Phagostimulatory effect of uptake of PLGA microspheres loaded with rifampicin on alveolar macrophages

In this work we obtain the thermodynamic properties of mixed (1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine) PC and (1-stearoyl-2-oleoyl-sn-glycero-3-phospho-l-serine (sodium salt)) PS monolayers. Measurements of compressibility (isotherms, bulk modulus, and excess area per molecule) and surface potential show that the properties of monolayers at the air–water interface depend on the concentration of ions (Na⁺ and K⁺) and the proportion of PS in the mixture. The dependence on PS arises because the molecule is originally bound to a Na⁺ counterion; by increasing the concentration of ions the entropy changes, creating a favorable system for the bound counterions of PS to join the bulk, leaving a negatively charged molecule. This change leads to an increase in electrostatic repulsions which is reflected by the increase in area per molecule versus surface pressure and a higher surface potential. The results lead to the conclusion that this mixture of phospholipids follows a non ideal behavior and can help to understand the thermodynamic behavior of membranes made of binary mixtures of a zwitterionic and an anionic phospholipid with a bound counterion.     

Molecular dynamics simulation of glycine zwitterion in aqueous solution

A classical molecular dynamics method was used to study the modifications of the solution structure and the properties of glycine zwitterion in aqueous solution due to the increase of glycine zwitterion concentration and the incorporation of Na(+) and Cl(-) ions to the solution. The glycine zwitterion had fundamentally a hydrophilic behavior at infinite dilution, establishing around six hydrogen bonds with the water molecules that surrounded it, which formed a strong hydration layer. Because of the increase of glycine zwitterion concentration, the hydration structure became more compact and the quantity of water molecules bound to this molecule decreased. The Na(+) ion bound to the CO(2) group of glycine, while the Cl(-) ion bound mainly to the NH(3) group of this molecule. The integration of the ions to the hydration layer of the glycine zwitterion produced modifications in the orientational correlation between atoms of glycine zwitterion and water that surrounded them and an increase of the approaches between the glycine zwitterion molecules. The incorporation of ions to the solution also produced changes in the water-water orientational correlation. Decreases of the water-water hydrogen bonds and diffusion coefficient of all molecules were observed when the glycine zwitterion concentration increased and when the ions were incorporated to the solution.     

Effects of Calcium Ions on Thermodynamic Properties of Mixed Bilirubin/Cholesterol Monolayers

The mixed monolayer behavior of bilirubin/cholesterol was studied through surface pressure-area (?-A) isotherms on aqueous solutions containing various concentrations of calcium ions. Based on the data of ?-A isotherms, the mean area per molecule, collapse pressure, surface compressibility modulus, excess molecular areas, free energy of mixing, and excess free energy of mixing of the monolayers on different subphases were calculated. The results show an expansion in the structure of the mixed monolayer with Ca2+ in subphase, and non-ideal mixing of the components at the air/water interface is observed with positive deviation from the additivity rule in the excess molecular areas. The miscibility between the components is weakened with the increase of concentration of Ca2+ in subphase. The facts indicate the presence of coordination between Ca2+ and the two components. The mixed monolayer, in which the molar ratio of bilirubin to cholesterol is 3:2, is more stable from a thermodynamic point of view on pure water. But the stable 3:2 stoichiometry complex is destroyed with the increase of the concentration of Ca2+ in subphase. Otherwise, the mixed monolayers have more thermodynamic stability at lower surface pressure on Ca2+ subphase.     

