The structure of the transient layer at the interface between air and the aqueous solution of silica nanoparticles with the size distribution of particles that has been determined from small-angle scattering has been studied by the X-ray reflectometry method. The reconstructed depth profile of the polarizability of the substance indicates the presence of a structure consisting of several layers of nanoparticles with the thickness that is more than twice as large as the thickness of the previously described structure. The adsorption of 1,2-distearoyl-sn-glycero-3-phosphocholine molecules at the hydrosol/air interface is accompanied by the condensation of anion silica nanoparticles at the interface. This phenomenon can be qualitatively explained by the formation of the positive surface potential due to the penetration and accumulation of Na+ cations in the phospholipid membrane.
The ordering of a multilayer consisting of DSPC bilayers on a silica sol substrate is studied within the model-independent approach to the reconstruction of profiles of the electron density from X-ray reflectometry data. It is found that the electroporation of bilayers in the field of anion silica nanoparticles significantly accelerates the process of their saturation with Na+ and H2O, which explains both a relatively small time of formation of the structure of the multilayer of 10^5 - 7x10^5 s and ~13 % excess of the electron density in it.
Nanoparticles with hydrophobic capping ligands and amphiphilic phospholipids are both found to self-assemble into monolayer films when deposited on the air water interface. By separately measuring the anisotropic stress response of these films under uniaxial compression, we obtain both the 2D compressive and shear moduli of a range of different thin nanoparticle and phospholipid films. The compressive moduli of both nanoparticle and lipid films in the solid phase are on the same order of magnitude, whereas the shear moduli of the lipid films are found to be significantly lower. Additionally th…
Amphiphilic phospholipids and nanoparticles functionalized with hydrophobic capping ligands have previously been extensively investigated for their capacity to self-assemble into Langmuir monolayers at the air/water interface. However, understanding of composite films consisting of both nanoparticles and phospholipids, and by extension, the complex interactions arising between nanomaterials and biological membranes, remains limited. In this work, dodecanethiol-capped gold nanoparticles (Au-NPs) with an average core diameter of 6 nm were incorporated into 1,2-dipalmitoyl-sn-glycero-3-phosphocho…
The dependence of the structure of a phospholipid layer (DSPC and SOPC) adsorbed on a hydrosol substrate on the concentration of NaOH in a solution of 5-nm silica particles has been studied by X-ray reflectrometry with the use of synchrotron radiation. Profiles of the electron density (polarizability) have been reconstructed from the experimental data within a model-independent approach. According to these profiles, the thickness of the lipid film can vary from a monolayer (~ 35 Angstrom) to several bilayers (~ 450 Angstrom). At the volume concentration of NaOH of ~ 0.5 mol/L, the film on the …
When inhaled nanoparticles (NPs) deposit in alveoli, they transit through the pulmonary surfactant (PS), a biofluid made of proteins and phospholipidic vesicles. They acquire a corona reflecting the PS-nanomaterials interaction. Since the corona determines directly the NPs biological fate, the question of its nature and structure is central. Here, we report on the corona architecture raising after incubation of positive or negative silica particles with Curosurf, a biomimetic pulmonary surfactant of porcine origin. Using optical, electron and cryo-electron microscopy (cryo-TEM), we determine t…
Certain membrane proteins, peptides, nanoparticles and nanotubes have rigid structure and fixed shape. They are often viewed as spheres and cylinders with certain surface properties. Single Chain Mean Field theory is used to model the equilibrium insertion of nanoscale spheres and rods into the phospholipid bilayer. The equilibrium structures and the resulting free energies of the nano-objects in the bilayer allow to distinguish different orientations in the bilayer and estimate the energy barrier of insertion.
The molecular structure of a multilayer of 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) adsorbed on the surface of the hydrosol of silica nanoparticles has been studied by the synchrotron radiation scattering method. According to the reflectometry data, the multilayer is formed by planar phospholipid bilayers with a thickness of 69 +/- 1 Angstrom and its total thickness is about 400 Angstrom. Grazing-incidence diffraction indicates that the bilayers are in the crystal state with an area of 41.6 +/- 0.7 Angstrom^2 per molecule.
