pH-Induced reorientation of cytochrome c on silica nanoparticles.

The orientation of cytochrome c molecules at the surface of silica nanoparticles was studied in a wide pH range by combining small-angle neutron scattering, adsorption measurements, and molecular dynamics simulations. The results indicate a reorientation of the ellipsoidal protein from head-on to side-on as the pH is increased. This is attributed to changes in the surface charge distribution of both the protein and the nanoparticles.

Adsorption and Depletion Regimes of a Nonionic Surfactant in Hydrophilic Mesopores: An Experimental and Simulation Study.

Adsorption and aggregation of nonionic surfactants at oxide surfaces has been studied extensively in the past, but only for concentrations below and near the critical micelle concentration. Here we report an adsorption study of a short-chain surfactant (C6E3) in porous silica glass of different pore sizes (7.5 to 50 nm), covering a wide composition range up to 50 wt % in a temperature range from 20 °C to the LCST. Aggregative adsorption is observed at low concentrations, but the excess concentration of C6E3 in the pores decreases and approaches zero at higher bulk concentrations. Strong depletion of surfactant (corresponding to enrichment of water in the pores) is observed in materials with wide pores at high bulk concentrations. We propose an explanation for the observed pore-size dependence of the azeotropic point. Mesoscale simulations based on dissipative particle dynamics (DPD) were performed to reveal the structural origin of this transition from the adsorption to the depletion regime. The simulated adsorption isotherms reproduce the behavior found in the 7.5 nm pores. The calculated bead density profiles indicate that the repulsive interaction of surfactant head groups causes a depletion of surfactant in the region around the corona of the surface micelles.

Analysis of the field-assisted permanent assembly of oppositely charged particles.

We characterize experimentally and analyze analytically a novel electric-field-assisted process for the assembly of permanent chains of oppositely charged microparticles in an aqueous environment. Long chains of oppositely charged particles are rapidly formed when an external electric field is applied and break up into permanent linear fragments upon switching off the field. The resulting secondary chains are stabilized by attractive electrostatic and van der Waals interactions between the particles. We find that the length of the permanent chains is strongly dependent on the relative size (microsphere diameter D) of small and large particles and can be tuned by varying the particle size ratio s = Dsm/Dlg and particle number ratio r = Nsm/Nlg. Three latex microsphere systems of different particle size ratio, s = 0.9, 0.45, and 0.225, were characterized at different particle number ratios r by determining experimentally the length distribution of the permanent chains. The results are compared with statistical models based on a one-step or two-step process of forming the primary chains. We find that the one-step model is applicable to the system of similarly sized particles (s = 0.9) and the two-step chaining model is applicable to the system of dissimilarly sized particles (s = 0.225), where the large particles form chains first and the small ones serve as binders, which are later drawn in the junctions. Long permanent chains are formed only from particles of dissimilar size for which our model predicts a linear increase in the mean chain length with increasing r. On the basis of these results, we formulate a set of assembly rules for permanent colloidal chain formation by oppositely charged particles. The results make possible the precise large-scale formation of particle chains of any length, which can serve as components in new gels, biomaterials, and fluids with controlled rheology.

Bridging interactions of proteins with silica nanoparticles: the influence of pH, ionic strength and protein concentration.

Charge-driven bridging of nanoparticles by macromolecules represents a promising route for engineering functional structures, but the strong electrostatic interactions involved when using conventional polyelectrolytes impart irreversible complexation and ill-defined structures. Recently it was found that the electrostatic interaction of silica nanoparticles with small globular proteins leads to aggregate structures that can be controlled by pH. Here we study the combined influence of pH and electrolyte concentration on the bridging aggregation of silica nanoparticles with lysozyme in dilute aqueous dispersions. We find that protein binding to the silica particles is determined by pH irrespective of the ionic strength. The hetero-aggregate structures formed by the silica particles with the protein were studied by small-angle X-ray scattering (SAXS) and the structure factor data were analyzed on the basis of a short-range square-well attractive pair potential (close to the sticky-hard-sphere limit). It is found that the electrolyte concentration has a strong influence on the stickiness near pH 5, where the weakly charged silica particles are bridged by the strongly charged protein. An even stronger influence of the electrolyte is found in the vicinity of the isoelectric point of the protein (pI = 10.7) and is attributed to shielding of the repulsion between the highly charged silica particles and hydrophobic interactions between the bridging protein molecules.