Thermodynamic characteristics and Langmuir-Blodgett deposition behavior of mixed DPPA/DPPC monolayers at air/liquid interfaces

The role of dipalmitoylphosphatic acid (DPPA) as a transfer promoter to enhance the Langmuir-Blodgett (LB) deposition of a dipalmitoylphosphatidylcholine (DPPC) monolayer at air/liquid interfaces was investigated, and the effects of Ca2+ ions in the subphase were discussed. The miscibility of the two components at air/liquid interfaces was evaluated by surface pressure-area per molecule isotherms, thermodynamic analysis, and by the direct observation of Brewster angle microscopy (BAM). Multilayer LB deposition behavior of the mixed DPPA/DPPC monolayers was then studied by transferring the monolayers onto hydrophilic glass plates at a surface pressure of 30 mN/m. The results showed that the two components, DPPA and DPPC, were miscible in a monolayer on both subphases of pure water and 0.2 mM CaCl2 solution. However, an exception occurs between X(DPPA)=0.2 and 0.5 at air/CaCl2-solution interface, where a partially miscible monolayer with phase separation may occur. Negative deviations in the excess area analysis were found for the mixed monolayer system, indicating the existence of attractive interactions between DPPA and DPPC molecules in the monolayers. The monolayers were stable at the surface pressure of 30 mN/m for the following LB deposition as evaluated from the area relaxation behavior. It was found that the presence of Ca2+ ions had a stabilization effect for DPPA-rich monolayers, probably due to the association of negatively charged DPPA molecules with Ca2+ ions. Moreover, the Ca2+ ions may enhance the adhesion of DPPA polar groups to a glass surface and the interactions between DPPA polar groups in the multilayer LB film structure. As a result, Y-type multilayer LB films containing DPPC could be fabricated from the mixed DPPA/DPPC monolayers with the presence of Ca2+ ions.     

Effect of Na+, Mg2+, and Zn2+ chlorides on the structural and thermodynamic properties of water/n-heptane interfaces

The effect on the structural and thermodynamic properties in water/n-heptane interfaces on addition of NaCl, MgCl(2), and ZnCl(2) has been examined through five independent 100-ns molecular dynamics simulations. Results indicate that the interfacial thickness within the framework of the capillary-wave model decreases on addition of electrolytes in the order Na(+) < Mg(2+) < Zn(2+), whereas the interfacial tension increases in the same order. Ionic density profiles and self-diffusion coefficients are strongly influenced by the strength of the first hydration shell, which varies in the order Na(+) < Mg(2+) < Zn(2+). On the other hand, the Cl(-) behavior, that is, diffusion and solvation sphere, is influenced by its counterion. Accordingly, cations are strongly expelled from the interface, which is especially remarkable for the small divalent cations. This fact alters the water geometry near the interface and in a lesser extent n-heptane order and number of hydrogen bonds per water molecule close to the interface.     

Specific influence of univalent cations on the ionization of alumina-coated TiO2 particles and on the adsorption of poly(acrylic)acid

A surface counterion titration method was used to monitor the interaction of monovalents cations (Li(+), Na(+), TMA(+)) with the surface of alumina-coated TiO(2) particles in concentrated media at different pH and electrolyte concentrations. This method allows measuring separately the negative and positive contribution to the surface charge. It showed that Cl(-) and TMA(+) are indifferent ions, but Li(+) and Na(+) specifically adsorb on the non-ionized alumina surface sites. The binding sequence of cations is Li(+)>Na(+)>TMA(+) at all ionic strengths investigated and is consistent with the structure-making and structure-breaking model developed a few decades ago. Polyacrylic acid (PAA) previously neutralized with the corresponding hydroxide (LiOH, NaOH, TMAOH) has been adsorbed on the alumina surface at different pH. The polymer counterion has a significant influence on the polymer adsorption. The sequence of the surface coverage as a function of the polymer counterion follows the order Li-PAA > Na-PAA > TMA-PAA. The much higher surface coverage with Li-PAA and Na-PAA compared to TMA-PAA is explained by the specific adsorption of Li-PAA and Na-PAA on the nonionized alumina surface sites, the same way LiCl and NaCl do.     

