Simple method to produce Janus colloidal particles in large quantity

A simple, generalizable, inexpensive method is demonstrated to synthesize Janus colloidal particles in large quantity. At the liquid-liquid interface of emulsified molten wax and water, untreated particles adsorb and are frozen in place when the wax solidifies. The exposed surfaces of the immobilized particles are modified chemically. Finally, wax is dissolved, and the inner surfaces are modified chemically. Gram-sized quantities or more of Janus particles can be synthesized by taking this approach.     

Controlling the geometry (Janus balance) of amphiphilic colloidal particles

A simple, generalizable method is described to produce Janus colloidal particles in large quantity with control over their respective hydrophobic and hydrophilic areas (Janus balance) in large quantity. To this end, charged particles adsorb onto the liquid-liquid interface of emulsions of molten wax and water in the presence of surfactants of opposite charge, whose concentration modifies how deeply particles penetrate the oil-water interface, and subsequent surface chemical modification of the resulting colloidosomes is performed after lowering temperature to solidify the wax. Silica particles modified in this way using different amounts of didodecyldimethylammonium bromide (DDAB) display contact angles that vary controllably between 37 degrees and 75 degrees. Janus balance also varies but over a more limited range with control of pH, salt concentration, or the presence of nonionic surfactant (Tween 20 or ethanol). Purity, Janus balance, and colloidosome structure are evaluated by a combination of fluorescence microscopy, flow cytometry, and scanning electron microscopy (SEM). The three-phase contact angle is obtained by observing SEM images of voids left by particles escaped from the surface. Colloidosomes made in the presence of DDAB are markedly improved with respect to the hexagonal close packing, which helps increase the efficiency of the method. Gram-sized quantities of particles are synthesized.     

Janus particles with a functional gold surface for control of surface plasmon resonance

We report in this study the presence of Janus particles, which are candidates for use with electronic color papers. We used negatively charged polystyrene particles (370 nm) as the core particles, and gold was then sputtered onto their packed monolayer under several conditions. The sputtered particles were next redispersed into the aqueous medium by gentle sonication. Gold nanoparticles localized on one side of the cores could also serve as seeds for subsequent shell growth by electroless gold plating. Through these treatments, a series of well-dispersed Janus particles were obtained with gold nanostructures of different size and shape only on one side. Their dispersions showed different colors originating from the surface plasmon resonance absorption of gold nanoparticles localized on the hemisphere. The particles obtained by this approach have potential applications such as in sensors and electronic color paper.     

Preparation and controlled self-assembly of Janus magnetic nanoparticles

Janus magnetic nanoparticles (~20 nm) were prepared by grafting either polystyrene sodium sulfonate (PSSNa) or polydimethylamino ethylmethacrylate (PDMAEMA) to the exposed surfaces of negatively charged poly(acrylic acid) (PAA)-coated magnetite nanoparticles adsorbed onto positively charged silica beads. Individually dispersed Janus nanoparticles were obtained by repulsion from the beads on reversal of the silica surface charge when the solution pH was increased. Controlled aggregation of the Janus nanoparticles was observed at low pH values, with the formation of stable clusters of approximately 2-4 times the initial size of the particles. Cluster formation was reversed, and individually dispersed nanoparticles recovered, by restoring the pH to high values. At intermediate pH values, PSSNa Janus nanoparticles showed moderate clustering, while PDMAEMA Janus nanoparticles aggregated uncontrollably due to dipolar interactions. The size of the stable clusters could be controlled by increasing the molecular weight of the grafted polymer, or by decreasing the magnetic nanoparticle surface availability for grafting, both of which yielded larger cluster sizes. The addition of small amounts of PAA-coated magnetic nanoparticles to the Janus nanoparticle suspension resulted in a further increase in the final cluster size. Monte Carlo simulation results compared favorably with experimental observations and showed the formation of small, elongated clusters similar in structure to those observed in cryo-TEM images.     