Assembling wormlike micelles in tubular nanopores by tuning surfactant-wall interactions.

Threadlike molecular assemblies are excluded from narrow pores unless attractive interactions with the confining pore walls compensate for the loss of configurational entropy. Here we show that wormlike surfactant micelles can be assembled in the 8 nm tubular nanopores of SBA-15 silica by adjusting the surfactant-pore-wall interactions. The modulation of the interactions was achieved by coadsorption of a surface modifier that also provides control over the partitioning of wormlike aggregates between the bulk solution and the pore space. We anticipate that the concept of tuning the interactions with the pore wall will be applicable to a wide variety of self-assembling molecules and pores.

Lysozyme as a pH-responsive valve for the controlled release of guest molecules from mesoporous silica.

Mesoporous silica nanoparticles show promise as a drug-carrier vehicle for biomedical applications, but the development of simple, biocompatible capping systems has remained a challenge. We have found that lysozyme molecules can act as a pH-responsive nanovalve to block and unlock the pore entrances of MCM-41 nanoparticles for guest molecules. Our experiments indicate that pore blocking is due to a pH-induced conformational change by which the effective size of the protein is changed in a reversible manner. This effect may form the basis of a controlled-release system without the need to functionalize the pore mouth and caps.

Aggregation of silica nanoparticles directed by adsorption of lysozyme.

The interaction of the globular protein lysozyme with silica nanoparticles of diameter 20 nm was studied in a pH range between the isoelectric points (IEPs) of silica and the protein (pH 3-11). The adsorption affinity and capacity of lysozyme on the silica particles is increasing progressively with pH, and the adsorbed protein induces bridging aggregation of the silica particles. Structural properties of the aggregates were studied as a function of pH at a fixed protein-to-silica concentration ratio which corresponds to a surface concentration of protein well below a complete monolayer in the complete-binding regime at pH > 6. Sedimentation studies indicate the presence of compact aggregates at pH 4-6 and a loose flocculated network at pH 7-9, followed by a sharp decrease of aggregate size near the IEP of lysozyme. The structure of the bridged silica aggregates was studied by cryo-transmission electron microscopy (cryo-TEM) and small-angle X-ray scattering. The structure factor S(q) derived from the scattering profiles displays characteristic features of particles interacting by a short-range attractive potential and can be represented by the square-well Percus-Yevick potential model, with a potential depth not exceeding 3k(B)T.

Structural characterization of surfactant aggregates adsorbed in cylindrical silica nanopores.

The self-assembly of nonionic surfactants in the cylindrical pores of SBA-15 silica with a pore diameter of 8 nm was studied by small-angle neutron scattering (SANS) at different solvent contrasts. The alkyl ethoxylate surfactants C(10)E(5) and C(12)E(5) exhibit strong aggregative adsorption in the pores as indicated by the sigmoidal shape of the adsorption isotherms. The SANS intensity profiles can be represented by a sum of two terms, one accounting for diffuse scattering from surfactant aggregates in the pores and the other for Bragg scattering from the pore lattice of the silica matrix. The Bragg reflections are analyzed with a form factor model in which the radial density profile of the surfactant in the pore is approximated by a two-step function. Diffuse scattering is represented by a Teubner-Strey-type scattering function which indicates a preferred distance between adsorbed surface aggregates in the pores. Our results suggest that adsorption starts with formation of discrete surface aggregates which increase in number and eventually merge to interconnected patches as the plateau value of the adsorption isotherm is approached. A grossly different behavior, viz. formation of micelles as in solution, is found for the maltoside surfactant C(10)G(2), in agreement with the observed weak adsorption of this surfactant in SBA-15.

Fluid adsorption in ordered mesoporous solids determined by in situ small-angle X-ray scattering.

