Real-time measurement of solute partitioning to lipid monolayers

The interaction of a peripheral protein with a lipid-water interface can show a pronounced dependence on the composition and two-dimensional packing density of the lipids that comprise the interface. We report a novel optical method for measuring the adsorption of macromolecules, such as proteins and nucleic acids, and smaller solutes, such as drugs, to lipid monolayers at the gas-liquid interface. Using fluorescence emission from proteins and a small molecule, we demonstrate that the emissions from these solutes when in the aqueous phase and when associated with the monolayer can be temporally separated. Such separation allows measurement of the extent of solute adsorption, spectral characterization of the adsorbed solute, and characterization of lipid organization using adsorption kinetics. The method does not require, but is compatible with, the solute having different spectral properties in the bulk and surface phases. Indeed, if optical signals from adsorbed and soluble solute are the same or their relationship is known, absolute surface excess of adsorbed solute can be calculated without independent calibration. With appropriate instrumental configuration, the method should be adaptable for screening solutes for interaction with planar monolayers having both well-defined composition and adjustable lipid packing density.     

New method for incorporating solvent influence into the evaluation of X-ray scattering intensity of proteins in solution

A new method, the surface integration method, is presented for taking into account the influence of solvent on the intensity of X-ray scattered from proteins in solution. It requires no averaging numerically over the solute orientation. The solvent is modeled by a continuous medium with electrons of uniform density. This method is applied to amino acids, peptides and native proteins to confirm its effectiveness. The solvent influence on the normalized scattering intensity I(K) I(0) is more noticeable for larger solutes and at larger scattering angles, where I(K) is the intensity of scattered X-ray with the magnitude of scattering vector K.     

Monte Carlo Simulation Study of Adsorption Characteristics in Slit-Like Micropores Under Supercritical Conditions

Abstract

Adsorption characteristics of a solute diluted in supercritical fluids has been investigated by using the Monte Carlo simulation techniques. The Lennard-Jones potential function is used for describing interactions for a model system of CO₂ + benzene in slit-like micropores with infinite graphitic carbon walls. A modified μVT ensemble method with particle exchange proposed by Cracknell, Nicholson and Quirke (1993) is found to be much superior to the conventional μVT ensemble method especially for dense mixtures in a pore. Adsorption isotherms of CO₂ and benzene, in equilibrium with a dilute benzene mixture in CO₂ (mole fraction of benzene = 0.001), are computed by varying pressure, temperature, the benzene–surface interaction potential, and the slitwidth. Adsorption isotherm curve of CO₂ increases with an increase in pressure while that of benzene shows a maximum at a pressure far below the critical pressure of CO₂ and then it decreases with increasing pressure. The decrease in benzene adsorption with increasing pressure is attributable to both the enhanced solubility in supercritical CO₂ and the competitive adsorption of CO₂. The isotherm curves of each component at two temperatures, 313.2 K and 323.2 K, show to cross at a pressure near the critical pressure due to the “density effect” on the chemical potentials of a solute at supercritical fluid conditions. When the interaction between a solute and a surface increases, the adsorption isotherm increases. Narrowing the slitwidth results in the increase in the adsorption of solute since the external potential from two walls becomes deeper.     

Molecular dynamics simulation of doxorubicin adsorption on a bundle of functionalized CNT

In this study, molecular dynamics simulation is used to investigate the adsorption of an anticancer drug, doxorubicin, on bundles of functionalized single-walled carbon nanotubes (SWNTs) in an aqueous solution. Carboxylic group has been selected as the functional group. Molecular dynamics (MD) simulations are performed for both separated systems containing a SWNT bundle and a functionalized carbon nanotube bundle, and results are compared with existing experimental data. MD results show that doxorubicin can be adsorbed on CNTs using different methods such as entrapment within CNT bundle, attachment to the side wall of the CNT, and adsorption on the CNT inner cavity. For functionalized CNT, the adsorption of drugs on the functional groups is essential for predicting the enhancement of drug loading on the functionalized nanotubes. Furthermore, the adsorption behavior of doxorubicin on CNTs is fitted with Langmuir and Freundlich isotherm models. The results show that Langmuir model can predict the adsorption behavior of doxorubicin on CNTs more accurately than Freundlich model does. As predicted by this isotherm model, the adsorption process of doxorubicin on CNTs is relatively difficult, but it can be improved by increasing the functional groups on the CNTs surface.     

