Assembly Of Janus Particles Research Articles

DNA sensing based on aggregation of Janus particles using dynamic light scattering

BackgroundThe aggregation of isotropic particles through interparticle reactions poses a challenge in control due to the ability of all surfaces to bind to each other, rendering the quantitative detection of such interparticle reactions based on particle size difficult. Here, we proposed a novel detection scheme for DNA utilizing an assembly of Janus particles (JPs) employing dynamic light scattering (DLS). DNA molecules are tethered on one hemisphere of the JP, while the other hemisphere retains its hydrophobic properties. ResultsAggregation of JPs was induced by the sandwich hybridization of target DNA between them. The assembly of JPs was effectively monitored by the changes in hydrodynamic diameter detected by DLS, revealing that aggregation peaks at 2–3 particles and further reaction was hindered due to the inability of one hemisphere of the JP to interact with another JP. The target DNA demonstrated detectability at concentrations as low as several tens of pM to several nM using a digital sensing method. The two types of target DNA, such as simple (14 base pairs) and HIV-2 specific sequences (20 base pairs) were detectable at nM and pM levels, respectively. Moreover, we substantiated the robustness of our detection scheme through stoichiometric calculations based on an equilibrium model. The present detection mechanism was well explained based on the binding affinity of DNA hybridization. SignificanceThis detection method harnesses the anisotropic nature of JPs and represents the first detection approach based on aggregation. By altering the modification molecules on JPs to match target molecules, such as proteins and organic compounds, a wide range of versatile molecules can be detected using this scheme with high sensitivity. This underscores the broad applicability of the present method.

On the Interfacial Assembly of Anisotropic Amphiphilic Janus Particles

AbstractIt has been shown both theoretically and experimentally that amphiphilic Janus particles are the most effective solid surfactants to stabilize interfaces. In most cases, the Janus particles investigated have uniform morphologies with Janus boundaries dividing the particle into halves. However, there are many examples of Janus particles where the hydrophilic and hydrophobic domains are not equally distributed. The effects of this uneven domain distribution on the mechanism and kinetics of Janus particle assembly, and final equilibrium state are not well‐understood. Dynamic pendant drop tensiometry offers a means to probe both the equilibrium assembly and the kinetics and mechanism of assembly. Here, the interfacial kinetics and assembly of spherical anisotropic Janus particles are investigated using dynamic pendant drop tensiometry. Systematic studies quantifying the time‐dependent interfacial behavior as a function of Janus particle morphology, chemical composition, particle concentration, and NaOH and HCl concentration are performed. These studies shed light on the assembly mechanism of more complex Janus particle morphologies and highlight their effectiveness as interface stabilizers.

Orientation-Controlled Ultralong Assembly of Janus Particles Induced by Bubble-Driven Instant Quasi-1D Interfaces

Constructing precisely oriented assemblies and exploring their orientation-dependent properties remain a challenge for Janus nanoparticles (JNPs) due to their asymmetric characteristics. Herein, we propose a bubble-driven instant quasi-1D interfacial strategy for the oriented assembly of JNP chains in a highly controllable manner. It is found that the rapid formation of templated bubbles can promote the interfacial orientation of JNPs kinetically, while the confined quasi-1D interface in the curved liquid bridge can constrain the disordered rotation of the particles, yielding well-oriented JNP chains in a long range. During the evaporation process, the interfacial orientation of the JNPs can be transferred to the assembled chains. By regulating the amphiphilicity of the JNPs, both heteraxial and coaxial JNP assemblies are obtained, which show different polarization dependences on light scattering, and the related colorimetric logic behaviors are demonstrated. This work demonstrates the great potential of patterned interfacial assembly with a manageable orientation and shows the broad prospect of asymmetric JNP assembly in constructing novel optoelectronic devices.

Reverse order-disorder transition of Janus particles confined in two dimensions.

Janus particles with different patch sizes, confined to two dimensions, generate a series of patterns of interest to the field of nanoscience. Here we observe reverse melting, where for some densities the system melts under cooling. For a broad range of hydrophobic patch sizes (60^{∘}<θ_{0}<90^{∘}), a reentrant transition from solid to liquid and then to an ordered phase emerges as temperature (T) decreases due to the formation of rhombus chains at low T. This reentrant phase has pseudo long-range orientational order but short-range translational order, similar to a hexatic phase. Our work provides guidelines to study the melting and assembly of Janus particles in two dimensions, as well as mechanisms to generate phases with specific symmetry.

Substrate wettability guided oriented self assembly of Janus particles

Self-assembly of Janus particles with spatial inhomogeneous properties is of fundamental importance in diverse areas of sciences and has been extensively observed as a favorably functionalized fluidic interface or in a dilute solution. Interestingly, the unique and non-trivial role of surface wettability on oriented self-assembly of Janus particles has remained largely unexplored. Here, the exclusive role of substrate wettability in directing the orientation of amphiphilic metal-polymer Bifacial spherical Janus particles, obtained by topo-selective metal deposition on colloidal Polymestyere (PS) particles, is explored by drop casting a dilute dispersion of the Janus colloids. While all particles orient with their polymeric (hydrophobic) and metallic (hydrophilic) sides facing upwards on hydrophilic and hydrophobic substrates respectively, they exhibit random orientation on a neutral substrate. The substrate wettability guided orientation of the Janus particles is captured using molecular dynamic simulation, which highlights that the arrangement of water molecules and their local densities near the substrate guide the specific orientation. Finally, it is shown that by spin coating it becomes possible to create a hexagonal close-packed array of the Janus colloids with specific orientation on differential wettability substrates. The results reported here open up new possibilities of substrate-wettability driven functional coatings of Janus particles, which has hitherto remained unexplored.