The adsorption of two organic fluids (n-pentane and perfluoropentane) in a periodic mesoporous silica material (SBA-15) is investigated by in situ small-angle X-ray scattering (SAXS) using synchrotron radiation. Structural changes are monitored as the ordered and disordered pores in the silica matrix are gradually filled with the fluids. The experiments yield integrated peak intensities from up to ten Bragg reflections from the 2D hexagonal pore lattice, and additionally diffuse scattering contributions arising from disordered (mostly intrawall) porosity. The analysis of the scattering data is based on a separation of these two contributions. Bragg scattering is described by adopting a form factor model for ordered pores of cylindrical symmetry which accounts for the filling of the microporous corona, the formation of a fluid film at the pore walls, and condensation of the fluid in the core. The filling fraction of the disordered intrawall pores is extracted from the diffuse scattering intensity and its dependence on the fluid pressure is analyzed on the basis of a three-phase model. The data analysis introduced here provides an important generalisation of a formalism presented recently (J. Phys. Chem. C, 2009, 13, 15201), which was applicable to contrast-matching fluids only. In this way, the adsorption behaviour of fluids into ordered and disordered pores in periodic mesoporous materials can be analyzed quantitatively irrespective of the fluid density.

Freezing and melting of water confined in silica nanopores.

In nanosized pores, liquid water can be thermodynamically stable down to temperatures well below the limit of homogeneous nucleation of bulk water ( approximately 235 K). Studies of water in such pores therefore offer an opportunity to reveal the anomalous behavior of deeply supercooled water. Herein we focus on recent studies of the limits of freezing and melting of water in the cylindrical pores of ordered mesoporous silicas with pore diameters in the range of 2-10 nm, based on vapor sorption measurements, calorimetric studies, NMR spectroscopy and cryoporometry, and neutron diffraction studies.

Dynamics of dehaloperoxidase-hemoglobin A derived from NMR relaxation spectroscopy and molecular dynamics simulation.

Dehaloperoxidase-hemoglobin is the first hemoglobin identified with biologically-relevant oxidative functions, which include peroxidase, peroxygenase and oxidase activities. Herein we report a study of the protein backbone dynamics of DHP using heteronuclear NMR relaxation methods and molecular dynamics (MD) simulations to address the role of protein dynamics in switching from one function to another. The results show that DHP's backbone helical regions and turns have average order parameters of S2 = 0.87 ±â€¯0.03 and S2 = 0.76 ±â€¯0.08, respectively. Furthermore, DHP is primarily a monomer in solution based on the overall tumbling correlation time τm is 9.49 ±â€¯1.65 ns calculated using the prolate diffusion tensor model in the program relax. A number of amino acid residues have significant Rex using the Lipari-Szabo model-free formalism. These include Lys3, Ile6, Leu13, Gln18, Arg32, Ser48, Met49, Thr56, Phe60, Arg69, Thr71 Cys73, Ala77, Asn81, Gly95, Arg109, Phe115, Leu127 and Met136, which may experience slow conformational motions on the microseconds-milliseconds time scale according to the model. Caution should be used when the model contains >4 fitting parameters. The program caver3.0 was used to identify tunnels inside DHP obtained from MD simulation snapshots that are consistent with the importance of the Xe binding site, which is located at the central intersection of the tunnels. These tunnels provide diffusion pathways for small ligands such as O2, H2O and H2O2 to enter the distal pocket independently of the trajectory of substrates and inhibitors, both of which are aromatic molecules.

NMR provides checklist of generic properties for atomic-scale models of periodic mesoporous silicas.

MCM-41 and SBA-15 silicas were studied by (29)Si solid-state NMR and (15)N NMR in the presence of (15)N-pyridine with the aim to formulate generic structural parameters that may be used as a checklist for atomic-scale structural models of this class of ordered mesoporous materials. High-quality MCM-41 silica constitutes quasi-ideal arrays of uniform-size pores with thin pore walls, while SBA-15 silica has thicker pore walls with framework and surface defects. The numbers of silanol (Q(3)) and silicate (Q(4)) groups were found to be in the ratio of about 1:3 for MCM-41 and about 1:4 for our SBA-15 materials. Combined with the earlier finding that the density of surface silanol groups is about three per nm(2) in MCM-41 (Shenderovich, et al. J. Phys. Chem. B 2003, 107, 11924) this allows us to discriminate between different atomic-scale models of these materials. Neither tridymite nor edingtonite meet both of these requirements. On the basis of the hexagonal pore shape model, the experimental Q(3):Q(4) ratio yields a wall thickness of about 0.95 nm for MCM-41 silica, corresponding to the width of ca. four silica tetrahedra. The arrangement of Q(3) groups at the silica surfaces was analyzed using postsynthesis surface functionalization. It was found that the number of covalent bonds to the surface formed by the functional reagents is affected by the surface morphology. It is concluded that for high-quality MCM-41 silicas the distance between neighboring surface silanol groups is greater than 0.5 nm. As a result, di- and tripodical reagents like (CH(3))(2)Si(OH)(2) and CH(3)Si(OH)(3) can form only one covalent bond to the surface. The residual hydroxyl groups of surface-bonded functional reagents either remain free or interact with other reagent molecules. Accordingly, the number of surface silanol groups at a given MCM-41 or SBA-15 silica may not decrease but increase after treatment with CH(3)Si(OH)(3) reagent. On the other hand, nearly all surface silanol groups could be functionalized when HN(Si(CH(3))(3))(2) was used.

