Concurrent adsorption and complex formation in reversed-phase liquid-liquid chromatography with tri-n-octylphosphine oxide

Summary Reversed-phase liquid-liquid chromatographic systems consisting of an aqueous mobile phase and an organic liquid stationary phase of the proton acceptor tri-n-octylphosphine oxide (TOPO) inn-decane, coated on LiChrosorb RP-8, have been studied. The solutes were hydrophilic aromatic carboxylic acids and phenol. The retention of the carboxylic acids shows a minimum at 10 mM of TOPO, whereas increasingly tailing peaks have been obtained with decreasing concentrations of TOPO. This behaviour is due to a concurrent complex formation by hydrogen bonding with TOPO in the liquid stationary phase and adsorption at the interface between the support and the liquid stationary phase. The adsorption of TOPO, ketones and aromatic acids from hexane on Li-Chrosorb RP-8 has been studied, and seems to be due to residual silanol groups. The adsorption isotherm of TOPO has been determined and can be described by a two-site Langmuir adsorption model. Non polar solutes are not adsorbed. The influence of TOPO on the retention and the peak symmetry of carboxylic acids in the liquid-liquid chromatographic system appears to be due to a competition between TOPO and the acids for the same adsorption sites. No competition was found for phenol.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Cross-linking epoxide resins with hydrolysates of chrome-tanned leather waste

Differential scanning calorimetry was employed to investigate the reaction of diglycidyl ethers of bisphenol A (DGEBA) of mean molecular mass 348–480 Da, with collagen hydrolysate of chrome-tanned leather waste in a solvent-free environment. The reaction leads to biodegradable polymers that might facilitate recycling of plastic parts in products of the automotive and/or aeronautics industry provided with protective films on this basis. The reaction proceeds in a temperature interval of 205–220°C, at temperatures approx. 30–40°C below temperature of thermal degradation of collagen hydrolysate. The found value of reaction enthalpy, 519.19 J g⁻¹ (= 101.24 kJ mol⁻¹ of epoxide groups) corresponds with currently found enthalpy values of the reaction of oxirane ring with amino groups. Reaction heat depends on the composition of reaction mixture (or on mass fraction of diglycidyl ethers in the reaction mixture); proving the dependence of kinetic parameters of the reaction (Arrhenius pre-exponential factor A (min⁻¹) and activation energy E _a (kJ mol⁻¹)) did not succeed. Obtained values of kinetic parameters are on a level corresponding to the assumption that reaction kinetics is determined by diffusion.     

DFT Investigations About Pyrazine Molecules on Si(100)-2×1 Surface

It is important to understand the interface of aromatic molecules on semiconductor surfaces because of the rich functionality of such molecules on semiconductor surfaces. The chemisorption of pyrazine molecules on the Si( 100)-2×1 surface has been investigated using the B3LYP density functional theory with Si9H12 one-dimer and Si15H16 twodimer cluster models. The calculated results predict that N-dative bonded-state, C2= C5 [ 4 2 ] and the tightbridge1, 2, 5,6 products may coexist on the Si(100)-2×1 surface.     

The application of the Dubinin-Astakhov equation to the characterization of microporous carbons

A study is made of the adsorption of carbon dioxide at 195 K on a series of microporous carbons. The adsorption data are analysed using the Dubinin-Astakhov equation. It is found that the adsorption isotherms obey the Dubinin-Astakhov equation over the pressure range studied.The characteristic energy of adsorption calculated from the slope of the Dubinin-Astakhov plot is shown to be in correlation with the mean value of the adsorption potential. The microporosity of carbons is interpreted in terms of the characteristic parameters of the adsorption pontential distribution, determined by means of the Dubinin-Astakhov equation. It is found good agreement between these parameters and the micropore size distribution.     