Validating affinities for ion-lipid association from simulation against experiment

Understanding biological membranes at physiological conditions requires comprehension of the interaction of lipid bilayers with sodium and potassium ions. These cations are adsorbed at palmitoyl-oleoyl-phosphatidylcholine (POPC) bilayers as indicated from previous studies. Here we compare the affinity of Na(+) and K(+) for POPC in molecular dynamics (MD) simulations with recent data from electrophoresis experiments and isothermal calorimetry (ITC) at neutral pH. NaCl and KCl were described using GROMOS or parameters matching solution activities on the basis of Kirkwood-Buff theory (KBFF), and K(+) was also described using parameters by Dang et al., all in conjunction with the Berger parameters for the lipids and the SPC water model. Apparent binding constants of GROMOS-Na(+) and KBFF-K(+) are the same within error and in good agreement with values from ITC. Although these force fields yield the same number of bound ions per number of lipids for Na(+) and K(+), they give a larger number of Na(+) ions per surface area compared to K(+), in agreement with the electrophoresis experiments, because Na(+) causes a stronger reduction in the area per lipid than K(+). The intrinsic binding constants, on the other hand, are reproduced by Dang-K(+) but overestimated by GROMOS-Na(+) and KBFF-K(+). That no ion force field reproduces the intrinsic and the apparent binding constant simultaneously arises from the fact that in MD simulations, implicitly meant to mimic neutral pH, pure PC is usually modeled with zero surface charge. In contrast, POPC at neutral conditions in experiment carries a low but significant negative surface charge and is uncharged only at acidic pH as indicated from electrophoretic mobilities. Implications for future simulation and experimental studies are discussed.     

The competitive adsorption of counter-ions at the surface of anionic surfactants solution

We have determined the surface excess of surface active anion and counter-ions in a non-aqueous polar solution of anionic surfactants blends, as well as their distributions near the solution surface. The blends of two anionic surfactants, sodium dodecyl sulfate (SDS) and cesium dodecyl sulfate (CDS), with different contents were used as solutes to prepare the solutions. According to the isotherms that are separately fitted to the pure SDS and the pure CDS solutions (C. Wang and H. Morgner, Langmuir, 2010, 26, 3121), CDS has a slightly but significantly higher surface excess than SDS (CDS is 14.8% higher) at the concentration of 0.04 molal kg(-1) solvent. Therefore, in this work we chose 0.04 molal kg(-1) solvent as total anion concentration and varied the contents of surfactants. From present experimental results, we found that the surface excess of anion increases slightly with the CDS in the bulk content. Importantly, the fractions of Cs(+) in cationic surface excess are higher than its contents in the bulk for all three solutions. This demonstrates that Cs(+) is more competitive than Na(+) in the adsorption. The surface structure of the solutions have been characterized by concentration-depth profiles, of Cs(+), Na(+) and of sulfur which is used to identify dodecyl sulfate. Those profiles evidence that Cs ions penetrate deeper than sodium ions into the layer formed by the heads of the anions, reducing the electrical potential of the surface more efficiently. This can be used to explain the adsorption competition between those two counter-ions. The cause that makes Cs(+) more competitive than Na(+) in the adsorption can be attributed to its less tightly bound solvation shell, and thus, to its effectively smaller ion size.     

Effect of the nature of the counterion on the interaction between cesium and tetraalkylammonium dodecylsulfates and poly(ethylene oxide) or poly(vinylpyrolidone)

The interaction between poly(ethylene oxide) or poly(vinylpyrrolidone) and cesium and tetraalkylammonium (tetramethyl to tetrabutyl ammonium) dodecylsulfate has been investigated by means of electrical conductivity measurements to determine the critical aggregation concentration (cac) of the surfactants in the presence of polymer. The cac values were compared to the values of the critical micellization concentration (cmc) of the surfactants in the absence of polymer. The value of the cac/cmc ratio increased with the radius of the counterion in the sequence: Na(+)相似文献   

Influence of alpha-hydroxylation of glycolipids on domain formation in lipid monolayers

