Adsorption Features of Flavonoids on Macroporous Adsorption Resins Functionalized with Ionic Liquids

A series of macroporous adsorption resins (MARs) with novel structures is synthesized via Friedel–Crafts catalyzed reaction. The adsorption kinetics of the synthetic resins with respect to the purification effect is systematically investigated by means of the response surface methodology (RSM). The kinetic data cannot be fitted to the classical model because it does not take multicompartments and desorption rates into consideration. A new multicompartment louver‐tide theory is thus developed considering that adsorption is an indefinite dynamic equilibrium process, which can be divided into innumerable ingredients with different desorption rates. This theory produces much better fits to the experimental data and provides a quantitative explanation with multicompartments and adsorption/desorption rates.     

Evaluation of Desorption Energy Distributions from TPD Spectra on a Heterogeneous Solid Surface

The condensation approximation (CA) and numerical regularization procedure (RP) methods used to solve a Fredholm integral equation of the first kind describing the adsorption equilibria on a heterogeneous solid surface under isothermal conditions have been adopted in the present study to evaluate desorption energy distributions from temperature-programmed desorption (TPD) spectra. From comparisons of the computational results obtained by means of these methods on the basis of simulated TPD spectra, it follows that the CA gives stable solutions for wide desorption energy distributions and it can be used successfully for calculations from wide and clear resolved peaks in the TPD spectra. The use of the RP is more advantageous for acquisition of the distributions from closely related narrow peaks in the TPD spectra. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetic study of the "surface explosion" phenomenon in the NO+CO reaction on Pt(100) through dynamic Monte Carlo simulation

The extremely narrow production peak of N2 and CO2 which occurs in the reaction of NO+CO on Pt(100), a phenomenon known as "surface explosion," is studied using a dynamic Monte Carlo method on a square lattice at low pressure under isothermal conditions. This analysis incorporates recent experimental evidence obtained for the same reaction on a Rh(111) surface, which has shown that N2 production occurs either from the classical N+N recombination step or by the formation and successive decay of a (N-NO)* intermediary species. Moreover, the NO dissociation rate is inhibited by coadsorbed NO and CO molecules and is enhanced both by the presence of empty sites and adsorbed N atoms as nearest neighbors. These effects are taken into account in this study, along with the experimental adsorption, desorption, and diffusion rates of the reactants. The "explosive" phenomenon is analyzed through the evolution over time of an adsorbed NO+CO monolayer at a fixed temperature of 400 K. Furthermore, as the diffusion processes of the adsorbates are included, cellular structures are observed. Our simulations show quantitative agreement in the position of maxima with those obtained through experiments using isothermal desorption mass spectroscopy.     

Adsorption and desorption of colloidal particles on glass in a parallel plate flow chamber—Influence of ionic strength and shear rate

The adsorption and desorption rates of 736 nm diameter polystyrene particles on glass were studiedin situ using a parallel plate flow chamber and automated image analysis. Adsorption and desorption rates were measured simultaneously during deposition, enabling the determination of initial deposition rates, blocked areas per particle, desorption rate coefficients, and the number of adhering particles in the stationary state. Deposition experiments were done from suspensions with different potassium nitrate concentrations (1, 10 and 50 mM) and at varying shear rates (15 to 200 s^–1). The initial deposition rate, the desorption rate, the blocked area per particle and the number of adhering particles in the stationary state showed major variations with the shear rate and the ionic strength of the suspension. At low ionic strength, the number of adhering particles showed an oscillatory behavior in time, presumably due to a varying interaction between particle and collector surface. Blocked areas, determined from deposition kinetics, ranged 705 to 2374 cross-sections at low ionic strength, and from 10 to 564 at high ionic strength and corresponded well with those estimated from local pair distribution functions which were obtained from an analysis of the spatial arrangement of the adhering particles.     