Secondary Confinement of Water Observed in Eutectic Melting of Aqueous Salt Systems in Nanopores.

Freezing and melting of aqueous solutions of alkali halides confined in the cylindrical nanopores of MCM-41 and SBA-15 silica was probed by differential scanning calorimetry (DSC). We find that the confinement-induced shift of the eutectic temperature in the pores can be significantly greater than the shift of the melting temperature of pure water. Greatest shifts of the eutectic temperature are found for salts that crystallize as oligohydrates at the eutectic point. This behavior is explained by the larger fraction of pore volume occupied by salt hydrates as compared to anhydrous salts, on the assumption that precipitated salt constitutes an additional confinement for ice/water in the pores. A model based on this secondary confinement effect gives a good representation of the experimental data. Salt-specific secondary confinement may play a role in a variety of fields, from salt-impregnated advanced adsorbents and catalysts to the thermal weathering of building materials.

Characterization of protein adsorption onto silica nanoparticles: influence of pH and ionic strength.

The adsorption of lysozyme and ß-lactoglobulin onto silica nanoparticles (diameter 21 nm) was studied in the pH range 2-11 at three different ionic strengths. Since the two proteins have a widely different isoelectric point (pI), electrostatic interactions with the negative silica surface lead to a different dependence of adsorption on pH. For lysozyme (pI ≈ 11), the adsorption level increases with pH and reaches a value corresponding to about two close-packed monolayers at pH = pI. In the multilayer adsorption region near pI, added electrolyte causes a decrease in adsorption, which is attributed to the screening of attractive interactions between protein molecules in the first and second adsorbed layer. For ß-lactoglobulin (pI ≈ 5), a pronounced maximum of the adsorbed amount is found at pH 4 in the absence of salt. It is attributed to the adsorption of oligomers of the protein that exist in the solution at this pH. An inversion in the influence of salt on the adsorbed amount occurs at pH > pI, where the protein and the surface are both negatively charged. This inversion is attributed to the screening of the repulsive protein-surface and protein-protein interactions. The adsorption isotherms were analyzed with the Guggenheim-Anderson-De Boer (GAB) model, which allows for two adsorption states (strongly and weakly bound protein).

Structural changes of poly(butadiene)-poly(ethyleneoxide) diblock-copolymer micelles induced by a cationic surfactant: scattering and cryogenic transmission electron microscopy studies.

Micelles of the diblock copolymer poly(butadiene)-poly(ethyleneoxide) (B40-b-EO62) and mixed micelles of this polymer with the cationic surfactant dodecyltrimethylammonium bromide (C12TAB) were investigated using static and dynamic light scattering and small-angle neutron scattering. It is shown that the surfactant induces a major structural change from large mainly rodlike aggregates to smaller spherical mixed micelles. The rodlike assemblies found in the absence of surfactant have a contour length L of ca. 500 nm and a diameter d approximately 30 nm. The spherical mixed micelles obtained upon addition of C12TAB possess a hydrodynamic radius of 15 nm and still contain several polymer molecules. The results of the scattering experiments are consistent with observations of the aggregates by cryogenic transmission electron microscopy.

Characterization of polybutadiene-poly(ethyleneoxide) aggregates in aqueous solution: a light-scattering and small-angle neutron-scattering study.

