Inhomogeneous Adsorption Research Articles

On perturbation around closed exclusion processes

We derive the formula for the stationary states of particle-number conserving exclusion processes infinitesimally perturbed by inhomogeneous adsorption and desorption. The formula not only proves but also generalises the conjecture proposed in [Phys. Rev. E 97, 032135] to account for inhomogeneous adsorption and desorption. As an application of the formula, we draw part of the phase diagrams of the open asymmetric simple exclusion process with and without Langmuir kinetics, correctly reproducing known results.

Effects of Short-Term Acidification on the Adsorption of Dissolved Organic Matter by Soil Minerals and Its Mechanism of Action

In order to investigate the impact of soil acidification on the adsorption of dissolved organic matter by soil minerals and understand its mechanism, this study selected commonly found minerals in soils, namely illite, kaolin, and hematite, as the research objects. Glucose and tannic acid were considered as the representative compounds for studying the adsorption of dissolved organic matter in soils. By analyzing the effects of the three minerals on the adsorption characteristics of glucose and tannic acid after a short-term acidification treatment, this study aimed to explore the underlying mechanism. To achieve this, scanning electron microscopy and a specific surface area analyzer were utilized. The results of this study indicate that the adsorption modes of the minerals studied were unaffected by short-term acidification. Chemisorption, as well as surface and mesopore diffusion, were found to dominate the adsorption process. In terms of adsorption behavior, the minerals exhibited multilayer inhomogeneous adsorption with glucose and kaolin, while tannic acid showed monolayer adsorption with illite and hematite. When exposed to the same acidification conditions, the saturated adsorption of glucose and tannic acid was found to be illite ≥ hematite > kaolin. The kinetic adsorption processes exhibited three stages: fast adsorption, slow adsorption, and adsorption equilibrium. Interestingly, as the intensity of the acidification increased, the saturated adsorption capacity generally followed the trend of S3 (test minerals with pH adjusted to 3 value) > S5 (test minerals with pH adjusted to 5 value) > CK (the control group). The acidification-induced solvation led to an increase in the specific surface area and the number of active adsorption sites on the minerals. Additionally, the protonation reaction triggered a change in the surface charge, which in turn affected the hydrogen bonding, ligand exchange, and charge transfer between the minerals and glucose and tannic acids. These interactions ultimately enhanced the adsorption capacity.

Resolving the Heterogeneous Adsorption of Antibody Fragment on a 2D Layered Molybdenum Disulfide by Super-Resolution Imaging.

The development of nanomaterials such as two-dimensional (2D) layered materials advanced applications in many fields, including biosensors format based on field-effect transistors. The unique physical and chemical properties of 2D layered materials enable the detection limit of biomolecules as low as ∼1 pg/mL. The majority of 2D layered materials contain different structural features and defects introduced in chemical synthesis and fabrication processing. These structural features have different physicochemical properties, causing heterogeneous adsorption of bioreceptors like antibodies, enzymes, etc. Understanding the correlation between the adsorption of bioreceptors and properties of structural features is essential for building highly efficient, sensitive biosensors based on 2D layered materials. Here, we utilize a single-molecule localization-based super-resolved fluorescence imaging method to unveil the inhomogeneous adsorption of antibody fragments on 2D layered molybdenum disulfide (MoS2). The surface coverage of antibody fragments on MoS2 thin flakes is quantitatively measured and compared at different structural features and different layer thicknesses. The methodology in the current work can be extended to study bioreceptor adsorption on other types of 2D layered materials and pave a way to improve biosensors' sensitivity based on defect engineering 2D layered materials.

Plasmonic Sensing: Connecting the Dots.

Plasmonic sensitivity of noble metals has often been attributed to the morphology of the nanostructures and dielectric effects of both the materials and the surrounding medium. The measurable plasmonic shift with respect to the change in local dielectric as a function of analyte concentrations within nanoscale volume forms the basis of plasmonic sensing. However, the situation of the surrounding medium in the presence of multicomponent systems and, moreover, inhomogeneous adsorption around the anisotropic nanostructures become seemingly complicated as the precise description of several individual components becomes nearly impossible. Therefore, we have designed a retrospective formalism through a critical condensation of the electromagnetic scattering theories, macroscopic mixing rules, and micromechanics at the metal-analyte interface that can be adopted as generalized model irrespective of morphology of the nanostructures and the nature of analytes to account for the response of all the individual (microscopic) components to the observed (macroscopic) plasmonic sensing.