Frontal analysis for characterizing the adsorption-desorption behavior of beta-lactoglobulin on immunoadsorbents

High-performance frontal affinity chromatography was employed to study the adsorption-desorption kinetics characterizing the retention of beta-lactoglobulin (beta-LG) onto polyclonal anti-beta-lactoglobulin (anti-beta-LG) chromatographic supports. The adsorption and desorption processes were studied by analyzing two different elution fronts separated by a relatively long rinsing step. The method consists in performing two successive frontal injections of the protein. In between, the column was rinsed with a given volume of mobile phase (buffer alone). During this rinsing stage, a partial desorption may occur and a novel amount of protein could be adsorbed in the second frontal injection step. The whole process (first adsorption, possible desorption, and second adsorption) was simulated by a numerical procedure, in which the column was divided into a large number of slices. A model based on bi-Langmuir type kinetics was used to describe the adsorption of the protein on the support. The model assumes a non-uniform adsorbent with two types of binding sites. At equilibrium the adsorption isotherm is of the bi-Langmuir type. A global adsorption effect was considered which includes the effective binding process and the mass transfer resistances due to the transport to the binding site. Therefore, the column capacity and the kinetic parameters of the model (apparent adsorption and desorption rate constants) were determined from the best fit of the first and second adsorption fronts to the experimental ones. The other parameters of the model are the saturation capacities for the adsorption on each type of sites. The equilibrium affinity constants were estimated in a single experiment from the ratio of the apparent adsorption and desorption rate constants. The high values found (around 10(8) M(-1)) reveal a strong interaction of beta-LG with the immunoadsorbent. Kinetic measurements were carried out at different flow rates. Both the apparent adsorption and desorption kinetics were faster at larger flow rates, indicating an important contribution of the mass transfer resistance in the stagnant fluid at the particle boundary. However, as expected, close values were found for the resulting equilibrium constants calculated from the ratio of the apparent adsorption and desorption rate constant determined at various flow rates.     

Adsorption of alpha-chymotrypsin onto mica in laminar flow conditions. Adsorption kinetic constant as a function of tris buffer concentration at pH 8.6

We examined the adsorption kinetics of alpha-chymotrypsin (pH 8.6, 10(-2) to 0.5 M Tris buffer) on muscovite mica in conditions of laminar flow through a slit. The range of buffer concentrations is between two limits: (i) no adsorption in 1 M Tris and (ii) no desorption in 10(-3) M Tris. Studying the dependence of adsorption kinetics on the wall shear rate leads to the determination of the interfacial adsorption kinetic constant ka and the diffusion coefficient. The obtained value for the diffusion coefficient is close to the one expected from the molecular size of alpha-chymotrypsin. The interfacial adsorption kinetic constant of alpha-chymotrypsin decreases when ionic strength increases, while the initial desorption constant (over a part of all the adsorbed population) shows the contrary. Although alpha-chymotrypsin is almost at its isoelectric point, the effect of ionic strength on the adsorption kinetics suggests the importance of electrostatic interactions between the protein and mica. We observed an increase in the adsorption rate, at a surface coverage near 0.14 microg cm(-2), for adsorption in 10(-2) M Tris and the low wall shear rates (<300 s(-1)). This change in the adsorption rate suggests a structural transition, that we assume again to be due to electrostatic interactions, but between proteins. The large dipole moment of the protein may induce this transition, illustrated here by the ferroelectric/antiferroelectric pattern. The variation of the zeta potential with interfacial concentration seems to be in agreement with such a model.     

Studies about the desorption of volatile halocarbons from activated carbon by application of static headspace gas chromatography

The analysis of volatile halocarbons (VHCs) in air or ground air is often performed after their adsorption and enrichment on activated carbon. The current procedure for their subsequent determination is based on their extraction from the activated carbon with a volatile organic solvent such as n-pentane, followed by gaschromatographic (GC) analysis. In order to avoid extraction steps, the static headspace method in combination with GC analysis using diphenylmethane as a desorption agent has been applied. Satisfactory desorption rates for the chloromethanes, for 1,1,1-trichloroethane, trichloroethene and for tetrachloroethene have been obtained after a sample equilibration of 45 min at 120 degrees C in the presence of diphenylmethane. The results have shown a higher recovering rate especially of the unsaturated VHCs compared to the extraction with n-pentane, whereby a potential loss of analytes by the latter procedure has been avoided.     

法拉第吸脱附偶联过程循环伏安行为的有限元分析

法拉第吸脱附偶联过程的电化学行为较为复杂,难以定量获得其表界面反应动力学信息. 本文通过COMSOL有限元软件对法拉第吸脱附偶联过程的循环伏安行为进行数值分析,研究了反应物或产物不同吸附条件下的循环伏安行为. 结果表明：当反应物或产物弱吸附时,可通过阴、阳极峰电流之差实现饱和吸附量的定量表征. 随着吸附平衡常数的增大,反应由弱吸附向强吸附过渡,峰电流由扩散峰与吸脱附峰相互重叠过渡到相互分离的吸脱附“前波”或“后波”特征. 该吸脱附特征峰的形状和位置与电势依赖的吸附平衡常数有关. 吸附平衡常数及其电势依赖程度越大,吸脱附峰偏离扩散峰越远,吸脱附峰越尖锐. 该模型为法拉第吸脱附偶联过程的循环伏安研究提供了一种定量研究方法,能够帮助研究者从复杂的吸脱附伏安行为中定量获得饱和吸附量和吸附平衡常数等信息,并对涉及吸脱附的电催化研究具有一定指导意义.     

