Cryo-electron tomography study of the evolution of wormlike micelles to saturated networks and perforated vesicles.

HYPOTHESIS: The formation of micellar aggregates and the changes in their morphology are crucial for numerous practical applications of surfactants. However, a proper structural characterization of complicated micellar nanostructures remains a challenge. This paper demonstrates the advances of cryo-electron tomography (cryo-ET) in revealing the structural characteristics that accompany the evolution of surfactant aggregates. EXPERIMENTS: By using cryo-ET in combination with cryo-transmission electron microscopy (cryo-TEM), small-angle neutron scattering (SANS), and rheometry, studies were carried out on a model system composed of zwitterionic and nonionic surfactants. In this system, the molecular packing parameter was increased gradually by increasing the molar fraction of nonionic surfactant. FINDINGS: A series of structural transformations was observed: linear wormlike micelles (WLMs) â†’ branched WLMs â†’ saturated network of multiconnected WLMs â†’ perforated vesicles (stomatosomes). The transformations occur through an increase in the number of branches at the expense of cylindrical subchains and semispherical endcaps. Exponential distribution of subchains length was confirmed experimentally for multiconnected saturated networks. The stomatosomes were formed when the length of subchains becomes much shorter than the persistence length, causing the three-dimensional (3D) structure to transform into a two-dimensional (2D) membrane. This work identifies the mechanism of the structural changes, which can be further used to design various surfactant self-assemblies.

Dual Semi-Interpenetrating Networks of Water-Soluble Macromolecules and Supramolecular Polymer-like Chains: The Role of Component Interactions.

Dual networks formed by entangled polymer chains and wormlike surfactant micelles have attracted increasing interest in their application as thickeners in various fields since they combine the advantages of both polymer- and surfactant-based fluids. In particular, such polymer-surfactant mixtures are of great interest as novel hydraulic fracturing fluids with enhanced properties. In this study, we demonstrated the effect of the chemical composition of an uncharged polymer poly(vinyl alcohol) (PVA) and pH on the rheological properties and structure of its mixtures with a cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride already exploited in fracturing operations. Using a combination of several complementary techniques (rheometry, cryo-transmission electron microscopy, small-angle neutron scattering, and nuclear magnetic resonance spectroscopy), we showed that a small number of residual acetate groups (2-12.7 mol%) in PVA could significantly reduce the viscosity of the mixed system. This result was attributed to the incorporation of acetate groups in the corona of the micellar aggregates, decreasing the molecular packing parameter and thereby inducing the shortening of worm-like micelles. When these groups are removed by hydrolysis at a pH higher than 7, viscosity increases by five orders of magnitude due to the growth of worm-like micelles in length. The findings of this study create pathways for the development of dual semi-interpenetrating polymer-micellar networks, which are highly desired by the petroleum industry.

Cobalt Ferrite Nanorods Synthesized with a Facile "Green" Method in a Magnetic Field.

We report a new facile method for the synthesis of prolate cobalt ferrite nanoparticles without additional stabilizers, which involves a co-precipitation reaction of Fe3+ and Co2+ ions in a static magnetic field. The magnetic field is demonstrated to be a key factor for the 1D growth of cobalt ferrite nanocrystals in the synthesis. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy are applied to characterize the morphology and structure of the obtained nanoparticles. According to TEM, they represent nanorods with a mean length of 25 nm and a diameter of 3.4 nm that have a monocrystalline structure with characteristic plane spacing of 2.9 Å. XRD and Raman spectroscopy confirm the spinel CoFe2O4 structure of the nanorods. After aging, the synthesized nanorods exhibit maximum saturation magnetization and coercivity equal to 30 emu/g and 0.3 kOe, respectively. Thus, the suggested method is a simple and "green" way to prepare CoFe2O4 nanorods with high aspect ratios and pronounced magnetic properties, which are important for various practical applications, including biomedicine, energy storage, and the preparation of anisotropic magnetic nanocomposites.

Double Photocrosslinked Responsive Hydrogels Based on Hydroxypropyl Guar.