Chromobodies have recently drawn great attention as bioimaging nanotools. They offer antigen binding specificity and affinity comparable to conventional antibodies, but much smaller size and higher stability. Importantly, chromobodies can be used in live cell imaging for highly specific spatio-temporal visualization of cellular processes. To date, functional application of chromobodies requires lengthy genetic manipulation of the target cell. Here, we developed multifunctional large-pore mesoporous silica nanoparticles (MSNs) as nanocarriers to directly transport chromobodies into living cells…
The structure and interactions of coated silica nanoparticles have been studied in water using molecular dynamics simulations. For 5 nm diameter amorphous silica nanoparticles we studied the effects of varying the chain length and grafting density of polyethylene oxide (PEO) on the nanoparticle coating's shape and on nanoparticle-nanoparticle effective forces. For short ligands of length $n=6$ and $n=20$ repeat units, the coatings are radially symmetric while for longer chains ($n=100$) the coatings are highly anisotropic. This anisotropy appears to be governed primarily by chain length, with …
Multifunctional mesoporous silica nanoparticles (MSN) have attracted substantial attention with regard to their high potential for targeted drug delivery. For future clinical applications it is crucial to address safety concerns and understand the potential immunotoxicity of these nanoparticles. In this study, we assess the biocompatibility and functionality of multifunctional MSN in freshly isolated, primary murine immune cells. We show that the functionalized silica nanoparticles are rapidly and efficiently taken up into the endosomal compartment by specialized antigen-presenting cells such …
Studies have shown that following exposure to particulate matter, the ultrafine fraction (< 100 nm) may deposit along the respiratory tract down to the alveolar region. To assess the effects of nanoparticles in the lungs, it is essential to address the question of their biophysicochemical interaction with the different pulmonary environments, including the lung lining fluids and the epithelia. Here we examine one of these interactive scenarios and study the role of supported lipid bilayers (SLB) on the fate of 40 nm fluorescent silica particles towards living cells. We first study the particle…
We investigated the formation of cocontinuous structures in polymer blends. These polymeric bijels (bicontinuous interfacially jammed emulsion gels) were composed of polystyrene oligomer, polybutene and fluorescent hydrophobic silica nanoparticles. A micron-sized cocontinuous morphology was stabilized by a monolayer of silica nanoparticles at the interface. Real-time observation of coalescence dynamics in co-continuous polymer blends stabilized by interfacial particles was for the first time achieved via laser scanning confocal microscopy. We demonstrated that suppression of coalescence arises…
Results of broadband dielectric spectroscopy and rheological studies of poly(propylene glycol) + SiO${_2}$ nanocomposites are presented. They show that the dynamics in high-concentrated composite is determined by confinement and adsorption effects, resulting from interactions of confined polymers correspond with the host system at the interface between PPG and solid nanoparticles. The evolution of relaxation times follows the clear Vogel-Fulcher-Tammann pattern, what is proved by the supplementary activation energy temperature index analysis. The strong influence of nanoparticles on the transi…
To prevent the flocculation and phase separation of nanoparticles in solution, nanoparticles are often functionalized with short chain surfactants. Here we present fully-atomistic molecular dynamics simulations which characterize how these functional coatings affect the interactions between nanoparticles and with the surrounding solvent. For 5 nm diameter silica nanoparticles coated with poly(ethylene oxide) (PEO) oligomers in water, we determined the hydrodynamic drag on two approaching nanoparticles moving through solvent and on a single nanoparticle as it approaches a planar surface. In mos…
We analyze the evolution of the mechanical response of a colloidal suspension to an external tensile stress, from fracture to flow, as a function of the distance from the sol-gel transition. We cease to observe cracks at a finite distance from the transition. In an intermediate region where the phenomenon is clearly hysteretic, we observe the coexistence of both flow and fracture. Even when cracks are observed, the material in fact flows over a distance that increases in the vicinity of the transition.
Some of our recent studies of the structure and mechanical properties of a special type of nanocomposite are reviewed here. In silica-latex systems, a latex film with silica inclusions is formed from a colloidal solution of both components. During drying of the solution, the formation of silica domains can be controlled via the physico-chemical properties of the solution. Well-defined silica aggregates embedded in a polymer matrix can be generated, and the mechanical properties of the resulting nanocomposite have been shown to be directly correlated to the average structure.