Adhesion force studies of Janus nanoparticles

Janus nanoparticles represent a unique nanoscale analogue to the conventional surfactant molecules, exhibiting hydrophobic characters on one side and hydrophilic characters on the other. Yet, direct visualization of the asymmetric surface structures of the particles remains a challenge. In this paper, we used a simple technique based on AFM adhesion force measurements to examine the two distinctly different hemispheres of the Janus particles at the molecular level. Experimentally, the Janus nanoparticles were prepared by ligand exchange reactions at the air-water interface. The particles were then immobilized onto a substrate surface with the particle orientation controlled by the chemical functionalization of the substrate surface, and an AFM adhesion force was employed to measure the interactions between the tip of a bare silicon probe and the Janus nanoparticles. It was found that when the hydrophilic side of the particles was exposed, the adhesion force was substantially greater than that with the hydrophobic side exposed, as the silicon probes typically exhibit hydrophilic properties. These studies provide further confirmation of the amphiphilic nature of the Janus nanoparticles.     

Production of large quantities of “Janus” nanoparticles using wax-in-water emulsions

For the first time, large amount of Janus silica particles as small as 100 nm in diameter were prepared through a simple method based on the elaboration of Pickering emulsions of wax-in-water. Controlling the kinetic stabilization of wax droplets allows the fabrication of gram-sized quantities of regular asymmetric inorganic particles with high yield. In fact, our method is based on a limited coalescence process, which allows one to predict the quantity of interface which is produced when working with a known mass of wax, and thus to be sure that all introduced silica particles are adsorbed on the wax surface. To this end, the hydrophilic surface of the silica particles was made partially hydrophobic by adsorbing a known amount of surfactant: cetyltrimethylammonium bromide (CTAB). Varying the concentration in surfactant results in tuning the penetration rate of the particles in the wax droplets, leading to various dimension of the modified area. The broken spherical symmetry of the particle surface was thereafter revealed by the selective adsorption of gold nanoparticles on the amino-modified surface.     

Amphiphilic Janus Gold Nanoparticles Prepared by Interface‐Directed Self‐Assembly: Synthesis and Self‐Assembly

Materials with Janus structures are attractive for wide applications in materials science. Although extensive efforts in the synthesis of Janus particles have been reported, the synthesis of sub‐10 nm Janus nanoparticles is still challenging. Herein, the synthesis of Janus gold nanoparticles (AuNPs) based on interface‐directed self‐assembly is reported. Polystyrene (PS) colloidal particles with AuNPs on the surface were prepared by interface‐directed self‐assembly, and the colloidal particles were used as templates for the synthesis of Janus AuNPs. To prepare colloidal particles, thiol‐terminated polystyrene (PS‐SH) was dissolved in toluene and citrate‐stabilized AuNPs were dispersed in aqueous solution. Upon mixing the two solutions, PS‐SH chains were grafted to the surface of AuNPs and amphiphilic AuNPs were formed at the liquid–liquid interface. PS colloidal particles decorated with AuNPs on the surfaces were prepared by adding the emulsion to excess methanol. On the surface, AuNPs were partially embedded in the colloidal particles. The outer regions of the AuNPs were exposed to the solution and were functionalized through the grafting of atom‐transfer radical polymerization (ATRP) initiator. Poly[2‐(dimethamino)ethyl methacrylate] (PDMAEMA) on AuNPs were prepared by surface‐initiated ATRP. After centrifugation and dissolving the colloidal particles in tetrahydrofuran (THF), Janus AuNPs with PS and PDMAEMA on two hemispheres were obtained. In acidic pH, Janus AuNPs are amphiphilic and are able to emulsify oil droplets in water; in basic pH, the Janus AuNPs are hydrophobic. In mixtures of THF/methanol at a volume ratio of 1:5, the Janus AuNPs self‐assemble into bilayer structures with collapsed PS in the interiors and solvated PDMAEMA at the exteriors of the structures.     