Double crosslinked hydrogels based on a biodegradable polymer were prepared by photocopolymerization of methacrylated hydroxypropyl guar (HPG-MA) and 3-acrylamidophenylboronic acid. Along with irreversible strong covalent crosslinks by methacrylic groups, these hydrogels contained labile boronate crosslinks formed as a result of the interaction of boronic acid with cis-diol moieties of HPG. These hydrogels demonstrated higher elasticity than HPG-MA hydrogels with only irreversible covalent crosslinks. Labile boronate crosslinks not only strengthened the hydrogels but also imparted to them pronounced responsive properties. It was demonstrated that the mechanical properties, the swelling behavior, as well as the uptake and release of some substances from the double crosslinked hydrogel were pH controlled. For instance, the hydrogels could release cationic disinfectant at a rate regulated by pH. Such photocrosslinkable in situ forming hydrogels are very promising for the production of smart coatings that release targeted substances at the desired rate.

Hybrid Polymer-Surfactant Wormlike Micelles for Concurrent Use for Oil Recovery and Drag Reduction.

We report on the effect of a hydrocarbon (n-dodecane) on the rheological properties and shapes of the hybrid wormlike micelles (WLMs) of a surfactant potassium oleate with an embedded polymer poly(4-vinylpyridine). With and without hydrocarbon solutions, the hybrid micelles exhibit the same values of viscosity at shear rates typical for hydraulic fracturing (HF) tests, as solutions of polymer-free WLMs. Therefore, similar to WLMs of surfactants, they could be applied as thickeners in HF fluids without breakers. At the same time, in the presence of n-dodecane, the hybrid micelles have much higher drag-reducing efficiency compared to microemulsions formed in polymer-free systems since they form "beads-on-string" structures according to results obtained using cryo-transmission electron microscopy (cryo-TEM), dynamic-light scattering (DLS), and small-angle X-ray scattering (SAXS). Consequently, they could also act as drag-reducing agents in the pipeline transport of recovered oil. Such a unique multi-functional additive to a fracturing fluid, which permits its concurrent use in oil production and oil transportation, has not been proposed before.

Salt-Induced Transformations of Hybrid Micelles Formed by Anionic Surfactant and Poly(4-vinylpyridine).

Salt-induced structural transformation of charged hybrid surfactant/polymer micelles formed by potassium oleate and poly(4-vinylpyridine) was investigated by cryo-TEM, SANS with contrast variation, DLS, and 2D NOESY. Cryo-TEM data show, that at small salt concentration beads-on-string aggregates on polymer chains are formed. KCl induces the transformation of those aggregates into rods, which is due to the screening of the electrostatic repulsion between similarly charged beads by added salt. In a certain range of salt concentration, the beads-on-string aggregates coexist with the rodlike ones. In the presence of polymer, the sphere-to-rod transition occurs at higher salt concentration than in pure surfactant system indicating that hydrophobic polymer favors the spherical packing of potassium oleate molecules. The size of micelles was estimated by DLS. The rods that are formed in the hybrid system are much shorter than those in polymer-free surfactant solution suggesting the stabilization of the semi-spherical endcaps of the rods by embedded polymer. 2D NOESY data evidence that in the spherical aggregates the polymer penetrates deep into the core, whereas in tighter packed rodlike aggregates it is located mainly at core/corona interface. According to SANS with contrast variation, inside the rodlike aggregates the polymer adopts more compact coil conformation than in the beads-on-string aggregates. Such adaptive self-assembled polymer-surfactant nanoparticles with water-insoluble polymer are very promising for various applications including drag reduction at transportation of fluids.

Universal Character of Breaking of Wormlike Surfactant Micelles by Additives of Different Hydrophobicity.