CO2选择性氧化甲烷制C2烃催化剂La2O3/ZnO的氧化还原和CO2吸附性能

Ｌａ２Ｏ３／ＺｎＯ催化剂体系在以二氧化碳作为氧化剂的甲烷氧化偶联反应中具有很高的Ｃ２烃选择性和稳定性．采用ＣＯ２－ＴＰＤ－ＭＳ和ＴＰＲ技术考察了Ｌａ２Ｏ３／ＺｎＯ对ＣＯ２的吸附性质及其氧化还原行为．结果表明：（１）Ｌａ２Ｏ３／ＺｎＯ催化剂体系存在着强、弱两种碱中心，其中弱碱中心数量随样品中Ｌａ２Ｏ３含量增加而减少，强碱中心强度随样品中Ｌａ２Ｏ３含量增加而增强．（２）由于组分相互作用，高温下，Ｌａ２Ｏ３／ＺｎＯ易产生晶格氧空位，使之对ＣＯ２的吸附增强，吸附后的ＣＯ２与晶格氧作用形成立方晶型Ｌａ２Ｏ２ＣＯ３．（３）Ｌａ２Ｏ３／ＺｎＯ表面的Ｌａ３＋和Ｚｎ２＋可以部分被还原，由于组分间的相互作用，使得二者的还原都较单一组分存在时更难．（４）Ｈ２－ＣＯ２－Ｈ２氧化还原循环实验表明，Ｌａ２Ｏ３／ＺｎＯ表面被部分还原后，ＣＯ２可以将部分被还原的表面再氧化．在此基础上对Ｌａ２Ｏ３／ＺｎＯ催化剂上甲烷与ＣＯ２转化为Ｃ２烃的机制也进行了讨论．     

Ellipsometry studies of fibronectin adsorption

The adsorption of fibronectin on a series of different surfaces was investigated with in situ ellipsometry. For silica and methylated silica, the adsorbed amount (Γ), the adsorbed layer thickness (δ_el) and the mean adsorbed layer refractive index (n_f) were obtained by a procedure involving studies of the bare substrate at two different ambient refractive indices, as well as four-zone averaging. It was found that the adsorbed amount of fibronectin was the same (1.9 ± 0.1 mg m⁻²) on both silica and methylated silica surfaces. However, the adsorbed layers formed on methylated silica were more extended and had a lower average protein concentration than those formed on silica. Furthermore, on both silica and methylated silica, an increasing adsorbed amount is achieved both by a denser packing of the fibronectin molecules and by a growth of the adsorbed layer normal to the surface. Furthermore, the adsorption of fibronectin on lipid surfaces was investigated. It was found that the adsorption of fibronectin on phosphatidic acid was quite significant (2.2 ± 0.2 mg m⁻²), while that on phosphatidylcholine, phosphatidylinositol and phosphatidylserine was much smaller (all 0.1 ± 0.05 mg m⁻²). These results are correlated to findings on the adsorption of fibrinogen on these surfaces, as well as on the opsonization of lipid-stabilized colloidal particles.     

Monte Carlo simulation of adsorption of binary and quaternary alkane isomers mixtures in zeolites: Effect of pore size and structure

Grand canonical Monte Carlo and configurational bias Monte Carlo techniques were employed to simulate the adsorption of binary mixtures of butane isomers and quaternary mixtures in nine zeolites at 300 K. For binary mixtures the results show there is a critical pore size, which is 10-membered-ring about 5.6 Å. The channel sizes of BEA, ISV, MOR and CFI are larger than this critical pore size, they prefer i-butane than n-butane, whereas TON with smaller channel size than critical pore size prefers n-butane than i-butane, but its selectivity decreases with pressure increasing. MFI, MEL and TER prefer i-butane than n-butane at low pressure, but with pressure increasing, the selectivity is reversed. BOG prefers i-butane than n-butane but the selectivity decreased with pressure increasing. It demonstrates that the adsorption and selectivity are controlled by both pore size and pore structure. The n-butane–i-butane–n-pentane–2-methylbutane quaternary mixtures adsorbed in these nine zeolites were studied, and the results show alkane chain length dependence at low pressure, but the adsorption is controlled by pore size and structure with pressure increasing in all the zeolites except for TON and BOG.     