Adsorption free energy of variable-charge nanoparticles to a charged surface in relation to the change of the average chemical state of the particles

Variable-charge nanoparticles such as proteins and humics can adsorb strongly to charged macroscopic surfaces such as silica and iron oxide minerals. To model the adsorption of variable-charge particles to charged surfaces, one has to be able to calculate the adsorption free energy involved. It has been shown that the change in the free energy of variable-charge particles is related to the change in their average chemical state upon adsorption, which is commonly described using surface complexation models. In this work, expressions for the free-energy change in variable-charge particles due to changes in chemical binding are derived for three ion-binding models (i.e., the Langmuir, Langmuir-Freundlich, and NICA models) and for changes due to nonspecific binding for the Donnan model. The expressions for the adsorption free energy of the variable-charge particles to a charged surface are derived on the basis of the equality of the (electro)chemical potential of the particles in the bulk solution and adsorption phase. The expressions derived are general in the sense that they account for the competition between charge-determining ions that bind chemically to the particles, and they also apply in case of the formation of chemical bonds between particle ligands and surface sites. The derived expressions can be applied in the future to model the adsorption of variable-charge nanoparticles to charged surfaces. The results obtained for the NICA-Donnan model make it possible to apply this advanced surface complexation model to describe the adsorption of humics to minerals.     

One-step fabrication of polymeric Janus nanoparticles for drug delivery

With its unique structure of two compartments, Janus particles can be used for many applications for which monomorphic particles are inadequate, including to be used as a drug delivery system to deliver multiple payloads with widely different solubility. Here we report on a fluidic nanoprecipitation system (FNPS), capable of fabricating biocompatible Janus polymeric nanoparticles comprised of the FDA-approved polymer poly(lactic-co-glycolic acid) (PLGA). The FNPS contains dual inlets, one for each half of the particle, that insert into the precipitation stream. The system provides a one-step approach for production of Janus polymeric particles with submicrometer diameters and is likely amenable to substantial scale-up. To the best of our knowledge, this is the first demonstration of biocompatible Janus nanoparticles that encapsulate a hydrophobic drug (paclitaxel) on one side and a hydrophilic drug (doxorubicin hydrochloride) on the other.     

Fabrication of a composite colloidal particle with unusual janus structure as a high-performance solid emulsifier

Core-shell particles with cross-linked core and shell were used as seed particles to produce composite Janus particles. It was found that when the shell has distinctly higher cross-linking degree than the core, Janus particles with very unusual structures can be obtained. These particles have two parts, with one part embraced partially or entirely by the other part, adjustable by parameters such as phase ratio or cross-linking degree. On the basis of experimental observations, a possible mechanism for the formation of such unusual Janus particles has been proposed. Janus particles with arms are used to emulsify water-toluene mixtures, forming oil-in-water (O/W) emulsions at very high internal phase content with rather low concentration of particles. Nonspherical emulsion droplets were observed, indicating that these Janus particles are likely to jam at the interface, forming a strong protecting layer to stabilize emulsions.     

Effect of associating polymer on the viscosity behavior of suspensions consisting of particles with different surface properties

Associating polymers which consist of water-soluble long-chain molecules containing a small fraction of hydrophobic groups (hydrophobes) behave as flocculants in aqueous suspensions. The effects of associating polymers on the rheological behavior are studied for single suspensions of particles with hydrophilic and hydrophobic surfaces, and their mixtures. For particles with hydrophilic surfaces, the suspensions are highly flocculated by a bridging mechanism, because the water-soluble chains adsorb onto hydrophilic surfaces. On the other hand, the particles with hydrophobic surfaces cannot be dispersed in water without polymer and the additions of a small amount of polymer are required for preparation of homogeneous suspensions. The associating polymer acts as a dispersant at low concentrations. However, further additions of polymer lead to a drastic increase in viscosity. Since the hydrophobes on one end of molecules adsorb onto hydrophobic surfaces and other hydrophobes tending from the particles can form micelles, the particles are connected by linkage of interchain associations. By mixing two suspensions of particles with hydrophilic and hydrophobic surfaces, the viscosity is substantially reduced and the flow becomes nearly Newtonian. The associating polymer in complex suspensions acts as a binder between the hydrophilic and hydrophobic surfaces. The hetero-flocculation which leads to the formation of composite particles may be responsible for the viscosity reduction of complex suspensions.     