Wormlike surfactant micelles are widely used in various applications including fracturing technology in oil industry, template synthesis of different nanoobjects, micellar copolymerization of hydrophilic and hydrophobic monomers, and so forth. Most of those applications suggest the solubilization of different additives in the micelles. The present paper is aimed at the comparative study of the effect of the solubilization of hydrophobic (n-decane and 1-phenylhexane) and hydrophilic (N-isopropylacrylamide and acrylamide) substances on the rheological properties and structure of the micelles using several complementary techniques including rheometry, small angle neutron scattering, dynamic light scattering, and diffusion ordered NMR spectroscopy. For these studies, mixed micelles of potassium oleate and n-octyltrimethylammonium bromide containing the excess of either anionic or cationic surfactants were used. It was shown that hydrophobic additives are completely solubilized inside the micelles being localized deep in the core (n-decane, 1-phenylhexane) or near the core/corona interface (1-phenylhexane). At the same time, only a small fraction of hydrophilic additives (14% of N-isopropylacrylamide and 4% of acrylamide) penetrate the micelles being localized at the corona area. Despite different localization of the additives inside the micelles, all of them induce the breaking of wormlike micelles with the formation of either ellipsoidal microemulsion droplets (in the case of hydrophobic additives) or ellipsoidal surfactant micelles (in the case of hydrophilic additives). The breaking of micelles results in the drop of viscosity of the solution up to water value. The main result of this paper consists in the observation of the fact that for all the additives under study, the dependences of the viscosity on the volume fraction of additive lie on the same master curve being shifted along the volume fraction axis by a certain factor depending on the hydrophobicity of the added species. Those data are quite useful for various applications of wormlike surfactant micelles suggesting the solubilization of different additives inside them.

Modeling Micellar Growth and Branching in Mixtures of Zwitterionic with Ionic Surfactants.

Zwitterionic surfactants are widely applied as drag-reducing or thickening agents because their aggregation patterns may drastically change in response to variations of the system composition or external stimuli, which provides controllable viscoelasticity. For predicting aggregation behavior of surfactant mixtures, classical molecular thermodynamic models have been widely used. Particularly, the results of modeling have been reported for zwitterionic/ionic surfactant mixtures. However, for solutions containing a zwitterionic surfactant, no molecular thermodynamic model has been proposed for a micellar branch. In this work we extend the classical molecular thermodynamic aggregation model to describe aggregation in the aqueous mixtures that contain a zwitterionic and an ionic surfactant. We derive analytical expressions (1) for the contribution of dipoles to the electrostatic term of the standard free energy of aggregation into micellar branches and (2) for the dipolar contribution to the persistence length of wormlike micelles. The dependence of micellar branching on the surfactant concentration is taken into account by including the population of micellar branches in the material balance equations. This model is applied to predict aggregation equilibrium in aqueous salt solutions of betaine (oleoylamidopropyl-N,N-dimethylbetaine) mixed with sodium dodecyl sulfate (SDS) and the longer tail sodium n-alkyl sulfates. We discuss the predicted properties of the aggregates and micellar networks and compare our predictions with available experimental data.

Antiseptic Polymer-Surfactant Complexes with Long-Lasting Activity against SARS-CoV-2.

Antiseptic polymer gel-surfactant complexes were prepared by incorporating the low-molecular-weight cationic disinfectant cetylpyridinium chloride into the oppositely charged, slightly cross-linked polymer matrices. Three types of polymers were used: copolymers of acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate; copolymers of acrylamide and sodium methacrylate; copolymers of vinylpyrrolidone and sodium methacrylate. It was shown that the rate of the release of the cationic disinfectant from the oppositely charged polymer gels could be tuned in a fairly broad range by varying the concentration of the disinfectant, the degree of swelling, and degree of cross-linking of the gel and the content/type of anionic repeat units in the polymer matrix. Polymer-surfactant complexes were demonstrated to reduce SARS-CoV-2 titer by seven orders of magnitude in as little as 5 s. The complexes retained strong virucidal activity against SARS-CoV-2 for at least one week.

Cationic Surfactants as Disinfectants against SARS-CoV-2.

The virucidal activity of a series of cationic surfactants differing in the length and number of hydrophobic tails (at the same hydrophilic head) and the structure of the hydrophilic head (at the same length of the hydrophobic n-alkyl tail) was compared. It was shown that an increase in the length and number of hydrophobic tails, as well as the presence of a benzene ring in the surfactant molecule, enhance the virucidal activity of the surfactant against SARS-CoV-2. This may be due to the more pronounced ability of such surfactants to penetrate and destroy the phospholipid membrane of the virus. Among the cationic surfactants studied, didodecyldimethylammonium bromide was shown to be the most efficient as a disinfectant, its 50% effective concentration (EC50) being equal to 0.016 mM. Two surfactants (didodecyldimethylammonium bromide and benzalkonium chloride) can deactivate SARS-CoV-2 in as little as 5 s.

Green nanocomposite gels based on binary network of sodium alginate and percolating halloysite clay nanotubes for 3D printing.