A theory of cell hydration governed by adsorption of water on cell proteins rather than by osmotic pressure

It is postulated that cell hydration is governed by adsorption of water on cell proteins in accord with the Bradley adsorption isotherm, and that the action of a solute in the surrounding solution is to lower the vapor pressure of the solution so that cell water adsorption is decreased by moving down the Bradley isotherm. From these concepts, it is derived that cell volume (V) should be related to solute concentration (x) by the equationV=−E log₁₀ x+F whereE andF are constants which are independent of type of solute. For a non-adsorbed solute this agrees well with experimental data. For solutes which are adsorbed by cell proteins, a correction in the above equation may be necessary at higher solute concentrations, which is shown to be compatible with various experimental data. The types of experiments which are generally used to support the osmotic pressure theory of cell hydration agree equally well with the adsorption theory. The virtue of the adsorption theory is that, unlike the osmotic pressure theory of cell swelling, it is compatible with permeability of the cell membrane to solutes, which has been experimentally observed for various solutes. The opinions and conclusions contained in this report are those of the author. They are not to be construed as necessarily reflecting the views or the endorsement of the Navy Department.     

Adsorption of fluorescein by protein crystals

Adsorption characteristics of native and cross-linked lysozyme crystals were examined using fluorescein as model adsorbate. The adsorption isotherms exhibited Langmuir or linear behavior. The affinity constant (b1) and the adsorption capacity (Qsat) for fluorescein were found to depend on the type and concentration of co-solute present in the solution. The dynamics of adsorption isotherm transition from Langmuir to linear showed that affinity of lysozyme for solutes increases in the order 2-(cyclohexylamino)ethanesulphonic acid (CHES), 4-morpholinepropanesulphonic acid (MOPS), acetate, fluorescein. Furthermore, the crystal morphology, the degree of cross-linking of the crystals, and, in particular, solution pH were identified as factors determining fluorescein adsorption by the lysozyme crystals. These factors seem to affect crystal capacity for the solute more than affinity for the solute. Adsorption of fluorescein by cross-linked tetragonal lysozyme crystals was exponentially dependent on the lysozyme net charge calculated from the final solution pH. The 3-5-fold increase in the fluorescein adsorption as a result of cross-linking is presumably due to the increasing hydrophobicity of the lysozyme crystal.     

Adsorption into the MFI zeolite of aromatic molecule of biological relevance. Investigations by Monte Carlo simulations

Adsorption of paracresol and water into the silicalite-1 (MFI) zeolite has been investigated using canonical and grand-canonical Monte Carlo simulations. The most stable sites of adsorption of paracresol are found to be located at the channel intersections. Grand-canonical simulations have shown that at low loading, water molecules adsorb preferably at the vicinity of paracresol molecules, whereas they are also located in the sinusoidal channels as the loading increases. In order to explain the experimental adsorption isotherm observed for the coadsorption of water and paracresol in the MFI zeolite we propose a new concept of apparent adsorption enthalpy that varies with the concentration of the solution. The mathematical expression for the apparent enthalpy is introduced in an adsorption isotherm model. We shall refer to this theoretical isotherm as a non-langmuirian isotherm. The non-linear expression for the apparent adsorption enthalpy accounts for a variable accessibility of the sites of adsorption with respect to the concentration of the solution. Figure Co-adsorption of paracresol and water in silicalite-1 zeolite and comparison between experimental and modelled adsorption isotherms.     

Structure of Lennard–Jones fluid near large spherical particles: further test of the “universality” of adjustable parameter in perturbation density functional theory

Grand canonical Monte Carlo simulation is used to study the density profiles of Lennard–Jones (LJ) fluid next to a large hard sphere (mimicking a colloidal particle) of various sizes. The LJ fluid in the inhomogeneous system thus maintains equilibrium with the bulk LJ fluid. The chosen density and potential parameters for the bulk fluid correspond to the conditions situated at “dangerous” regions of the phase diagram, i.e. near the critical temperature or close to the gas–liquid coexistence curve. The aim of present extensive simulations is to provide exact data for the broad range of the bulk parameters against which the “universality” of adjustable parameter associated with a perturbation density functional approximation (DFA) can be tested. Here the term “universality” means independence of this parameter on the particular external field responsible for the generation of a non-uniform density profile of the fluid. It is shown that the “universality” of this parameter associated with a third order+second order perturbation DFA holds also in the present case of a large spherical particle as a source of external potential, similarly as established in previous studies dealing with other interaction potential and other external fields [J. Chem. Phys., 122, 064503 (2005); J. Chem. Phys., 123 124708 (2005)]. This DFA can be used as input into a recently proposed framework for the calculation of interparticle potential of mean force (PMF).     