By means of fluorescence and scanning force microscopy (SFM), we investigated the phase behavior of lipid monolayers composed of a mixture of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, sphingomyelin, and cholesterol (5/2/3) with either alpha-hydroxylated or nonhydroxylated galactocerebroside. Fluorescence images of lipid monolayers at the air-water interface demonstrate that, independent of the lipid mixture, phase separation occurs at low surface pressure up to 4-6 mN m(-1), while an almost homogeneous phase is observed at larger surface pressures. However, by means of SFM of lipid monolayers transferred by the Langmuir-Blodgett technique at around 30 mN m(-1), nanometer-sized domains became discernible in those lipid mixtures that contained galactocerebroside, while, in that without a glycolipid, no such domain formation was visible. Moreover, the alpha-hydroxy group of the galactocerebroside alters the size and the total area of the domains significantly.     

Lithium ion induced stabilization of the liquid crystalline DNA

A comparative study of the effects of alkali metal ions Li(+), Na(+), K(+), Rb(+), and Cs(+) on the liquid crystalline organization of high-molecular-weight calf thymus DNA using polarized light microscopy was performed. Major differences in the behavior of Li(+) as compared to the other ions were found. Critical DNA concentration expected to exhibit anisotropic behavior was found to be the same for all the monovalent ions, except for Li(+). DNA initially showed cholesteric textures, which later changed to higher ordered columnar phase for all ions, with the cholesteric-columnar transition facilitated upon increasing the size of the counterion. For Li(+) ion, a nematic schlieren-like texture was formed initially, which after a few days changed to a highly stable (for more than 2 months) biphasic cholesteric-columnar arrangement. The observed differences between Li(+) and other alkali metal ions could be rationalized on the basis of the higher number of hydration water molecules of Li(+) and its complexation behavior. Highly stable DNA mesophases may find applications in the field of nanoelectronics, in designing biosensing units, and in DNA chips.     

Influence of the Hofmeister series of anions on the molecular organization of positively ionized monolayers of a viologen derivative

The effects of the Hofmeister series of ions are ubiquitous in chemistry and biology. In this paper specific ion effects on the surface behavior of a viologen dication, namely 1,1(')-dioctadecyl-4,4(')-bipyridilium, are shown. Surface pressure and surface potential vs area isotherms were obtained on aqueous subphases containing potassium salts with several representative counterions in the Hofmeister series (C6H5O3-7, SO2 -4, HPO2-4, Cl-, Br-, NO-3, I-, and ClO-4). The parameters obtained from the compression isotherms (area per molecule, phase transitions, Young modulus, initial surface potential, and variation of the surface potential upon compression) are dependent on the nature of the counterion, indicating ion specificity. Aqueous subphases containing C6H5O3-7, SO2-4, and HPO2-4 anions yield more expanded viologen monolayers and these anions do not effectively penetrate into the monolayer. Brewster angle microscopy was used to map the different phases of the viologen monolayers at the air-water interface. The Langmuir films were also characterized by UV-vis spectroscopy, with quantitative analysis of the reflection spectra supporting an organizational model in which the viologen chromophore undergoes a gradual transition to a more vertical position with respect to the water surface upon compression. A comparison of the tilt angles of the viologen on the different subphases indicates that anions that can more easily penetrate in the monolayer permit the viologen moieties to adopt a slightly more vertical position with respect to the water surface.     

Characterisation via electrospray ionisation multistage mass spectrometry of three related series of nitrido technetium complexes containing phosphinothiolate and dithiocarbamate ligands