Alginate hydrogels with embedded rigid percolating network of halloysite clay nanotubes were evaluated as a novel ink for 3D printing. Hydrophilic alginate macromolecules adsorbing on halloysite stabilize the network of the nanotubes and form their own network of interlaced polymer chains. The effect of halloysite content on the structure and properties of the hydrogels was studied by rheometry, thermogravimetric analysis, FTIR-spectroscopy, dynamic light scattering, transmission electron microscopy, and 3D cryo-electron microscopy. Hydrogels demonstrate a very pronounced shear-thinning at extrusion and rather quick viscosity recovery after extrusion assigned to rapid rearrangement of the network structure promoted by mobile alginate chains. Even at low volume fractions (up to 0.054) the nanotubes reinforce the hydrogel increasing its storage modulus up to 650 Pa and inducing the appearance of yield stress. These properties make the alginate/halloysite hydrogels promising for the application in 3D printing for fabrication of green and sustainable nanocomposite materials made from natural components.

Double dynamic hydrogels formed by wormlike surfactant micelles and cross-linked polymer.

HYPOTHESIS: Interpenetrating networks consisting of a polymer network with dynamic cross-links and a supramolecular network allow obtaining hydrogels with significantly enhanced mechanical properties. EXPERIMENTS: Binary hydrogels composed of a dynamically cross-linked poly(vinyl alcohol) (PVA) network and a transient network of entangled highly charged mixed wormlike micelles (WLMs) of surfactants (potassium oleate and n-octyltrimethylammonium bromide) were prepared and studied by rheometry, SANS, USANS, cryo-TEM, and NMR spectroscopy. FINDINGS: Binary hydrogels show significantly enhanced rheological properties (a 3400-fold higher viscosity and 27-fold higher plateau modulus) as compared to their components taken separately. This is due to the microphase separation leading to local concentrating of PVA and WLMs providing larger number of polymer-polymer contacts for cross-linking and longer WLMs with more entanglements. Such materials are very promising for the application in many areas, ranging from enhanced oil recovery to biomedical uses.

Printable Alginate Hydrogels with Embedded Network of Halloysite Nanotubes: Effect of Polymer Cross-Linking on Rheological Properties and Microstructure.

Rapidly growing 3D printing of hydrogels requires network materials which combine enhanced mechanical properties and printability. One of the most promising approaches to strengthen the hydrogels consists of the incorporation of inorganic fillers. In this paper, the rheological properties important for 3D printability were studied for nanocomposite hydrogels based on a rigid network of percolating halloysite nanotubes embedded in a soft alginate network cross-linked by calcium ions. Particular attention was paid to the effect of polymer cross-linking on these properties. It was revealed that the system possessed a pronounced shear-thinning behavior accompanied by a viscosity drop of 4-5 orders of magnitude. The polymer cross-links enhanced the shear-thinning properties and accelerated the viscosity recovery at rest so that the system could regain 96% of viscosity in only 18 s. Increasing the cross-linking of the soft network also enhanced the storage modulus of the nanocomposite system by up to 2 kPa. Through SAXS data, it was shown that at cross-linking, the junction zones consisting of fragments of two laterally aligned polymer chains were formed, which should have provided additional strength to the hydrogel. At the same time, the cross-linking of the soft network only slightly affected the yield stress, which seemed to be mainly determined by the rigid percolation network of nanotubes and reached 327 Pa. These properties make the alginate/halloysite hydrogels very promising for 3D printing, in particular, for biomedical purposes taking into account the natural origin, low toxicity, and good biocompatibility of both components.

Dual Transient Networks of Polymer and Micellar Chains: Structure and Viscoelastic Synergy.

Dual transient networks were prepared by mixing highly charged long wormlike micelles of surfactants with polysaccharide chains of hydroxypropyl guar above the entanglement concentration for each of the components. The wormlike micelles were composed of two oppositely charged surfactants potassium oleate and n-octyltrimethylammonium bromide with a large excess of anionic surfactant. The system is macroscopically homogeneous over a wide range of polymer and surfactant concentrations, which is attributed to a stabilizing effect of surfactants counterions that try to occupy as much volume as possible in order to gain in translational entropy. At the same time, by small-angle neutron scattering (SANS) combined with ultrasmall-angle neutron scattering (USANS), a microphase separation with the formation of polymer-rich and surfactant-rich domains was detected. Rheological studies in the linear viscoelastic regime revealed a synergistic 180-fold enhancement of viscosity and 65-fold increase of the longest relaxation time in comparison with the individual components. This effect was attributed to the local increase in concentration of both components trying to avoid contact with each other, which makes the micelles longer and increases the number of intermicellar and interpolymer entanglements. The enhanced rheological properties of this novel system based on industrially important polymer hold great potential for applications in personal care products, oil recovery and many other fields.