For diblockcopolymers of polybutadiene-poly(ethyleneoxide) (PB-PEO) type, water is a selective solvent. In dependence of the length of both blocks and the block length ratio, these polymers form a multitude of self-assembled structures in solution. In the present work scattering methods are used to investigate the water-soluble polymer PB125-PEO155 . It is found to form long rodlike micelles, which are characterized with respect to the aggregate length L , the cross sectional radius RCS , the radial scattering length density profile sigma r, and the radial aggregation number Nrad. Model-independent as well as model-based approaches are used for the scattering data analysis. From dynamic light scattering (DLS) and static light scattering (SLS) experiments the weight averaged length Lw of these stiff elongated aggregates is determined to Lw=350 nm . Small angle neutron scattering (SANS) reveals a cross sectional radius of RCS=17 nm and in combination with results from the SLS the radial aggregation number is found to be Nrad=70 .

Co-assembly of oppositely charged particles into linear clusters and chains of controllable length.

Colloidal particles with strongly attractive interactions snap on contact and form permanent, but disordered aggregates. In contrast, AC electric fields allow directional assembly of chains or crystals from repulsive particles by dielectrophoresis (DEP), but these structures fall apart once the field is switched off. We demonstrate how well-organized, permanent clusters and chains of micron-sized particles can be assembled by applying DEP to mixtures of oppositely charged microspheres. We found that the length of the formed chains depends on size ratio as well as the number ratio of the two species, and formulated a statistical model for this assembly mechanism, which is in excellent agreement with the experimental results. The assembly rules resulting from this study form a basis for tailoring new classes of permanent supracolloidal clusters and gels.

Effect of nanoparticle size on the morphology of adsorbed surfactant layers.

The surface aggregate structure of dimethyldodecylamine-N-oxide (C(12)DAO) in three silica dispersions of different particle sizes (16-42 nm) was studied by small-angle neutron scattering (SANS) in a H(2)O/D(2)O solvent mixture matching the silica. At the experimental conditions (pH 9), the surfactant exists in its nonionic form, and the structure of the adsorbed layer is not affected by added electrolyte. It is found that C(12)DAO forms spherical surface micelles of 2 nm diameter on the 16 nm silica particles, but oblate ellipsoidal surface micelles are formed on the 27 and 42 nm particles. The dimensions of these oblate surface aggregates (minor and major semiaxes R(n) and R(lat)) are similar to those of C(12)DAO micelles in the aqueous solutions. It is concluded that the morphological transition from spherical to ellipsoidal surface aggregates is induced by the surface curvature of the silica particles. A comparison of the shape and dimensions of the surface aggregates formed by C(12)DAO and C(12)E(5) on the 16 nm silica particles demonstrates that the nature of the surfactant head group does not determine the morphology of the surface aggregates but has a strong influence on the number of surface aggregates per particle due to the different interactions of the head groups with the silica surface.

Adsorption of dodecyltrimethylammonium bromide and sodium bromide on gold studied by liquid chromatography and flow adsorption microcalorimetry.

Here, we report on a new aspect of the adsorption of Br- on the surface of gold. The adsorption of dodecyltrimethylammonium bromide (C12TABr) from aqueous solutions onto macroporous gold particles was studied by continuous flow frontal analysis solid/liquid chromatography and flow adsorption microcalorimetry. The material balance and enthalpy balance of adsorption and the change in the solution pH were measured simultaneously. Initially, Br- is irreversibly bound to high-affinity surface sites counterbalanced by the adsorption of H+ from the aqueous phase. The surface speciation is accompanied by the formation of C12TAOH, which in turn results in a significant pH increase in the bulk solution. The net process was found to be strongly exothermic (-280 kJ.mol(-1)), which is indicative of the occurrence of chemisorption. The specific adsorption of Br- is followed by the reversible adsorption of C12TABr to produce a firmly bound monolayer in a head-to-surface arrangement (-53 kJ.mol(-1)). In a relatively narrow range of the surface coverage, various composite structures may develop on the top layer and eventually transform to full-cylindrical surface aggregates. The surface aggregation was found to be reversible, with an enthalpy change of -11 kJ.mol(-1). The importance of the specific binding of Br- to the surface of gold was confirmed by measurement of the initial adsorption of NaBr on the microparticles. The initial adsorption was found to be irreversible, with an enthalpy change of approximately -240 kJ.mol(-1). This process involved the formation of an AuBr-/H+ electric double layer at the gold/water interface, accompanied by a dramatic increase in the solution pH due to the release of a copious amount of OH- in the bulk liquid phase.