations with multi-parameters are valid when the adsorbed mounts are larger and show non-linear logarithmic relationships. Tests with a homologue of are-matic alcohols by frontal analysis in reversed phase liquid chro-matography demonstrate that the experimental results fit those equations well. In addition, the predicted values by the multi-parameters were found to fit the experimental values well also. The parameters have physical meaning only for the two-param-eter equation for the aromatic alcohols.  相似文献   

15.
The ionic exchange of the NaX zeolite by Ni2+ and Cr3+ cations was progressively driven and studied by adsorption of nitrogen and carbon dioxide. For each cation-exchanged X zeolite sample, the development of characteristics such as profile of isotherms, RI criterion, isosteric adsorption heat and microporous volume using both the Dubinin–Radushkevich (DR) equation and the t-plot, was followed through the nitrogen adsorption. Results show that the cationic exchange process, in the case of Cr3+ introduced at middle degree, is accompanied by a textural damage for Cr(x)X, in contrast to Ni2+-exchanged X zeolites. This degradation occurs without significant presence of mesopores, because the RI criterion values were found to be much lower than 2.2. The CO2 adsorption isotherms were measured at intervals of 30 K from 273 K and the equilibrium pressures ranged from 0.5 to 600 Torr. The experimental data were correlated by the Toth model. The associated three adjustable parameters were estimated by nonlinear least-squares analysis. The effect of temperature on the model parameters and the Henry’s law slope, K H , represented by the product of Toth parameters, are discussed.  相似文献   

16.
Three novel vic-dioxime ligands containing the 1,8-diamino-3,6-dioxaoctane group, N,N′-(1,8-diamino-3,6-dioxaoctane)-p-tolylglyoxime (L1SL1H4), N,N′-(1,8-diamino-3,6-dioxaoctane)-phenylglyoxime (L2SL2H4), and N,N′-(1,8-diamino-3,6-dioxaoctane)-glyoxime (L3SL3H4) have been prepared from 1,8-diamino-3,6-dioxaoctane with anti-p-tolylchloroglyoxime, anti-phenylchloroglyoxime or anti-monochloroglyoxime. Polynuclear complexes [M(L x SL x )] n or [M(L x SL x )(H2O)] n (x = 1, 2 and 3), where M = CuII, CoII, and NiII, have been obtained with 1:1 metal/ligand ratio. The CuII and NiII poly-metal complexes of these ligands are proposed to be square planar, while also the prepared CoII complexes are proposed to be octahedral with two water molecules as axial ligands. The detection of H-bonding in the [Ni(L1SL1)] n , [Ni(L2SL2)] n and [M(L3SL3)(H2O)] n metal complexes by FT i.r. spectra revealed the square planar or octahedral [MN4·H2O)] n coordination of poly-nuclear metal complexes. [MN4] n coordination of the [Ni(L1SL1)] n and [Ni(L2SL2)] n complexes were also determined by 1H-n.m.r. spectroscopy. The ligands and poly-metal complexes were characterized by elemental analyses, FT-i.r., u.v.-vis., 1H and 13C-n.m.r. spectra, magnetic susceptibility measurements, molar conductivity, cyclic voltammetry, and differential pulse voltammetric (DPV) techniques.  相似文献   

17.
Dodecyl polyoxyethylene(4) polyoxypropylene(5) ether (LS45) is an outstanding microemulsifier in supercritical CO2. The dynamic surface tension (DST) of this nonionic surfactant was investigated by using the maximum bubble pressure instrument. The effects of concentration and temperature on DST parameters (n, ti, t*, tm, and R1/2) and its adsorption mechanism were discussed by Rosen's empirical equation and the asymptotic Ward and Tordai equation for the LS45 solution system. Finally, the parameters at 1 s related to Draves's wetting performance, pC20(1s), C1s (i)*, and C1s*, analyzed. The results showed that were with increase of bulk concentration and temperature, dynamic surface activity increased. Parameters at 1 s indicated that LS45 is of high surface activity and a very good wetting agent. One‐second related parameters, C1s (i)* and C1s*, are valuable in the treatment of practical applications of surfactants. Optimum wetting can be expected at the concentration of 4.8×10?4 mol/dm3 for LS45 solution.  相似文献   

18.
Abstract

A nonlinear thermodynamic model is applied to the prediction of both the bioconcentration factor (Kbw) in the guppy (Poecilia reticulata) and the n-octanol-water partition coefficient (Kow) of chlorinated dibenzofurans and dibenzo-p-dioxins. To this end molar liquid volumes, heats of vaporization and empirically fitted parameters of the pertinent solute and solvents are used. Calculated log Kbw and log Kow values are obtained with correlation coefficients (r = 0.85 and 0.992) and mean deviations (< dev > = 0.19 and 0.17), which compare favourably with experimental data.

In addition the model enables an explanation of the well-known nonlinear log-log relationship between the two properties for compounds with high Kow values on the basis of differences between the properties of biotic lipid and n-octanol. It is suggested that the breakdown of the linear relationship is caused by entropic effects related to the number of chlorine atoms in the solute molecules and to the structures of the lipid and n-octanol.  相似文献   

19.
The aim of this study was to evaluate the surface adsorption capacity of CrFeO3 nanoparticle‐loaded activated carbon (CrFeO3‐NPs–AC) for the removal of a cationic dye (methyl violet, MV). CrFeO3‐NPs were hydrothermally synthesized and loaded on AC followed by characterization using X‐ray diffraction, field‐emission scanning electron microscopy and energy‐dispersive and Fourier transform infrared spectroscopies. The CrFeO3‐NPs were tested for in vitro antibacterial activities against Gram‐positive (Staphylococcus aureus) and Gram‐negative (Pseudomonas aeruginosa) bacteria. Minimum inhibitory and minimum bactericidal concentrations of CrFeO3‐NPs–AC were obtained to be 50 and 100 μg ml?1, respectively, against S. aureus and 25 and 50 μg ml?1 against P. aeruginosa. These results indicated the antibacterial properties of CrFeO3‐NPs–AC. To investigate the adsorption process, several systematic experiments were designed by varying parameters such as adsorbent mass, pH, initial MV concentration and sonication time. The adsorption process was modelled and the optimal conditions were determined to be 0.013 g, 7.4, 15 mg l?1 and 8 min for adsorbent mass, pH, MV concentration and sonication time, respectively. The real experimental data were found to be efficiently explained by response surface methodology and genetic algorithm model. Kinetic studies for MV adsorption showed rapid sorption dynamics described by a second‐order kinetic model, suggesting a chemisorption mechanism. Then, the experimental equilibrium data obtained at various concentrations of MV and adsorbent masses were fitted to conventional Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. Dye adsorption equilibrium data were fitted well to the Langmuir isotherm. From the Langmuir model, the maximum monolayer capacity was calculated to be 65.67 mg g?1 at optimum adsorbent mass.  相似文献   

20.
The objective of this work is to study the removal of malachite green (MG) from water by adsorbents obtained from pyrolysis of two paper industry waste materials: one de-inking paper sludge (HP) and one organic sludge from virgin pulp mill (RT). Both adsorbents showed elevated MG removal. Maximum adsorption Q 0 obtained by Langmuir equation was higher for the adsorbent from HP (HP-3, 982 mg/g) than RT (RT-3, 435 mg/g). However, K L (Langmuir) and 1/n (Freundlich) indicated that affinity and intensity of adsorption is higher for the adsorbents from RT. Thermal analysis (TG, DTG and DTA) of adsorbents before and after MG removal was performed in N2 atmosphere.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号