Remote Control of T Cell Activation Using Magnetic Janus Particles

We report a strategy for using magnetic Janus microparticles to control the stimulation of T cell signaling with single‐cell precision. To achieve this, we designed Janus particles that are magnetically responsive on one hemisphere and stimulatory to T cells on the other side. By manipulating the rotation and locomotion of Janus particles under an external magnetic field, we could control the orientation of the particle–cell recognition and thereby the initiation of T cell activation. This study demonstrates a step towards employing anisotropic material properties of Janus particles to control single‐cell activities without the need of complex magnetic manipulation devices.     

Adsorption of the fusogenic peptide B18 onto solid surfaces: insights into the mechanism of peptide assembly

The adsorption and assembly of B18 peptide on various solid surfaces were studied by reflectometry techniques and atomic force microscopy. B18 is the minimal membrane binding and fusogenic motif of the sea urchin protein bindin, which mediates the fertilization process. Silicon substrates were modified to obtain hydrophilic charged surfaces (oxide layer and polyelectrolyte multilayers) and hydrophobic surfaces (octadecyltrichlorosilane). B18 does not adsorb on hydrophilic positively charged surfaces, which was attributed to electrostatic repulsion since the peptide is positively charged. In contrast, the peptide irreversibly adsorbs on negatively charged hydrophilic as well as on hydrophobic surfaces. B18 showed higher affinity for hydrophobic surfaces than for hydrophilic negatively charged surfaces, which must be due to the presence of hydrophobic side chains at both ends of the molecule. Atomic force microscopy provided the indication that lateral diffusion on the surface affects the adsorption process of B18 on hydrophobic surfaces. The adsorption of the peptide on negatively charged surfaces was characterized by the formation of globular clusters.     

两亲性Janus粒子在蜂窝状多孔聚合物膜上的自组装性能

采用具有两亲性的两面体(Janus)粒子实现稳定的粒子界面组装与水滴模板法自组装过程相结合的方法获得了粒子在蜂窝状多孔聚合物薄膜内壁的高效定向修饰.通过与均质粒子组装形貌的对比,证明了Janus粒子因其特殊的界面自组装活性,可以获得高粒子加量条件下的规则多孔结构,解决了使用均质粒子时存在的结构有序性和粒子修饰密度之间的矛盾.而在较低粒子加量的条件下,Janus粒子也展示出与均质粒子极为不同的组装形貌.这一方法的建立,为新型表面功能化材料的制备提供了一个新的思路.     

Preparation of various Janus composite particles with two components differently combined

Janus composite particles with a combination of organic and inorganic substances were synthesized by soap-free emulsion polymerization in which an amphoteric initiator of 2,2′-azobis[N-(2-carboxyethyl)-2-2-methylpropionamidine] (VA-057) was employed to introduce a polystyrene (PSt) lobe onto silica cores surface-modified with 3-methacryloxypropyltrimethoxy silane (MPTMS). Thermogravimetric analysis and X-ray photoelectron spectroscopy were used to characterize the surface-modified silica particles and showed that a small amount of MPTMS introduced onto the surface of silica particles could successfully prepare SiO₂–PSt Janus particles. The oxide part of SiO₂–PSt Janus particles obtained with the polymerization was further surface-modified with 3-aminopropyltriethoxysilane (APS) to introduce positively charged amino groups on the silica surface. The silica surface modified with APS was covered with gold by electroless deposition in which a gold precursor of auric chloride was reduced with ascorbic acid in the presence of polyvinylpyrrolidone. The electroless deposition of gold successfully produced Janus particles with a combination of gold and PSt surfaces. Furthermore, dissolution of the polymer component of the Au–PSt Janus particles in tetrahydrofuran led to another Janus type of particles with an inorganic combination of Au and SiO₂.     

Settling of paraffin crystals in cooled middle distillate fuels

The mechanism of action of additives that control the sedimentation of paraffin crystals after their crystallization in model diesel oil has been studied by means of a new experimental approach. The chemical analysis of the crystals and detailed measurements of the sedimentation phenomenon give new insights into this complex process. Thus, the wax antisettling additives used for preventing wax crystal sedimentation adsorb at the surfaces of wax particles and provide them with enhanced colloidal stability. The settling rate is not related to the size of the crystals or the viscosity of the liquid medium, but to the ability of the additives to prevent the aggregation of wax crystals. The reported methodology makes it possible to investigate the fundamental mechanisms, but also to evaluate structure-activity relationships of the various additives used in the petroleum industry.     