Cells use homeostatic mechanisms to maintain an optimal composition of distinct types of phospholipids in cellular membranes. The hydrophilic dipolar layer at the membrane interface, composed of phospholipid headgroups, regulates the interactions between cell membranes and incoming molecules, nanoparticles, and viruses. On the other hand, the membrane hydrophobic core determines membrane thickness and forms an environment for membrane-bound molecules such as transmembrane proteins. A fundamental open question is to what extent the motions of these regions are coupled and, consequently, how str…
We investigate by scattering techniques the structure of water-based soft composite materials comprising a crystal made of Pluronic block-copolymer micelles arranged in a face-centered cubic lattice and a small amount (at most 2% by volume) of silica nanoparticles, of size comparable to that of the micelles. The copolymer is thermosensitive: it is hydrophilic and fully dissolved in water at low temperature (T ~ 0°C), and self-assembles into micelles at room temperature, where the block-copolymer is amphiphilic. We use contrast matching small-angle neuron scattering experiments to probe indepen…
Effective and controlled drug delivery systems with on-demand release and targeting abilities have received enormous attention for biomedical applications. Here, we describe a novel enzyme-based cap system for mesoporous silica nanoparticles (MSNs) that is directly combined with a targeting ligand via bio-orthogonal click chemistry. The capping system is based on the pH-responsive binding of an aryl-sulfonamide-functionalized MSN and the enzyme carbonic anhydrase (CA). An unnatural amino acid (UAA) containing a norbornene moiety was genetically incorporated into CA. This UAA allowed for the si…
Reinforcement of elastomers by colloidal nanoparticles is an important application where microstructure needs to be understood - and if possible controlled - if one wishes to tune macroscopic mechanical properties. Here the three-dimensional structure of big aggregates of nanometric silica particles embedded in a soft polymeric matrix is determined by Small Angle Neutron Scattering. Experimentally, the crowded environment leading to strong reinforcement induces a strong interaction between aggregates, which generates a prominent interaction peak in the scattering. We propose to analyze the tot…
We introduced silica nanoparticles into poly ($N$,$N$-dimethylacrylamide) gel, (PDAM-NC gel), and poly (acrylamide) gel (PAM-NC gel), and carried out SAXS measurements under uniaxial elongation. It is well known that PDAM chains are strongly adsorbed onto silica nanoparticles while PAM chains are not. Interestingly, we found from SAXS measurements that scattering profiles depend on the polymer-nanoparticle interaction. A four-spot pattern was observed in the 2D structure factors of PDAM-NC gel, which was assigned to a movement of the nanoparticles affinely under elongation. However, unexpected…
The authors present a review of the systematic studies of the structure of macroscopically planar thin films at the air-liquid interface (water, alkali solution and silica hydrosol). A common feature of the considered works is the application of a model-independent approach to the analysis of X-ray reflectometry data, which does not require a priori assumptions about the structure of the object under study. It is shown that the experimental results obtained with the laboratory source in some cases are qualitatively on par with the results of those obtained with the use of synchrotron radiation…
We report on the interaction of pulmonary surfactant composed of phospholipids and proteins with nanometric alumina (Al2O3) in the context of lung exposure and nanotoxicity. We study the bulk properties of phospholipid/nanoparticle dispersions and determine the nature of their interactions. The clinical surfactant Curosurf, both native and extruded, and a protein-free surfactant are investigated. The phase behavior of mixed surfactant/particle dispersions was determined by optical and electron microscopy, light scattering and zeta potential measurements. It exhibits broad similarities with tha…
The structural features of polystyrene brushes grafted on spherical silica nanoparticles immersed in polystyrene are investigated by means of a Monte Carlo methodology based on polymer mean field theory. The nanoparticle radii (either 8 nm or 13 nm) are held constant, while the grafting density and the lengths of grafted and matrix chains are varied systematically in a series of simulations. The primary objective of this work is to simulate realistic nanocomposite systems of specific chemistry at experimentally accessible length scales and study the structure and scaling of the grafted brush. …
The self-assembly of two nonionic surfactants, pentaethylene glycol monododecyl ether (C12E5) and n-dodecyl-ß-maltoside (ß-C12G2), in the presence of a purpose-synthesized silica sol of uniform particle size (diameter 16 nm) has been studied by adsorption measurements, dynamic light scattering and small-angle neutron scattering (SANS) using a H2O/D2O mixture matching the silica, in order to highlight the structure of the surfactant aggregates. For C12E5 strong aggregative adsorption onto the silica beads, with a high plateau value of the adsorption isotherm above the CMC was found. SANS measur…