Inhomogeneity of polylysine adsorption layers on lipid membranes revealed by theoretical analysis of electrokinetic data and molecular dynamics simulations

The adsorption of large polycations on a charged lipid membrane is qualitatively different from the small inorganic cations, which almost uniformly populate the membrane surface. We assume that the polycationic adsorption layer might be laterally inhomogeneous starting from a certain polymer length, and this effect can be more visible for membranes with low anionic lipid content. To study systems with inhomogeneous adsorption layers, we carried out electrokinetic measurements of mobility of liposomes containing anionic and neutral phospholipids in the presence of polylysine molecules. Some of these systems were simulated by all-atom molecular dynamics. Here we proposed a theoretical approach accounting for the formation of separated regions at the membrane surface, which differ in charge density and surface potential. Our model allowed us to determine the adsorption layer’s geometric parameters such as surface coverage and surface-bound monomer fraction of polymer, which correlate with the molecular dynamics (MD) simulations. We demonstrated that the configuration polylysine adopts on the membrane surface (tall or planar) depends on the polymer/membrane charge ratio. Both theory and MD indicate a decrease in the anionic lipid content, alongside with a decrease in the bound monomer fraction and corresponding increase in the extension length of the adsorbed polymers.

Effect of PCEs with Different Functional Groups on the Performance of Cement Paste

The adsorption behaviors and dispersing properties of polycarboxylate superplasticizer (PCE) with different functional groups were systematically analyzed to reveal the theory and methods of modifying PCE molecular structures and regulating PCE performances. By substituting carboxylic groups with sulfonic groups, ester groups or acylamino groups, respectively, modified PCEs with different functional groups were synthesized. Results show that introducing low amount of ester groups or sulfonic groups into the PCE molecules has no negative effects on the fluidity of cement paste, while introducing acylamino groups into PCE molecules significantly weakens the fluidity of cement paste. At low amount (when the molar ratio of sodium methallyl sulfonate to TPEG is lower than 0.4), the rapid adsorption of sulfonic groups onto the cement particles contributes to the high dispersing performance of the sulfonic group modified PCEs. When the substitution ratio of acrylic acid by sulfonic acid is higher than 0.4, the viscosity and the yield stress of cement paste increases sharply. Redundant sulfonic groups lead to the excessive charge density of the PCE, which contributes to the inhomogeneous adsorption on the cement grains and hence results in the decline of the dispersing performance. Substitution of carboxylic group by acylamino group or ester group slightly changes the viscosity as well as the yield stress of cement paste. Introducing sulfonic group into PCE molecule improves the adsorption behavior of PCEs, while introducing ester group or acylamino group into PCE depresses the adsorption properties.

The efficiency calibration of radioxenon isotopes of inhomogeneous adsorption column for HPGe γ spectrometry

In this paper, a new efficiency calibration scheme is proposed for the inhomogeneous adsorption column, in which the segment efficiencies modeled by the Monte Carlo toolkit Geant4 are weighted according to the fraction distributions of the adsorbed radioxenon based on the equilibrium adsorption theory. In order to verify the scheme, an experiment of efficiency calibration of HPGe detector by employing radon daughters was performed, and as a result the relative errors between the measured value and simulated value was less than ± 2.3%. This method developed in this paper is useful for the development of rapid test device of radioactive gas.

Experimental Investigation of the Self-Propelled Motion of a Sodium Oleate Tablet and Boat at an Oil-Water Interface.

The self-propelled behaviors of macroscopic inanimate objects at surfaces and interfaces are ubiquitous phenomena of fundamental interest in interface science. However, given the existence of a large variety of systems with their own inherent chemical properties, the kinematics of the self-propelled motion and the dynamics of the forces driving these systems often remain largely unknown. Here, we experimentally investigate the spontaneous motion of a sodium oleate tablet at a water-nitrobenzene interface, under nonequilibrium and global isothermal conditions, through measurements of the interfacial tension with the noninvasive, quasi-elastic laser scattering method. The sodium oleate tablet was self-propelled due to an imbalance in the interfacial tension induced by the inhomogeneous adsorption of oleate/oleic acid molecules. The kinetics of the self-propelled motion of a boat-shaped plastic sheet bearing sodium oleate tablets at a sodium oleate aqueous solution-nitrobenzene interface was also studied. The interfacial tension difference between the front and rear of the boat was quantitatively identified as the force pushing the boat forward, although the Marangoni flow due to the uneven distribution of the interfacial tension behind the boat tended to decelerate the motion.