Synthesis of Monodisperse Bi‐Compartmentalized Amphiphilic Janus Microparticles for Tailored Assembly at the Oil–Water Interface

Janus particles endowed with controlled anisotropies represent promising building blocks and assembly materials because of their asymmetric functionalities. Herein, we show that using the seeded monomer swelling and polymerization technique allows us to obtain bi‐compartmentalized Janus microparticles that are generated depending on the phase miscibility of the poly (alkyl acrylate) chains against the polystyrene seed, thus minimizing the interfacial free energy. When tetradecyl acrylate is used, complete compartmentalization into two distinct bulbs can be achieved, while tuning the relative dimension ratio of compartmented bulb against the whole particle. Finally, we have demonstrated that selectively patching the silica nanoparticles onto one of the bulb surfaces gives amphiphilicity to the particles that can assemble at the oil–water interface with a designated level of adhesion, thus leading to development of a highly stable Pickering emulsion system.     

Adsorption orientations and interactions of methyl orange on negatively and positively charged colloidal silver particles

Both positively and negatively charged colloidal silver particles were prepared from chemical deoxidized methods. Then UV-visible absorption, fluorescence, and surface-enhanced Raman scattering of methyl orange adsorbed onto surfaces of these two kinds of particles were observed and compared with each other. The results indicate that dye molecules may adsorb onto these two kinds of silver surface in differing adsorption orientations with different interactions, which caused the different phenomena.     

The structure of ions and zwitterionic lipids regulates the charge of dipolar membranes

In pure water, zwitterionic lipids form lamellar phases with an equilibrium water gap on the order of 2 to 3 nm as a result of the dominating van der Waals attraction between dipolar bilayers. Monovalent ions can swell those neutral lamellae by a small amount. Divalent ions can adsorb onto dipolar membranes and charge them. Using solution X-ray scattering, we studied how the structure of ions and zwitterionic lipids regulates the charge of dipolar membranes. We found that unlike monovalent ions that weakly interact with all of the examined dipolar membranes, divalent and trivalent ions adsorb onto membranes containing lipids with saturated tails, with an association constant on the order of ～10 M(-1). One double bond in the lipid tail is sufficient to prevent divalent ion adsorption. We suggest that this behavior is due to the relatively loose packing of lipids with unsaturated tails that increases the area per lipid headgroup, enabling their free rotation. Divalent ion adsorption links two lipids and limits their free rotation. The ion-dipole interaction gained by the adsorption of the ions onto unsaturated membranes is insufficient to compensate for the loss of headgroup free-rotational entropy. The ion-dipole interaction is stronger for cations with a higher valence. Nevertheless, polyamines behave as monovalent ions near dipolar interfaces in the sense that they interact weakly with the membrane surface, whereas in the bulk their behavior is similar to that of multivalent cations. Advanced data analysis and comparison with theory provide insight into the structure and interactions between ion-induced regulated charged interfaces. This study models biologically relevant interactions between cell membranes and various ions and the manner in which the lipid structure governs those interactions. The ability to monitor these interactions creates a tool for probing systems that are more complex and forms the basis for controlling the interactions between dipolar membranes and charged proteins or biopolymers for encapsulation and delivery applications.     

Surfaces with self-repairable ultrahydrophobicity based on self-organizing freely floating colloidal particles

We report an approach for the design of materials with self-repairable ultrahydrophobic properties. The materials are based on highly fluorinated crystalline fusible wax with incorporated colloidal particles. Due to the highly pronounced tendency of the wax to crystallize, the formation of blends with rough fractal surfaces was observed. In order to prove their self-repairing ability, we mechanically damaged them by scratching, which removed most of the particles from the surface. Melting of the damaged blend resulted in reorganization of the particles at the wax-air interface, restoring the initial structure and thus the ultrahydrophobic behavior.