We present a new convenient and efficient "grafting from" method to obtain well defined polystyrene (PS) silica nanoparticles. The method, based on Nitroxide-Mediated Polymerization (NMP), consists to bind covalently the alkoxyamine, which acts as initiator controller agent, at the silica nanoparticles surface in two steps. The first step is a reaction between the aminopropylsilane and the silica particles in order to functionalize the particles surface with amino group. In a second step, the initiating-controlling alkoxyamine moiety is introduced via an over grafting reaction between the amin…
Self-propelled particles and, in particular, those based on mesoporous silica, have raised considerable interest due to their potential applications in the environmental and biomedical fields thanks to their biocompatibility, tunable surface chemistry and large porosity. Although spherical particles have been widely used to fabricate nano- and micromotors, not much attention has been paid to other geometries, such as nanorods. Here, we report the fabrication of self-propelled mesoporous silica nanorods (MSNRs) that move by the catalytic decomposition of hydrogen peroxide by a sputtered Pt laye…
Oils and fragrances can be encapsulated by using composite shells of silica nanoparticles, polymer and surfactant (potassium oleate). The template for the creation of the core-shell structure is a particle stabilized (Pickering) emulsion. The surfactant adsorbs on the nanoparticles and leads to their reversible hydrophobization and adsorption on the oil-water interface. The outer layer of the self-assembled shell represents a layer from crosslinked polymer. The procedure of encapsulation is simple and includes single homogenization by ultrasound of the formulation that contains all ingredients…
The surface aggregates structure of dimethyldodecylamine-N-oxide (C12DAO) in three silica dispersions of different particle sizes (16 - 42 nm) was studied by small-angle neutron scattering (SANS) in a H2O/D2O 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 C12DAO 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 dime…
It is shown that porous spherical particles can be obtained via the freezing of silica nanoparticle aqueous suspensions emulsified in a continuous oil phase. After two freeze-thaw cycles, nanoparticles turn aggregated into flocculated objects with microstructure that depends upon emulsion volume fraction and droplet size. For low volume fractions, regular microspheres are produced while for large ones, irregular beads with several tens of micrometer radius are formed. Electronic microscopy, mercury porosimetry and nitrogen adsorption are used to get insights into these porous particles typical…
Porous magnetic silica beads are promising materials for biological and environmental applications due to their enhanced adsorption and ease of recovery. This work aims to develop a new, inexpensive and environmentally friendly approach based on agglomeration of nanoparticles in aqueous droplets. The use of an emulsion as a geometrical constraint is expected to result in the formation of spherical beads with tunable composition depending on the aqueous phase content. Magnetic silica beads are produced at room temperature by colloidal destabilization induced by addition of calcium chloride to a…
Model microemulsion networks of oil droplets stabilized by non ionic surfactant and telechelic polymer C18-PEO(10k)-C18 have been studied for two droplet-to-polymer size ratios. The rheological properties of the networks have been measured as a function of network connectivity and can be described in terms of simple percolation laws. The network structure has been characterised by Small Angle Neutron Scattering. A Reverse Monte Carlo approach is used to demonstrate the interplay of attraction and repulsion induced by the copolymer. These model networks are then used as matrix for the incorpora…
We study the potential of mean force (PMF) between atomistic silica and gold nanoparticles in the vacuum by using molecular dynamics simulations. Such an investigation is devised in order to fully characterize the effective interactions between atomistic nanoparticles, a crucial step to describe the PMF in high-density coarse-grained polymer nanocomposites. In our study, we first investigate the behavior of silica nanoparticles, considering cases corresponding to different particle sizes and assessing results against an analytic theory developed by Hamaker for a system of Lennard-Jones interac…
The structure of silica-latex nanocomposites of three matrix chain masses (20, 50, and 160 kg/mol of poly(ethyl methacrylate)) are studied using a SAXS/TEM approach, coupled via Monte Carlo simulations of scattering of fully polydisperse silica nanoparticle aggregates. At low silica concentrations (1 vol. %), the impact of the matrix chain mass on the structure is quantified in terms of the aggregation number distribution function, highest mass leading to individual dispersion, whereas the lower masses favor the formation of small aggregates. Both simulations for SAXS and TEM give compatible a…