Studies about the desorption of volatile halocarbons from activated carbon by application of static headspace gas chromatography

The analysis of volatile halocarbons (VHCs) in air or ground air is often performed after their adsorption and enrichment on activated carbon. The current procedure for their subsequent determination is based on their extraction from the activated carbon with a volatile organic solvent such as n-pentane, followed by gaschromatographic (GC) analysis. In order to avoid extraction steps, the static headspace method in combination with GC analysis using diphenylmethane as a desorption agent has been applied. Satisfactory desorption rates for the chloromethanes, for 1,1,1-trichloroethane, trichloroethene and for tetrachloroethene have been obtained after a sample equilibration of 45 min at 120° C in the presence of diphenylmethane. The results have shown a higher recovering rate especially of the unsaturated VHCs compared to the extraction with n-pentane, whereby a potential loss of analytes by the latter procedure has been avoided.     

Structure of adsorbed n-dodecyl-beta-D-maltoside layers on hematite

The composition, structure, and thickness of n-dodecyl-beta-D-maltoside self-assembled layers on hematite have been evaluated using infrared external reflection spectroscopy and spectral simulation techniques. From the qualitative and quantitative analysis of the reflection spectra of the same sample recorded at different specific angles of incidence and two polarizations, the orientation of the sugar ring and hydrocarbon chain were obtained. Both of these molecular groups are positioned parallel to hematite surface, the adsorbed molecules being at low (2.2-nm-thick layer) as well as higher (11-nm) coverages. The maltoside is adsorbed through interaction of sugar ring OH groups with hematite surface hydroxyl groups. The adsorption of maltoside is not very strong and desorption takes place easily from acidic and low-basic solutions but with more difficulty from strong-basic solution.     

ATR-FTIR studies on the adsorption/desorption kinetics of dimethylarsinic acid on iron-(oxyhydr)oxides

Dimethylarsinic acid (DMA) is an organoarsenical compound that, along with monomethylarsonic acid, poses a health and an environmental risk, and a challenge to the energy industry. Little is known about the surface chemistry of DMA at the molecular level with materials relevant to geochemical environments and industrial sectors. We report herein the first in situ and surface-sensitive rapid kinetic studies on the adsorption and desorption of DMA to/from hematite and goethite at pH 7 and I = 0.01 M KCl using ATR-FTIR. Values for the apparent rates of adsorption and desorption were extracted from experimental data as a function of spectral components, flow rate of the aqueous phase, film thickness of hematite, and using chloride and hydrogen phosphate as desorbing agents. The adsorption kinetic data show fast and slow rates, consistent with the formation of more than one type of adsorbed DMA. Apparent adsorption and desorption rate constants were extracted from the dependency of the initial adsorption rates on [DMA(aq)]. Desorption rate constants were also extracted from desorption experiments using hydrogen phosphate and chloride solutions, and were found to be higher by 1-2 orders of magnitude than those using chloride. In light of the complex ligand exchange reaction mechanism of DMA desorption by phosphate species at pH 7, apparent desorption rate constants were found to depend on [hydrogen phosphate] with an order of 0.3. The impact of our studies on the environmental fate of DMA in geochemical environments, and the design of technologies to reduce arsenic content in fuels is discussed.     

Adsorption, desorption, and diffusion of nitrogen in a model nanoporous material. I. Surface limited desorption kinetics in amorphous solid water

The adsorption and desorption kinetics of N2 on porous amorphous solid water (ASW) films were studied using molecular beam techniques, temperature programed desorption (TPD), and reflection-absorption infrared spectroscopy. The ASW films were grown on Pt(111) at 23 K by ballistic deposition from a collimated H2O beam at various incident angles to control the film porosity. The experimental results show that the N2 condensation coefficient is essentially unity until near saturation, independent of the ASW film thickness indicating that N2 transport within the porous films is rapid. The TPD results show that the desorption of a fixed dose of N2 shifts to higher temperature with ASW film thickness. Kinetic analysis of the TPD spectra shows that a film thickness rescaling of the coverage-dependent activation energy curve results in a single master curve. Simulation of the TPD spectra using this master curve results in a quantitative fit to the experiments over a wide range of ASW thicknesses (up to 1000 layers, approximately 0.5 microm). The success of the rescaling model indicates that N2 transport within the porous film is rapid enough to maintain a uniform distribution throughout the film on a time scale faster than desorption.     