Nine nitrido technetium compounds comprising bis-substituted Tc(N)(PS)(2) (1-4) (PS = bidentate phosphinothiolate ligands) and Tc(N)(dtc)(2) (5, 6) derivatives (dtc = bidentate dithiocarbamate), and mixed-ligand Tc(N)(PS)(dtc) (7-9) species, were subjected to electrospray ionisation mass spectrometry and MS(n) experiments. Bis-substituted phosphinothiolato complexes 1-4 lead to the straightforward formation of dinuclear species reasonably originating from proton bound dimers. These dinuclear species do not show, under collisionally induced fragmentation processes, the formation of monomeric units but cleavages related to the ligand framework, thereby proving the high stability of the [Tc--H(+)--Tc] bond. Bis-dithiocarbamate compounds 5 and 6 show, instead, abundant [M+H](+), [M+Na](+) and [2M+Na](+) ions, and their collisionally induced fragmentations are highly favoured with cleavages related to the C--N and C--S bonds. During these processes, the coordination of a water molecule to [MH-L](+) product ions is observed, as proved by the collisionally induced H(2)O loss detected for this species. Mixed-ligand compounds 7 and 8 show the protonated molecules and Na(+)-cationised ions with fragmentation processes related to the dithiocarbamate moiety. This behaviour indicates that coordination of ether- and ester-substituted dithiocarbamates to the [Tc [triple chemical bond] N] group is weaker than that of phosphinothiolates. Conversely, diethyldithiocarbamate inserted in mixed complex 9 enhances both C--N and Tc--S bonds, and fragmentation processes suggest that metal-phosphinothiolate and metal-dithiocarbamate show comparable strength.     

Effect of counterion species on colloidal crystal

The effect of counterion species on the colloidal crystal structure in a dispersion was carefully investigated as a function of the degree of neutralization (alpha) by the ultra-small-angle X-ray scattering technique. The nearest neighbor interparticle distance (2D(exp)) first increased with decreasing alpha, and then decreased after passing through the maximum. This behavior was confirmed for K(+), Li(+), Ca(2+), TMA(+) (tetramethylammonium) as a counterion, and Na(+) in our previous report (Harada, T.; Matsuoka, H.; Ikeda, T.; Yamaoka, H. Langmuir 2000, 16, 1612). However, the alpha value of the maximum position (alpha(max)) largely depended on the counterion species, and it was in the order K(+) < Na(+) < TMA(+) approximately Li(+). This behavior was well characterized by the specific features of each ion: the alpha(max) map could be well superimposed in the Stokes radius-crystal ion radius relationship of counterions. The alpha(max) dependence on Stokes radius was very similar to that of the B coefficient by Jones and Dole except in the case of Ca(2+). In principle, the smaller the value for B, the smaller alpha(max), indicating that a water structure breaker such as K(+) can more easily destroy the colloidal crystal structure. In other words, the effect of the counterion species on colloidal crystal stability follows the Hofmeister series. Including Ca(2+), the relationship was linear for the alpha(max) values plotted as a function of the limiting equivalent conductivity of small ions. A counterion with larger conductivity would be a stronger breaker for the colloidal crystal structure.     

Aqueous NaCl and CsCl solutions confined in crystalline slit-shaped silica nanopores of varying degree of protonation

All-atom molecular dynamics simulations were conducted to study the dynamics of aqueous electrolyte solutions confined in slit-shaped silica nanopores of various degrees of protonation. Five degrees of protonation were prepared by randomly removing surface hydrogen atoms from fully protonated crystalline silica surfaces. Aqueous electrolyte solutions containing NaCl or CsCl salt were simulated at ambient conditions. In all cases, the ionic concentration was 1 M. The results were quantified in terms of atomic density distributions within the pores, and the self-diffusion coefficient along the direction parallel to the pore surface. We found evidence for ion-specific properties that depend on ion-surface, water-ion, and only in some cases ion-ion correlations. The degree of protonation strongly affects the structure, distribution, and the dynamic behavior of confined water and electrolytes. Cl(-) ions adsorb on the surface at large degrees of protonation, and their behavior does not depend significantly on the cation type (either Na(+) or Cs(+) ions are present in the systems considered). The cations show significant ion-specific behavior. Na(+) ions occupy different positions within the pore as the degree of protonation changes, while Cs(+) ions mainly remain near the pore center at all conditions considered. For a given degree of protonation, the planar self-diffusion coefficient of Cs(+) is always greater than that of Na(+) ions. The results are useful for better understanding transport under confinement, including brine behavior in the subsurface, with important applications such as environmental remediation.     