Strain-induced growth instability and nanoscale surface patterning in perovskite thin films.

Despite extensive studies on the effects of epitaxial strain on the evolution of the lattice and properties of materials, considerably less work has explored the impact of strain on growth dynamics. In this work, we demonstrate a growth-mode transition from 2D-step flow to self-organized, nanoscale 3D-island formation in PbZr0.2Ti0.8O3/SrRuO3/SrTiO3 (001) heterostructures as the kinetics of the growth process respond to the evolution of strain. With increasing heterostructure thickness and misfit dislocation formation at the buried interface, a periodic, modulated strain field is generated that alters the adatom binding energy and, in turn, leads to a kinetic instability that drives a transition from 2D growth to ordered, 3D-island formation. The results suggest that the periodically varying binding energy can lead to inhomogeneous adsorption kinetics causing preferential growth at certain sites. This, in conjunction with the presence of an Ehrlich-Schwoebel barrier, gives rise to long-range, periodically-ordered arrays of so-called “wedding cake” 3D nanostructures which self-assemble along the [100] and [010].

Impact of the iron saturation of bovine lactoferrin on adsorption to a strong cation exchanger membrane

Bovine lactoferrin (bLf) is a high-value iron-binding whey protein used for infant nutrition because of several health-promoting activities. The bLf concentration in whey is very low. Most methods for Lf enrichment use ion exchange chromatography since it is highly selective. However, established processes and emerging methods result in a rather low yield, partly due to inhomogeneous adsorption behaviour. To date, reasons for this have not been investigated. In this study, the impact of the state of iron binding on the adsorption of bLf to cation exchangers was investigated as affected by medium conditions. It was found that the iron-depleted apo Lf has a lower adsorption affinity than iron-saturated holo Lf in the acidic pH-range; e.g., at pH 4.8, close to the pH-value of acid whey, less than 70% of apo Lf adsorbed, whereas >85% of holo Lf bound. At physiological pH values, more than 90% of both forms bound.

Adsorption Kinetics and Surface Characterization of Microorganisms Grown under Different Conditions

The adsorption of bacteria onto minerals is the premise for bioleaching and plays an important role in minerals oxidation. Understanding of the adsorption kinetics onto the surface will give information on the effectiveness of bioleaching. Three kinds of mixed bacteria (Acidithiobacillus ferrooxidans, Leptospirillum ferrooxidans, Sulfobacillus) were cultured in different substrates - copper concentrate, elemental sulfur and ferrous iron and adsorbed onto different solid surface of elemental sulfur, silica and copper concentrate. Adsorption kinetics was examined and surface properties were investigated by Zeta-potential and FT-IR spectroscopy. Bacterial adsorption equilibrium data for bacteria grown on three different substrates were well fitted to Freundlich isotherms, indicating inhomogeneous and selective adsorption. Microorganisms grown on copper concentrate and S0 showed similar adsorption kinetics whereby cell adsorptions proceeded rapidly and reached equilibrium within 30 mins of interaction. With the average KF value of 46.2, most copper concentrate-grown cells were strongly adsorbed to three solid surfaces. Microorganisms grown on copper concentrate and S0 also showed higher hydrophobicity and higher isoelectric point (IEP) (pH 3.4-3.8) as compared to the soluble Fe2+-grown cells (pH 2.1), indicating higher amount of EPS and proteins on the surfaces. The FT-IR spectra indicated the presence of COOH, NH2, OH and PO4 groups on all cell surfaces. However, more proteinaceous compounds were found on cells grown on copper concentrate and S0 substrates.

Polymers undergoing inhomogeneous adsorption: Order parameters for a partially directed walk model.

We consider partially directed walk models of polymers undergoing inhomogeneous adsorption. The inhomogeneity can be in the polymer, in the surface, or in both. For the cases where the polymer is either a homopolymer or a strictly alternating copolymer and where the surface is either homogeneous or has stripes of width 1, we calculate detailed order parameters and show that these provide important information about the ways in which the polymer adsorbs.