离子交换树脂固态胺复合材料的制备、表征及CO2吸附

以离子交换树脂（D001）为载体,四乙烯五胺（TEPA）为改性剂,采用三种不同的方法制备了一系列固态胺吸附剂。采用N₂吸附-脱附、傅里叶变换红外光谱（FT-IR）、热重分析（TGA）等手段对吸附剂进行表征。在固定床反应器中考察了TEPA负载量、吸附温度、进气流量和CO₂分压等因素对CO₂吸附性能的影响。结果表明,配位法制得的固态胺吸附剂分散性和稳定性较好,且在TEPA负载量为40%,吸附温度为65℃,进气流量为40 mL/min时有最大CO₂吸附量达4 mmol/g。经过10次吸附-脱附循环实验后,CO₂吸附量下降3.98%。热力学、动力学研究结果表明,CO₂吸附是物理吸附和化学吸附的结果。     

On the equilibrium nature of thermodesorption processes. TPD-NH3 studies of surface acidity of Ni/MgO-Al2O3 catalysts

This article deals with a quantitative analysis of thermodesorption spectra of ammonia: a technique commonly applied to study the surface acidity of solids. The method used for determination of adsorption energy distributions of ammonia is the same as that published recently for the case of hydrogen thermodesorption (Panczyk, T.; et al. Langmuir 2005, 21, 7311). The developed theoretical expression describing the thermodesorption process is based on the statistical rate theory (SRT) and its analysis leads to the conclusion that majority of thermodesorption processes, carried out under flow conditions, are in fact quasi-equilibrium ones. Similar conclusion has already been drawn by some authors applying the classical absolute rate theory (ART) for analysis of thermodesorption data. This conclusion has important practical consequences. Namely, it greatly simplifies the quantitative analysis of thermodesorption processes since there is no need to use any kinetic approaches to that purpose. The quantitative analysis of thermodesorption spectra can thus be based on commonly accepted relations following from equilibrium thermodynamics. It is worth noting that in quasiequilibrium conditions either the SRT or the ART lead to this same expression with only a slightly different meaning of some constants. Thus, in quasiequilibrium conditions there is no need to decide which theoretical approach should be applied. As an illustration, the ammonia thermodesorption spectra from the modified nickel catalysts are analyzed. The catalysts were prepared by the coprecipitation method and differ by the amount of MgO and NiO, whereas the amount of Al(2)O(3) is constant and equals 30%. It was stated that the presence of MgO reduces the number of acid centers corresponding to high values of ammonia adsorption energy.     

超高真空质谱法研究氧在电解银上的吸附态

运用超高真空程序升温反应(TPRS)技术研究了氧在电解银上的化学吸附。在宽广的压力范围内(1—10~(-8) torr)考察了几种吸附氧种的变化规律, 并观察到在覆盖度为0.2—0.6时表面吸附物种的突变。用同位素交换和CO滴定实验证实了在电解银表面存在三种氧吸附态: (1) 弱的未解离的分子态吸附(E_d=92 kJ mol~(-1), v=4×10~(11) S~(-1)); (2) 强的解离的原子态吸附(E_d=134 kJ mol~(-1), v=4.7×10~(13) S~(-1)); (3)氧在银体相中扩散。进一步的实验发现, 分子态吸附氧与表面杂质的存在有关。用等温脱附技术研究了氧在银中的扩散, 得到了扩散量随温度增加的定性规律。     

Kinetics of adsorption of oxalic acid on different titanium dioxide samples

FTIR-ATR kinetic studies on the adsorption of oxalic acid on different TiO(2) films were performed. The particulate films were obtained through the evaporation of TiO(2) suspensions. The evolution of the IR bands followed a pseudo-first-order behavior, as previously observed. Systematic studies as a function of the oxalic acid concentration afforded the specific rate constant for adsorption (k(a)) and desorption (k(d)). The influence of physical parameters of the samples, i.e., specific BET area, crystalline domain size, TiO(2) load, film area, and pore size, on the kinetic parameters k(a) and k(d) was analyzed. A mechanism in which the adsorption and desorption processes are controlled by the diffusion through the pores of the films is proposed (intraparticle diffusion). It is concluded that all the samples behave in the same way. Thicker films or those with smaller particle size (higher specific surface area, smaller pores) show the slowest rates of adsorption and desorption. These results are relevant for the design of efficient heterogeneous catalysts and sensors, and for the interpretation of pollutant adsorption.     