Molecular simulation of adsorption from dilute solutions

Adsorption of biomolecules on surfaces is a perennial and general challenge relevant to many fields in biotechnology. A change of the Helmholtz free energy DeltaA takes place when a molecule becomes adsorbed out of a bulk solution. The purpose of our investigations is to explore routes for the calculation of DeltaA by molecular simulations. DeltaA can be obtained both by integration over the mean force on a molecule and via the local density. It turns out that the route via the potential of mean force prevails over the latter due to better consistency. In this work we present results for systems of 1-centre and 2-centre Lennard-Jones mixtures at a 9/3 Lennard-Jones wall.     

Adsorption and structure of benzene confined in disordered porous carbons: effect of pore heterogeneity and surface chemistry

Molecular simulations are used to study the adsorption of benzene at 300?K in atomistic models of disordered nanoporous carbons. These models, named as CS400, CS1000 and CS1000a, differ in density and chemical compositions, and reproduce the morphological and topological features present in real nanoporous carbons. We found that the adsorption phenomena depend upon the local structure of nanoporous carbons. To understand the effect of surface chemistry on adsorption and structure of confined benzene, functional groups (–COOH and –C=O) were added to these models. The presence of functional groups led to the onset of adsorption process at a low pressure. The carboxyl groups (–COOH) have a greater impact on adsorption as compared to carbonyl (–C=O) groups. The CS1000a models have wide micropores and thus it exhibits a jump in adsorption isotherm. The jump shifts towards lower pressure on the addition of functional groups, with –COOH groups showing a larger shift. The presence of functional groups also increases the isosteric heat of adsorption, with –COOH groups showing higher values. The coulombic contribution to total fluid–wall interaction energy is higher for –COOH functional groups and decreases on increasing pressure. Benzene confined in CS1000a models exhibit a liquid-like structure.     

Optimum Sorption Isotherm by Linear and Nonlinear Methods for Safranin onto Alkali-Treated Rice Husk

Rice husk, a lignocellulosic by-product of the agroindustry, was treated with alkali and used as a low-cost adsorbent for the removal of safranin from aqueous solution in batch adsorption procedure. In order to estimate the equilibrium parameters, the equilibrium adsorption data were analyzed using the following two-parameter isotherms: Freundlich, Langmuir, and Temkin. A comparison of linear and nonlinear regression methods in selecting the optimum adsorption isotherm was applied on the experimental data. Six linearized isotherm models (including four linearized Langmuir models) and three nonlinear isotherm models are thus discussed in this paper. In order to determine the best-fit isotherm predicted by each method, seven error functions namely, coefficient of determination (r ²), the sum of the squares of the errors (SSE), sum of the absolute errors (SAE), average relative error (ARE), hybrid fractional error-function (HYBRID), Marquardt's percent standard deviation (MPSD), and the chi-square test (χ²) were used. It was concluded that the nonlinear method is a better way to obtain the isotherm parameters and the data were in good agreement with the Langmuir isotherm model.     

Molecular dynamics simulation of water confined in a nanopore of amorphous silica

Molecular dynamics simulations are performed to study the transport and structural properties of water confined in a cylindrical silica nanopore. The pore wall is amorphous and mimics a typical mesoporous silica material. The diameters of silica pores studied are 4.75, 9.51, 20 and 25 Å. The self-diffusion of water calculated decreases with pore size and indicates much slower transport compared to the bulk phase. Strong adsorption of water to the silica wall is observed in the density profiles, indicating the hydrophilic nature of the wall. The hydrogen-bonding network is strongly affected by water–silica wall interaction. The average number of hydrogen bonds per water decreased with decreasing pore diameter.     

Tension at the Surface: Which Phase Is More Important,Liquid or Vapor?