Hydration shell exchange dynamics during ion transfer across the liquid/liquid interface

We examine using molecular dynamics simulations the rate and mechanism of water molecules exchange around the Li(+) and Na(+) ions during ion transfer across the interface between water and nitrobenzene. As the ions are transferred from the water to the organic phase, they keep their first hydration shell and an incomplete second shell. The rate of water exchange between the first shell and the rest of the interfacial water molecule decreases during the transfer, which is consistent with an increase in the barrier along the ion-water potential of mean force. While in bulk water the exchange of water molecules around the Li(+) follows an associative (A) or associative interchange (I(a)) type mechanism, the fraction of exchange events of type A increases at the interface. In contrast, while in bulk water the exchange of water molecules around the six coordinated Na(+) hydrated species mainly follows a dissociative mechanism, the situation at the interface involves an equilibrium interchange between the four- and five-coordinated hydrated ion. Simulation of the reversed process, in which the hydrated Li(+) ion is transferred to the aqueous phase, shows the same general behavior as a function of location from the interface.     

Effect of Metal Ions on the Formation and Properties of Monolayers and Nanosized Langmuir-Blodgett Films Based on Diphilic Aminomethylated Calix[4]resorcinarenes

The behavior of the monolayers of three diphilic aminomethylated calix[4]resorcinarene (CRA) derivatives on the surface of a pure aqueous subphase and subphase containing copper(II), nickel(II), europium(III), terbium(III), and lanthanum(III) ions was investigated. The monolayer transfer to the quartz and single-crystal silicon substrates was accomplished by the Langmuir-Blodgett (LB) technique. The films were studied by ellipsometry and mass-spectrometry. Metal ions were found to exert effect on the limit area per one CRA molecule in the monolayer, on the surface collapse pressure and transfer coefficient of monolayer, and on the thickness and refractive index of the CRA-based LB films.     

磷酯酰乙醇胺与硬脂酸和十八醇二元混合体系单层膜的热力学特性和AFM观测

利用表面压力-平均分子面积(π-A)曲线的关系, 分别研究了在水/空气界面上形成的磷酯酰乙醇胺(PE)与硬脂酸(SA)和十八醇(OD)二元混合体系的热力学特性. 根据对弹性模量(C_S^-1)、过量分子面积(A_ex)以及表面过量吉布斯自由能(ΔG_ex)等热力学参数的数据计算, 定量分析了混合单层膜分子之间的相互作用. 实验结果表明, PE/SA和PE/OD单层膜两种组分之间摩尔比对其热力学参数有影响. 热力学分析表明, 在X_SA=0.2, 0.8和X_OD=0.8处, PE/SA和PE/OD二元混合体系的热力学参数[过量分子面积(A_ex)和表面过量吉布斯自由能(ΔGex)]相对理想状态均表现为负偏差作用, 说明分子之间的作用为引力作用. 相反, PE/OD二元体系在X_OD=0.2, 0.4, 0.6处, 表现为正偏差作用, 这说明分子之间的作用为斥力作用. AFM观测为PE/SA和PE/OD单层膜热力学特性的理论分析提供了有力的支持.     

Hydration of alkali ions from first principles molecular dynamics revisited

Structural and dynamical properties of the hydration of Li(+), Na(+), and K(+) in liquid water at ambient conditions were studied by first principles molecular dynamics. Our simulations successfully captured the different hydration behavior shown by the three alkali ions as observed in experiments. The present analyses of the dependence of the self-diffusion coefficient and rotational correlation time of water on the ion concentration suggest that Li(+) (K(+)) is certainly categorized as a structure maker (breaker), whereas Na(+) acts as a weak structure breaker. An analysis of the relevant electronic structures, based on maximally localized Wannier functions, revealed that the dipole moment of H(2)O molecules in the first solvation shell of Na(+) and K(+) decreases by about 0.1 D compared to that in the bulk, due to a contraction of the oxygen lone pair orbital pointing toward the metal ion.