A chelating resin containing S, N and O atoms: Synthesis and adsorption properties for Hg(II)

A novel chelating resin containing S, N and O atoms (PSME-EDA) was synthesized by using poly(2-hydroxyethylmercaptomethylstyrene) (PSME) and diethanolamine (EDA) as materials. Its structure was characterized by elemental analysis, Fourier transform-infrared spectra (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The adsorption of the resin for Hg²⁺ was investigated. The saturated adsorption capacity of PSME-EDA for Hg²⁺ could reach to about 1.1 mmol/g at 25 °C when the initial Hg²⁺ concentration was 0.02 mol/l. Some factors affecting the adsorption such as temperature, reaction time and ion concentration were also studied. The results showed that adsorption was controlled by liquid film diffusion. The increasing of temperature was beneficial to adsorption. The Langmuir model was better than the Freundlich model to describe the isothermal process. The values of ΔG, ΔH, and ΔS calculated at 25 °C were −7.99 kJ mol⁻¹, 22.5 kJ mol⁻¹ and 34.4 J mol⁻¹ K⁻¹, respectively. The adsorption mechanism of PSME-EDA resin for Hg(II) was confirmed by X-ray photoelectron spectroscopy (XPS).     

Adsorption of<Emphasis Type="Italic"> N</Emphasis>-dodecyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethyl-3-ammonio-1-propanesulfonate (DDAPS), a model zwitterionic surfactant,on the Au(111) electrode surface

Electrochemical measurements including cyclic voltammetry, differential capacity, and chronocoulometry have been used to characterize the adsorption behaviors of the zwitterionic surfactant N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDAPS) on the Au(111) electrode surface. The thermodynamics of the ideally polarized electrode have been employed to determine the Gibbs excess and the Gibbs energy of adsorption. The results show that the adsorption of DDAPS has a multistate character. The first two states are observed at potentials close to zero charge. At low bulk DDAPS concentrations, it corresponds to the formation of a film of nearly flat adsorbed molecules. At higher concentrations it is converted into a hemimicellar state. The second state is formed at negative potentials and charge densities close to 0 C cm^–2. It corresponds to a film of tilted molecules oriented with the hydrocarbon tail towards the metal and the polar head toward the solution.Dedicated to Professor Zbigniew Galus on the occasion of his 70^th birthday and in recognition of his many contributions to electrochemistry.     

Protein adsorption in fused-silica and polyacrylamide-coated capillaries

The model proteins cytochrome c, myoglobin, ovalbumin, and beta-lactoglobulin were investigated with regard to their adsorption properties on capillaries for electrophoresis. The model compounds were selected to cover a wide range of properties. Cytochrome c is a basic protein (isoelectric point (pI): 9.6; M(r): 11.7 kDa), beta-lactoglobulin is rather acidic (pI: 5.4, M(r): 18.4 kDa), myoglobin was chosen as a neutral reference protein (pI: 6.8-7.4, M(r): 17.8 kDa), and ovalbumin (pI: 5.1, M(r): 45.0 kDa) was selected as a relatively larger analyte. First, the pH dependence of adsorption was investigated for the bare fused silica. A clear correlation to the respective pIs was noted. For myoglobin and ovalbumin, none or negligible adsorption was found above the pI, whereas strong adsorption was noted just below this parameter. Cytochrome c and beta-lactoglobulin already showed distinct adsorption above their pIs. However, none of the proteins showed any significant adsorption more than one pH unit above the pIs. For linear polyacrylamide-coated capillaries, a decreased but not a complete lack of adsorption was observed. Here, pH-dependent adsorption was noted as well. Regeneration of the capillaries by rinsing with buffers containing 200 mM SDS was also investigated. This method was completely successful for myoglobin, but that too for only freshly-adsorbed protein. After a storage time of 24 h and due to the aging of the adsorbate, a sufficient regeneration was no longer possible.