Molecular Self‐Assembly on Graphene

The formation of ordered arrays of molecules via self-assembly is a rapid, scalable route towards the realization of nanoscale architectures with tailored properties. In recent years, graphene has emerged as an appealing substrate for molecular self-assembly in two dimensions. Here, the first five years of progress in supramolecular organization on graphene are reviewed. The self-assembly process can vary depending on the type of graphene employed: epitaxial graphene, grown in situ on a metal surface, and non-epitaxial graphene, transferred onto an arbitrary substrate, can have different effects on the final structure. On epitaxial graphene, the process is sensitive to the interaction between the graphene and the substrate on which it is grown. In the case of graphene that strongly interacts with its substrate, such as graphene/Ru(0001), the inhomogeneous adsorption landscape of the graphene moiré superlattice provides a unique opportunity for guiding molecular organization, since molecules experience spatially constrained diffusion and adsorption. On weaker-interacting epitaxial graphene films, and on non-epitaxial graphene transferred onto a host substrate, self-assembly leads to films similar to those obtained on graphite surfaces. The efficacy of a graphene layer for facilitating planar adsorption of aromatic molecules has been repeatedly demonstrated, indicating that it can be used to direct molecular adsorption, and therefore carrier transport, in a certain orientation, and suggesting that the use of transferred graphene may allow for predictible molecular self-assembly on a wide range of surfaces.

Entropic effects in diffusion-adsorption processes in micropores

We analyze the kinetics of diffusion-adsorption processes of one component systems in micropores. In realistic situations, the pores exhibit irregular forms which give rise to inhomogeneous adsorption with preferred sites for the adsorbing particles. By modeling the tortuosity of the pores by means of entropic barriers, we obtain a kinetic equation for the averaged concentration of particles along the pore and on its surface. The analysis performed yields expressions for the adsorption rate, the effective diffusion coeffcient, the adsorption isotherms and the concentration of the adsorbed particles. It is shown that this last quantity strongly depends on the form of the pore. This feature opens the possibility to design micropores with an optimal adsorption rate at selected sites. Our results show that to consider the geometry of the pore in the reaction-diffusion scheme is crucial to reproduce experimental observations of the concentration of adsorbed particles in micropores.

Development of Classical Molecule–Surface Interaction Potentials Based on Density Functional Theory Calculations: Investigation of Force Field Representability

A simple classical force field, based only on Coulomb and Lennard-Jones potentials, was developed to describe the interaction of an ethanol molecule physisorbed on the α-alumina (0001) surface. A range of adsorption structures were calculated using density functional theory (DFT) and these results were used for the force field parametrization. This system has a very inhomogeneous adsorption energy landscape, and the importance of the choice of data set used for fitting the force field was investigated. It was found that a Lennard-Jones and Coulombic potential can describe the ethanol–alumina interaction in reasonable qualitative agreement with the DFT reference data, provided that the data set was representative of both short- and long-range interactions and high- and low-energy configurations. Using a few distance-dependent adsorption energy curves at different surface sites gives the best compromise between computing time and accuracy of a Lennard-Jones based force field. This approach demonstrates a systematic way to test the quality of a force field and provides insight into how to improve upon the representability for a complex adsorption energy landscape.

Polymers undergoing inhomogeneous adsorption: exact results and Monte Carlo simulations

We consider several types of inhomogeneous polymer adsorption. In each case, the inhomogeneity is regular and resides in the surface, in the polymer or in both. We consider two different polymer models: a directed walk model that can be solved exactly and a self-avoiding walk model which we investigate using Monte Carlo methods. In each case, we compute the phase diagram. We compare and contrast the phase diagrams and give qualitative arguments about their forms.

