page_title: Janus particles
section_title: Masking
hierarchical_section_title: Janus particles / Synthesis / Masking
caption_attribution_description: English: (a) Schematic representation of the microfabrication process. After creating a monolayer of fluorescent particle, bilayers of 1:10 Ti/Au are deposited on the top half of particles. The wafer is then placed in a becher with 2 ml DI water and sonicated for 2 h, where JPs are resuspended. (b) SEM micrographs show the three types of JPs fabricated. Scale bar represents 500 nm.
context_page_description: Janus particles are special types of nanoparticles or microparticles whose surfaces have two or more distinct physical properties. This unique surface of Janus particles allows two different types of chemistry to occur on the same particle. The simplest case of a Janus particle is achieved by dividing the particle into two distinct parts, each of them either made of a different material, or bearing different functional groups. For example, a Janus particle may have one-half of its surface composed of hydrophilic groups and the other half hydrophobic groups, the particles might have two surfaces of different color, fluorescence, or magnetic properties. This gives these particles unique properties related to their asymmetric structure and/or functionalization.
context_section_description: Masking was one of the first techniques developed for the synthesis of Janus nanoparticles. This technique was developed by simply taking synthesis techniques of larger Janus particles and scaling down to the nanoscale. Masking, as the name suggests, involves the protection of one side of a nanoparticle followed by the modification of the unprotected side and the removal of the protection. Two masking techniques are common to produce Janus particles, evaporative deposition and a technique where the nanoparticle is suspended at the interface of two phases. However, only the phase separation technique scales well to the nanoscale.
  The phase interface method involves trapping homogeneous nanoparticles at the interface of two immiscible phases. These methods typically involve the liquid–liquid and liquid–solid interfaces, but a gas–liquid interface method has been described.
  The liquid–liquid interface method is best exemplified by Gu et al., who made an emulsion from water and an oil and added nanoparticles of magnetite. The magnetite nanoparticles aggregated at the interface of the water-oil mixture, forming a Pickering emulsion. Then, silver nitrate was added to the mixture, resulting in the deposition of silver nanoparticles on the surface of the magnetite nanoparticles. These Janus nanoparticles were then functionalized by the addition of various ligands with specific affinity for either the iron or silver. This method can also use gold or iron-platinum instead of magnetite.
  A similar method is the gas–liquid interface method developed by Pradhan et al. In this method, hydrophobic alkane thiolate gold nanoparticles were placed in water, causing the formation of a monolayer of the hydrophobic gold nanoparticles on the surface. Air pressure was then increased, forcing the hydrophobic layer to be pushed into the water, decreasing the contact angle. When the contact angle was at the desired level, a hydrophilic thiol, 3-mercaptopropane-1,2-diol, was added to the water, causing the hydrophilic thiol to competitively replace the hydrophobic thiols, resulting in the formation of amphiphilic Janus nanoparticles.
  The liquid–liquid and gas–liquid interface methods do have an issue where the nanoparticles can rotate in solution, causing the deposition of silver on more than one face. A liquid–liquid/liquid–solid hybrid interface method was first introduced by Granick et al. as a solution to this liquid–liquid method problem. In this method, molten paraffin wax was substituted for the oil, and silica nanoparticles for the magnetite. When the solution was cooled, the wax solidified, trapping half of each silica nanoparticle in the wax surface, leaving the other half of the silica exposed. The water was then filtered off and the wax-trapped silica nanoparticles were then exposed to a methanol solution containing (amino-
  propyl)triethoxysilane, which reacted with the exposed silica surfaces of the nanoparticles. The methanol solution was then filtered off and the wax was dissolved with chloroform, freeing the newly made Janus particles.  Liu et al. reported the synthesis of acorn- and mushroom-shaped silica–aminopropyl–trimethoxysilane Janus nanoparticles using the hybrid liquid–liquid/liquid–solid method developed by Granick et al. They exposed homogenous aminopropyl-trimethoxysilane functionalized silica nanoparticles embedded in wax to an ammonium fluoride solution, which etched away the exposed surface. The liquid–liquid/liquid–solid hybrid method also has some drawbacks; when exposed to the second solvent for functionalization, some of the nanoparticles may be released from the wax, resulting in homogenous instead of Janus nanoparticles. This can partially be corrected by using waxes with higher melting points or performing functionalization at lower temperatures. However, these modifications still result in significant loss. Cui et al. designed a more enduring mask made of polydimethylsiloxane (PDMS) polymer film to create a liquid–liquid/liquid–solid interface. The exposed-to-be-modified portion of particle surface can be adjus
caption: (a) Schematic representation of a masking microfabrication process. After creating a monolayer of fluorescent particles, bilayers of 1:10 Ti/Au are deposited on the top half of particles. The wafer is then placed in a beaker with 2 ml DI water and sonicated for 2 h to resuspend them. (b) SEM micrographs show the three types of JPs fabricated. Scale bar represents 500 nm.[21]
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