Tension at the surface is a most fundamental physicochemical property of a liquid surface. The concept of surface tension has widespread implications in numerous natural, engineering and biomedical processes. Research to date has been largely focused on the liquid side; little attention has been paid to the vapor—the other side of the surface, despite over 100 years of study. However, the question remains as to whether the vapor plays any role, and to what extent it affects the surface tension of the liquid. Here we show a systematic study of the effect of vapor on the surface tension and in particular, a surprising observation that the vapor, not the liquid, plays a dominant role in determining the surface tension of a range of common volatile organic solutions. This is in stark contrast to results of common surfactants where the concentration in the liquid plays the major role. We further confirmed our results with a modified adsorption isotherm and molecular dynamics simulations, where highly structured, hydrogen bonded networks, and in particular a solute depletion layer just beneath the Gibbs dividing surface, were revealed.     

On the Bond-angle Distributions in Liquids and Liquid Solutions

Bond-angle distributions are used for the study of local orientational order in liquid systems. Bond-angles between a central particle and particles in both the first and second coordination shells are considered. Molecular dynamics calculations are carried out for determining the bond-angle distributions in a Lennard Jones liquid. The resulting distributions are compared with those obtained from stochastic simulations of a subset of atoms (solute) of the same system (solution). Although the radial distribution functions from the two simulations are in agreement, the bond-angle distributions show noticeable difference. Computer simulation findings are compared with results obtained by using both the superposition and convolution approximations. The reliability of the generalized Langevin dynamics simulation method is discussed.     

Statistical mechanics approach to inhomogeneous van der Waals fluids

A general methodology is proposed to formulate density functional approximation (DFA) for inhomogeneous van der Waals fluids. The present methodology needs as input only a hard sphere DFA, second order direct correlation function (DCF) and pressure of coexistence bulk fluid, and therefore can be applicable to both supercitical and subcritical temperature regions. As illustrating example, the present report combines a recently proposed hard sphere “Formally exact truncated non-uniform excess Helmholtz free energy density functional approximation” with the present methodology, and applies the resultant DFA to calculate density profile of the inhomogeneous Lennard-Jones (LJ) fluid in coexistence with a bulk LJ fluid being situated at “dangerous” regions, i.e. the coexistence bulk state is near the critical temperature or the gas-liquid coexistence line. The theoretical predictions are in very good agreement with the recent simulation results, it is concluded that the present DFA is a globally excellent one. A discussion is given why the present methodology can lead to so excellent DFA.     

Effect of blood flow on near-the-wall mass transport of drugs and other bioactive agents: a simple formula to estimate boundary layer concentrations

Transport of bioactive agents through the blood is essential for cardiovascular regulatory processes and drug delivery. Bioactive agents and other solutes infused into the blood through the wall of a blood vessel or released into the blood from an area in the vessel wall spread downstream of the infusion/release region and form a thin boundary layer in which solute concentration is higher than in the rest of the blood. Bioactive agents distributed along the vessel wall affect endothelial cells and regulate biological processes, such as thrombus formation, atherogenesis, and vascular remodeling. To calculate the concentration of solutes in the boundary layer, researchers have generally used numerical simulations. However, to investigate the effect of blood flow, infusion rate, and vessel geometry on the concentration of different solutes, many simulations are needed, leading to a time-consuming effort. In this paper, a relatively simple formula to quantify concentrations in a tube downstream of an infusion/release region is presented. Given known blood-flow rates, tube radius, solute diffusivity, and the length of the infusion region, this formula can be used to quickly estimate solute concentrations when infusion rates are known or to estimate infusion rates when solute concentrations at a point downstream of the infusion region are known. The developed formula is based on boundary layer theory and physical principles. The formula is an approximate solution of the advection-diffusion equations in the boundary layer region when solute concentration is small (dilute solution), infusion rate is modeled as a mass flux, and there is no transport of solute through the wall or chemical reactions downstream of the infusion region. Wall concentrations calculated using the formula developed in this paper were compared to the results from finite element models. Agreement between the results was within 10%. The developed formula could be used in experimental procedures to evaluate drug efficacy, in the design of drug-eluting stents, and to calculate rates of release of bioactive substances at active surfaces using downstream concentration measurements. In addition to being simple and fast to use, the formula gives accurate quantifications of concentrations and infusion rates under steady-state and oscillatory flow conditions, and therefore can be used to estimate boundary layer concentrations under physiological conditions.     