Novel Trends in the Development of Surfactant-Based Hydraulic Fracturing Fluids: A Review.

Viscoelastic surfactants (VES) are amphiphilic molecules which self-assemble into long polymer-like aggregates-wormlike micelles. Such micellar chains form an entangled network, imparting high viscosity and viscoelasticity to aqueous solutions. VES are currently attracting great attention as the main components of clean hydraulic fracturing fluids used for enhanced oil recovery (EOR). Fracturing fluids consist of proppant particles suspended in a viscoelastic medium. They are pumped into a wellbore under high pressure to create fractures, through which the oil can flow into the well. Polymer gels have been used most often for fracturing operations; however, VES solutions are advantageous as they usually require no breakers other than reservoir hydrocarbons to be cleaned from the well. Many attempts have recently been made to improve the viscoelastic properties, temperature, and salt resistance of VES fluids to make them a cost-effective alternative to polymer gels. This review aims at describing the novel concepts and advancements in the fundamental science of VES-based fracturing fluids reported in the last few years, which have not yet been widely industrially implemented, but are significant for prospective future applications. Recent achievements, reviewed in this paper, include the use of oligomeric surfactants, surfactant mixtures, hybrid nanoparticle/VES, or polymer/VES fluids. The advantages and limitations of the different VES fluids are discussed. The fundamental reasons for the different ways of improvement of VES performance for fracturing are described.

Unmodified Silica Nanoparticles Enhance Mechanical Properties and Welding Ability of Epoxy Thermosets with Tunable Vitrimer Matrix.

Epoxy/silica thermosets with tunable matrix (vitrimers) were prepared by thermal curing of diglycidyl ether of bisphenol A (DGEBA) in the presence of a hardener-4-methylhexahydrophthalic anhydride (MHHPA), a transesterification catalyst-zinc acetylacetonate (ZAA), and 10-15 nm spherical silica nanoparticles. The properties of the resulting material were studied by tensile testing, thermomechanical and dynamic mechanical analysis. It is shown that at room temperature the introduction of 5-10 wt% of silica nanoparticles in the vitrimer matrix strengthens the material leading to the increase of the elastic modulus by 44% and the tensile stress by 25%. Simultaneously, nanoparticles enhance the dimensional stability of the material since they reduce the coefficient of thermal expansion. At the same time, the transesterification catalyst provides the thermoset with the welding ability at heating, when the chain exchange reactions are accelerated. For the first time, it was shown that the silica nanoparticles strengthen welding joints in vitrimers, which is extremely important, since it allows to repeatedly use products made of thermosets and heal defects in them. Such materials hold great promise for use in durable protective coatings, adhesives, sealants and many other applications.

Remotely Self-Healable, Shapeable and pH-Sensitive Dual Cross-Linked Polysaccharide Hydrogels with Fast Response to Magnetic Field.

The development of actuators with remote control is important for the construction of devices for soft robotics. The present paper describes a responsive hydrogel of nontoxic, biocompatible, and biodegradable polymer carboxymethyl hydroxypropyl guar with dynamic covalent cross-links and embedded cobalt ferrite nanoparticles. The nanoparticles significantly enhance the mechanical properties of the gel, acting as additional multifunctional non-covalent linkages between the polymer chains. High magnetization of the cobalt ferrite nanoparticles provides to the gel a strong responsiveness to the magnetic field, even at rather small content of nanoparticles. It is demonstrated that labile cross-links in the polymer matrix impart to the hydrogel the ability of self-healing and reshaping as well as a fast response to the magnetic field. In addition, the gel shows pronounced pH sensitivity due to pH-cleavable cross-links. The possibility to use the multiresponsive gel as a magnetic-field-triggered actuator is demonstrated.