Controlling the interaction of poly(ethylene imine) adsorption layers with oppositely charged surfactant by tuning the structure of the preadsorbed polyelectrolyte layer

This study contributes to the understanding of how the structure of preadsorbed polyelectrolyte layers affects their interaction with oppositely charged surfactants. The adsorbed amount, and thus the adsorption layer structure of poly(ethylene imine), (PEI), was tuned by the pH (4, 6 and 9) of the PEI adsorption. Following the PEI adsorption, each adsorption layer was rinsed with 10 mM NaCl solution (pHRinse = 6) to establish identical conditions for further SDS binding. The structure of the PEI adsorption layers was investigated in situ by dual polarization interferometry (DPI). By comparing the DPI results with ellipsometry results and by performing DPI and ellipsometry simulations it could be demonstrated the first time that PEI forms a vertically inhomogeneous adsorption layer that can be described as having a compact bottom part, which contains PEI molecules with a large number of surface contacts, and a swollen outer part, which includes loosely bound PEI molecules that extend far into the bulk phase. The pH of the adsorption controls not only the adsorbed mass but also the structure of the adsorbed layer, which can be further tuned by changing the pH of the rinsing solution. To investigate how the structure of the preadsorbed PEI layer affects its interfacial association with SDS, the preadsorbed polymer layers were rinsed with SDS solutions under identical conditions (10 mM NaCl, pHRinse = 6). It was found that the structure of the preadsorbed PEI layer has a profound effect on the PEI/surfactant interaction. For instance, when the outer part of the PEI layer contained a sufficient amount of polymer segments, desorption of PEI could be prevented. In contrast, when the outer part of the PEI layer was depleted in polymer segments complete desorption could be achieved provided the polymer layer was rinsed with a high concentration (∼cmc) surfactant solution under continuous flow.

Formation of linear carbon chains during the initial stage of nanostructured carbon film growth

The initial stage of nanostructured carbon film growth is investigated by molecular dynamics simulations. The carbon film exhibits amorphous structures with linear chains and cyclic rings on the surface at low incident energies. The structural transformations from linear chains to cyclic rings and to atom networks are observed during the growth process, which is explained in terms of system stability. The atomic adsorption behavior is analyzed through the calculation of the surface potential field. The formation of linear chain structure is due to the predominance of inhomogeneous adsorption of incident atoms on the surface and preferential growth at the tip of the chain. The formation of nanostructures on the surface is argued to be the initial nucleation process of amorphous carbon films.

Comparison between Inhomogeneous Adsorption of Charged Surfactants on Air−Water and on Solid−Water Interfaces by Self-Consistent Field Theory

We use a realistic molecular model to study the interfacial behavior of hydrocarbon sulfate surfactants within a self-consistent field model and consider the adsorption both at the air-water interface and at a hydrophobic solid-water interface. We focus on the structural properties of the hemimicelles at the critical interface aggregation concentration (CIAC) for the air-water system and the critical surface aggregation concentration (CSAC) for the solid-water system. The major difference between the two systems is that the liquid interface is penetrable but the solid surface is intrinsically impenetrable for the molecular species. At the LG interface the hemimicelles have a lens shape with their centers of mass positioned slightly toward the aqueous side and feature an aspect ratio of approximately 2, with the long dimension parallel to the interface. Hemimicelle formation occurs below a critical (interfacial) area per molecule and above a critical surface pressure depending on tail length and ionic strength. Hemimicelles are not expected at air-water interfaces for a surfactant with a tail length ( t) lower than 15 CH2 units. In contrast, at a hydrophobic solid the formation of laterally inhomogeneous micelles even takes place for surfactants with the tail length as short as t = 12. This difference is attributed to the screening of the lateral interactions in the vapor phase. The shape of surface hemimicelles is caplike (or half-lens) with an aspect ratio lower than 2 and the long dimension parallel to the solid surface. The tail length, the ionic strength, the adsorption energies, and the surfactant concentration have an effect on the surface micelle properties such as the aggregation number and size and shape.

Crystallization kinetics of thin amorphous water films on surfaces: Theory and computer modeling

This paper presents a theoretical investigation of the crystallization kinetics of thin adsorbed amorphous water films mainly based on our recently published experimental results [Lofgren et al., Langmuir 19 (2003) 265]. A nucleation simulation model, in which the time course of the growth of each crystalline grain is explicitly modelled, is presented and used to determine the location of the nucleation to be both in the bulk and at the substrate/water interface. The model also shows that a non-zeroth order of desorption from the bulk layer can be related to inhomogeneous adsorption. Further, a thermodynamic analysis of the experimental data is presented. At 145 K the critical size of a (bulk) ice nucleus is approximately 40 water molecules and the nucleation rate constant is 10−6 s−1.