Effect of various surface conditions on nanochannel flows past permeable walls

In this paper, effects of surface conditions on the gas flow in nanochannels with permeable walls have been investigated by molecular dynamics simulations. The hydrodynamic characteristics of the gas flow in nanochannels, including the density distributions, slip length and boundary friction coefficient, have been significantly influenced by the molecular interactions between gas molecules and wall atoms. The density layering phenomena are observed at the fluid–wall interface under a strong fluid–wall interaction (FWI). Particularly, there is a peak of the gas density on the permeable surface where the gas density is increased and about 3 times larger than the bulk one under the strong FWI. It indicates a strong non-continuum density distribution on the permeable surface and the step down in density from nanopores to the bulk region. On the other hand, the nanoscale vortices are produced in the nanopores. Moreover, the mass flux of gas flow in nanopores is reduced, and the hydrodynamic boundary has been shifted above the permeable surface further under the weak FWI. Slip characteristics on the permeable surface under various conditions are explored. It has been found that the slip length on the permeable surface may vary as a logarithmic function with the molecular mean free path. Apparently, the skin friction on the permeable surface is affected by the velocity slip. These results are significant in the understanding of nanoscale hydrodynamics.     

Adsorption affinity of tea catechins onto polymeric resins: Interpretation from molecular orbital theory

Adsorption of certain tea catechins such as (+) catechin (C), (−) epicatechin (EC), (+) gallocatechin (GC), (−) epigallocatechin (EGC), (+) catechin gallate (CG), (−) epicatechin gallate (ECG), (+) gallocatechin gallate (GCG), and (−) epigallocatechin gallate (EGCG) have been studied using three types of polymeric resins as adsorbents. Adsorption affinity expressed as the slope of the linear region of the isotherm for a solute is found to be different for different adsorbents, and this difference can be interpreted from the chemical nature of the sorbents. Molecular interactions on polymeric resins have been studied based on molecular orbital theory. Electronic states of adsorbent and adsorbate were calculated using the semiempirical molecular orbital (MO) method from which energy of adsorption in aqueous solution was estimated. The adsorptive interaction on the polymeric resins computed on the basis of frontier orbital theory seems to correlate well with the experimentally measured adsorption affinity and enthalpy.     

The effects of structural parameters of zeolite on the adsorption of hydrogen: a molecular simulation study

The adsorption isotherm of hydrogen in zeolites FAU, LTA, KFI, RWY, RHO and TSC has been simulated employing grand canonical Monte Carlo procedure for a temperature range of 77 to 95 K and different pressures. The effects of structural composition, unit cell volume, framework density and specific surface area of zeolite on hydrogen adsorption in zeolites were investigated. The results clearly show that the adsorption of hydrogen in zeolites with the same silica density is a function of oxygen density at low pressures, and it is approximately the same at intermediate pressures. Nevertheless, at high pressures, the adsorption of hydrogen is a function of pore diameter for zeolites with same silica density. The effect of specific surface area on the adsorption isotherm of hydrogen on zeolites with approximately the same specific surface area is significant at low and high pressures. The results clearly indicate that the adsorption of hydrogen in RWY zeolite has maximum value at 77 K and at high pressures. The optimum condition of pressure for hydrogen adsorption isotherm in RWY zeolite is determined to be 600 bar. At a temperature of 77 K and a pressure of 600 bar, the adsorption of hydrogen in RWY zeolite is 6.93 wt %.     

Molecular simulation on the interaction of Ethinylestradiol (EE2) with polymer membranes in wastewater purification

Molecular dynamics (MD) simulations are performed to study the adsorption of solute organic molecules (Ethinylestradiol (EE2) and testosterone) with different polymer membranes such as polyether sulfone (PES), polyvinylidene fluoride (PVDF). The equilibrium MD simulations results for the membrane solution interface system show that the interaction of EE2 with PES is specific and strong, whereas the interaction is weak and non-specific for PVDF. The binding free energies, the non-bonded short range interaction energies and mobility are also consistent with the interaction behaviour found in experiments. The adsorption of testosterone onto PES and PVDF is considered as control system. The result shows that binding free energies of PES and PVDF interacting with organic solute are consistent with experimental result in the order as; PES-EE2 > PES-Testosterone > PVDF-EE2 > PVDF-Testosterone. The formation hydrogen bonds and π–π interactions are observed between the EE2 and PES. In addition, adsorption of EE2 onto polyamide 6-12 (PA612) and polystyrene (PS) membranes are predicted. This simulation study provides molecular insights on the experimental observations and helps as a computational methodology to screen the membrane materials for EE2 removal from wastewater.