The effect of silica nanoparticles on transient microemulsion networks made of microemulsion droplets and telechelic copolymer molecules in water is studied, as a function of droplet size and concentration, amount of copolymer, and nanoparticle volume fraction. The phase diagram is found to be affected, and in particular the percolation threshold characterized by rheology is shifted upon addition of nanoparticles, suggesting participation of the particles in the network. This leads to a peculiar reinforcement behaviour of such microemulsion nanocomposites, the silica influencing both the modul…
The gelation kinetics of silica nanoparticles is a central process in physical chemistry, yet it is not fully understood. Gelation times are measured to increase by over 4 orders of magnitude, simply changing the monovalent salt species from CsCl to LiCl. This striking effect has no microscopic explanation within current paradigms. The trend is consistent with the Hofmeister series, pointing to short-ranged solvation effects not included in the standard colloidal (DLVO) interaction potential. By implementing a simple form for short-range repulsion within a model that relates the gelation times…
Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here we present an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-cry…
The present communication reports the first direct measurement of the conformation of a polymer corona grafted around silica nano-particles dispersed inside a nanocomposite, a matrix of the same polymer. This measurement constitutes an experimental breakthrough based on a refined combination of chemical synthesis, which permits to match the contribution of the neutron silica signal inside the composite, and the use of complementary scattering methods SANS and SAXS to extract the grafted polymer layer form factor from the inter-particles silica structure factor. The modelization of the signal o…
The evolution of the polymer structure during nanocomposite formation and annealing of silica-latex nanocomposites is studied using contrast-variation small angle neutron scattering. The experimental system is made of silica nanoparticles (Rsi \approx 8 nm) and a mixture of purpose-synthesized hydrogenated and deuterated nanolatex (Rlatex \approx 12.5 nm). The progressive disappearance of the latex beads by chain interdiffusion and release in the nanocomposites is analyzed quantitatively with a model for the scattered intensity of hairy latex beads and an RPA description of the free chains. In…
The accurate characterization of electrical double layer properties of nanoparticles is of fundamental importance for optimizing their physicochemical properties for specific biotechnological and biomedical applications. In this article, we use classical solvation density functional theory and a surface complexation model to investigate the effects of pH and nanoparticle size on the structural and electrostatic properties of an electrolyte solution surrounding a spherical silica oxide nanoparticle. The formulation has been particularly useful for identifying dominant interactions governing the…
Whereas it is experimentally known that the inclusion of nanoparticles in hydrogels can lead to a mechanical reinforcement, a detailed molecular understanding of the adhesion mechanism is still lacking. Here we use coarse-grained molecular dynamics simulations to investigate the nature of the interface between silica surfaces and solvated polymers. We show how differences in the nature of the polymer and the polymer--solvent interactions can lead to drastically different behavior of the polymer--surface adhesion. Comparing explicit and implicit solvent models, we conclude that this effect cann…
The spatial structure of the transition region between an insulator and an electrolyte solution was studied with x-ray scattering.The electron density profile across the n-hexane/silica sol interface (solutions with 5-nm, 7-nm, and 12-nm colloidal particles) agrees with the theory of the electrical double layer and shows separation of positive and negative charges. The interface consists of three layers, i.e., a compact layer of Na+, a loose monolayer of nanocolloidal particles as part of a thick diffuse layer, and a low-density layer sandwiched between them. Its structure is described by a mo…
We propose and demonstrate a method to achieve large effective Soret coefficient in colloids by suitably mixing two different particles, e.g., silica beads and Fe3O4 nanoparticles. It is shown that the thermophoretic motion of Fe3O4 nanoparticles out of the heating region results in a large nonequlibrium depletion force for silica beads. Consequently, silica beads are driven quickly to the heating region, forming a three-dimensional crystal with few defects and dislocations. The binding of silica beads is so tight that a colloidal photonic crystal can be achieved after the complete evaporation…
We present the results of a systematic study of photoelectron emission from gasphase dielectric nanoparticles (SiO2) irradiated by intense 25 fs, 780 nm linearly polarized laser pulses as a function of particle size (20 nm to 750 nm in diameter) and laser intensity. We also introduce an experimental technique to reduce the effects of focal volume averaging. The highest photoelectron energies show a strong size dependence, increasing by a factor of six over the range of particles sizes studied at a fixed intensity. For smaller particle sizes (up to 200 nm), our findings agree well with earlier …