Transformations of wormlike surfactant micelles induced by a water-soluble monomer.

HYPOTHESIS: Wormlike surfactant micelles (WLMs) are prospective as nanoreactors for micellar copolymerization of hydrophilic and hydrophobic monomers. Hydrophilic monomers can destroy WLMs. Large size and cylindrical shape of micelles can be preserved by high salt content favoring closer packing of surfactant heads. EXPERIMENTS: The effect of a water-soluble monomer (acrylamide) on the structure and rheological properties of giant WLMs of an anionic surfactant potassium oleate at different salt content was investigated by combined experimental (SANS, rheometry, fluorescence and NMR spectroscopy, tensiometry) and molecular dynamics simulations studies. FINDINGS: At low salt content, when WLMs are linear, acrylamide induces their shortening and transformation into spherical micelles as a result of its incorporation into the micellar corona, leading to the drop of viscosity. At high salt content providing branched WLMs, monomer first triggers their transition to long linear chains, which enhances the viscoelasticity, and then to rods. This is the first report showing that the effect of monomer on the rheological properties is quite different for linear and branched micelles. Using branched micelles allows preserving large WLMs at high water-soluble monomer content, which is favorable for their use as nanoreactors for synthesis of copolymers with high degree of blockiness, which give mechanically tough polymer gels.

Disruption of Cationic/Anionic Viscoelastic Surfactant Micellar Networks by Hydrocarbon as a Basis of Enhanced Fracturing Fluids Clean-Up.

Studies of the effects produced by the solubilization of hydrophobic substances by micellar aggregates in water medium are quite important for applications of viscoelastic surfactant solutions for enhanced oil recovery (EOR), especially in hydraulic fracturing technology. The present paper aims at the investigation of the structural transformations produced by the absorption of an aliphatic hydrocarbon (n-decane) by mixed wormlike micelles of cationic (n-octyltrimethylammonium bromide, C8TAB) and anionic (potassium oleate) surfactants enriched by C8TAB. As a result of contact with a small amount (0.5 wt%) of oil, a highly viscoelastic fluid is transformed to a water-like liquid. By small-angle neutron scattering (SANS) combined with cryo-TEM, it was shown that this is due to the transition of long wormlike micelles with elliptical cross-sections to ellipsoidal microemulsion droplets. The non-spherical shape was attributed to partial segregation of longer- and shorter-tail surfactant molecules inside the surfactant monolayer, providing an optimum curvature for both of them. As a result, the long-chain surfactant could preferably be located in the flatter part of the aggregates and the short-chain surfactant-at the ellipsoid edges with higher curvature. It is proven that the transition proceeds via a co-existence of microemulsion droplets and wormlike micelles, and upon the increase of hydrocarbon content, the size and volume fraction of ellipsoidal microemulsion droplets increase. The internal structure of the droplets was revealed by contrast variation SANS, and it was shown that, despite the excess of the cationic surfactant, the radius of surfactant shell is controlled by the anionic surfactant with longer tail. These findings open a way for optimizing the performance of viscoelastic surfactant fluids by regulating both the mechanical properties of the fluids and their clean-up from the fracture induced by contact with hydrocarbons.

Magnetic-field-assisted synthesis of anisotropic iron oxide particles: Effect of pH.

The synthesis of magnetite (Fe3O4) nanorods using reverse co-precipitation of Fe3+ and Fe2+ ions in the presence of a static magnetic field is reported in this work. The phase composition and crystal structure of the synthesized material were investigated using electron diffraction, Raman spectroscopy, and transmission electron microscopy. It was shown that the morphology of the reaction product strongly depends on the amount of OH- ions in the reaction mixture, varying from Fe3O4 nanorods to spherical Fe3O4 nanoparticles. Fe3O4 nanorods were examined using high-resolution transmission electron microscopy proving that they are single-crystalline and do not have any preferred crystallographic orientation along the axis of the rods. According to the data obtained a growth mechanism was proposed for the rods that consists of the dipole-dipole interaction between their building blocks (small hexagonal faceted magnetite nanocrystals), which are formed during the first step of the reaction. The study suggests a facile, green and controllable method for synthesizing anisotropic magnetic nanoparticles in the absence of stabilizers, which is important for further modification of their surfaces and/or incorporation of the nanoparticles into different media.