Adsorption and desorption of HCl on Pt(111)

The adsorption and desorption of HCl on Pt(111) is investigated by temperature programmed desorption, infrared reflection absorption spectroscopy, and low energy electron diffraction. Five peaks are identified in the desorption spectra prior to the onset of multilayer desorption. At low coverage ( < 0.25 monolayers (ML)), desorption peaks at approximately 135 and 200 K are observed and assigned to recombinative desorption of dissociated HCl. At higher coverages, desorption peaks at 70, 77, and 84 K are observed. These peaks are assigned to the desorption of molecularly adsorbed HCl. The infrared spectra are in agreement with these assignments and show that HCl deposited at 20 K is amorphous but crystallizes when heated above 60 K. Kinetic analysis of the desorption spectra reveals a strong repulsive coverage dependence for the desorption energy of the low coverage features ( < 0.25 ML). The diffraction data indicate that at low temperature the adsorbed HCl clusters into ordered islands with a (3 x 3) structure and a local coverage of 4/9 with respect to the Pt(111) substrate.     

A 2,5-dihydroxybenzoic acid/N,N-dimethylaniline matrix for the analysis of oligosaccharides by matrix-assisted laser desorption/ionization mass spectrometry

The use of a novel 2,5-dihydroxybenzoic acid/N,N-dimethylaniline (DHB/DMA) matrix-assisted laser desorption/ionization (MALDI) matrix for detection and quantitative analysis of native N-linked oligosaccharides was investigated in this study. Substantial improvements in sensitivity were observed relative to the signals obtained with a traditional DHB matrix. Moreover, the morphology of the matrix crystal layer was very uniform, unlike that of DHB. This resulted in highly homogeneous sample distribution throughout the spot, allowing reproducible and consistent mass spectra to be obtained without spot-to-spot variations in signal. Here, we also demonstrate an approach for performing sensitive and accurate quantitative analysis of native N-linked glycans with this novel matrix using an internal standard method.     

Characterizing the adsorption of proteins on glass capillary surfaces using electrospray-differential mobility analysis

We quantify the adsorption and desorption of a monoclonal immunoglobulin-G antibody, rituxamab (RmAb), on silica capillary surfaces using electrospray-differential mobility analysis (ES-DMA). We first develop a theory to calculate coverages and desorption rate constants from the ES-DMA data for proteins adsorbing on glass capillaries used to electrospray protein solutions. This model is then used to study the adsorption of RmAb on a bare silica capillary surface. A concentration-independent coverage of ≈4.0 mg/m(2) is found for RmAb concentrations ranging from 0.01 to 0.1 mg/mL. A study of RmAb adsorption to bare silica as a function of pH shows maximum adsorption at its isoelectric point (pI of pH 8.5) consistent with literature. The desorption rate constants are determined to be ≈10(-5) s(-1), consistent with previously reported values, thus suggesting that shear forces in the capillary may not have a considerable effect on desorption. We anticipate that this study will allow ES-DMA to be used as a "label-free" tool to study adsorption of oligomeric and multicomponent protein systems onto fused silica as well as other surface modifications.     

Petroleum resins adsorption onto quartz sand: near infrared (NIR) spectroscopy study

In this paper we have tried to evaluate adsorption parameters of petroleum resins. Near infrared (NIR) spectroscopy is applied for resins bulk concentration evaluation during adsorption process. NIR experimental scheme and parameters are provided. NIR spectra range of 9000-13,000 cm(-1) is chosen. Quartz sand (0.2-0.8 mm fraction) is used as adsorbent; benzene is used as solvent. Different approaches of "NIR spectra-resins concentration" calibration model building are discussed. Partial least squares (PLS) regression method is used. Langmuir model is chosen for experimental data fitting. Combined usage of kinetic and isothermic data gives us ability to evaluate the maximal adsorbed mass density, the equilibrium constant of adsorption, and the rate constants of adsorption (and desorption). The rate constants of resins adsorption and desorption are found to be concentration independent.