Research Advances in the Synthesis, Application, Assembly, and Calculation of Janus Materials

Janus materials with anisotropy shapes and chemical compositions, including Janus particles, Janus nanosheets, and Janus membranes, have a great significance in the development of new functional materials and expansion of the properties and applications of materials. This review summarizes recent works on Janus materials of preparation, application, assembly, and calculation. First, we briefly sort out the methods of preparing Janus particles and discuss the factors influencing the structure, shape, and size of Janus particles, pointing out their advantages and the direction of improvement. Then, we introduce in detail the applications field from a single Janus particle, assembly of Janus particles, 2D Janus nanosheet, and Janus membrane. We summarize the recent research on the self-assembly of Janus particles and point out the role of the combination of computational simulation and experiment in the research of Janus material. Finally, the research process of Janus materials is reviewed, and the development tendencies of Janus materials and the problems to be solved are summarized.

Surfactant-Mediated Assembly of Amphiphilic Janus Spheres.

We investigate how amphiphilic Janus particle assembly structures, including clusters and striped two-dimensional (2D) crystals, are influenced by the addition of surfactant molecules. Janus particles are fabricated using silica particles coated with Au on one side, which is further modified with a hydrophobic self-assembled monolayer. Analysis on the cluster assembly structures suggests that in addition to hydrophobic attraction, van der Waals (VDW) attraction plays a significant role in the assembly process, which is modulated by the Au coating thickness. This is manifested by the cluster formation induced primarily by VDW forces when the hydrophobic attraction between particles is diminished by adding the surfactant. In the 2D crystal case, sodium dodecyl sulfate (SDS) and Tween 20 show opposite trends in how they affect assembly structures and particle dynamics. SDS shortens the stripes in 2D crystals and accelerates the rotation of particles, whereas Tween 20 extends the straight stripes and slows down the particle rotation. We interpret the results by considering SDS adsorption on the Au-coated hemisphere of the Janus particles and Tween 20 forming hydrogen bonds with the silica hemisphere of Janus particles. Our study offers a simple approach to change the assembly structures of Janus particles, and it provides principles and guidance for potential applications of Janus particles coupled with small amphiphilic molecules.

Cooperative assembly of Janus particles and amphiphilic oligomers: the role of Janus balance.

Cooperative assembly of nanoparticles and amphiphiles has emerged as a significant strategy for constructing hybrid nanocomposites with desired architectures and properties. It is of great significance to develop novel hybrid nanostructures with controlled spatial localization of nanoparticles within hybrid assemblies. Here, by adopting dissipative particle dynamics simulations, the cooperative assembly of Janus particles and amphiphilic oligomers is studied. We demonstrate that a variety of defined hybrid nanostructures such as balls, sticks, disks, lines, vesicles, and networks can be achieved by the cooperative assembly of Janus particles and amphiphilic oligomers. Furthermore, the investigation of the kinetic pathway illustrates that the formation of hybrid assemblies is an entropy-driven process. Our simulation results suggest that the Janus balance of nanoparticles can significantly affect the structure and size of hybrid aggregates and the spatial localization of Janus particles within hybrid assemblies. These findings not only enrich our understanding of the cooperative assembly of Janus nanoparticles and amphiphiles, but also offer a feasible strategy to prepare hybrid materials with controlled localization of nanoparticles.

Shear-induced interfacial assembly of Janus particles

Numerical simulations demonstrate that shearing a cluster of randomly oriented Janus spheres adsorbed at the interface between two immiscible fluids drives their assembly into ordered chains due to the formation of capillary dipoles and the resulting interparticle capillary-induced interactions.

Reversible Janus particle assembly via responsive host-guest interactions.

Reversible assembly of Janus particles was manipulated by host-guest interaction of β-cyclodextrin (β-CD) and azobenzene. One side of every Janus particle was modified with β-CD. Superstructures of Janus particles were formed by adding azobenzene-containing polymers to the dispersion of Janus particles. The superstructures were reversibly disassembled by adding α-CD or light irradiation.

Selective Janus Particle Assembly at Tipping Points of Thermally‐Switched Wetting

Thermal wetting can simply, selectively and reversibly join patchy particles into clusters (2D and 3D) and also colloidal crystals over the narrow temperature range of 1-2 °C. This is demonstrated with Janus particles (gold half-coated silica spheres) immersed in a binary mixture of water/2,6-lutidine, such that the relative strength of gold-gold bonding through hydrophobic interaction and silica-silica bonding through the wetting-induced attraction is reversibly switched according to temperature.

Selective Janus Particle Assembly at Tipping Points of Thermally‐Switched Wetting

AbstractThermal wetting can simply, selectively and reversibly join patchy particles into clusters (2D and 3D) and also colloidal crystals over the narrow temperature range of 1–2 °C. This is demonstrated with Janus particles (gold half‐coated silica spheres) immersed in a binary mixture of water/2,6‐lutidine, such that the relative strength of gold–gold bonding through hydrophobic interaction and silica–silica bonding through the wetting‐induced attraction is reversibly switched according to temperature.

Capillary interactions between spherical Janus particles at liquid–fluid interfaces

We study the interactions of spherical Janus particles at non-equilibrium orientations adsorbed at flat oil–water interfaces. At equilibrium, the orientation of Janus spheres results in each hemisphere being exposed to its more favored fluid. Experimental observations suggest that some of these particles may take a tilted orientation at the interface, giving rise to energetic inter-particle interactions. The interface shape around the particles is obtained numerically by minimizing the total surface energy of the system comprising the interface and particle-fluid regions. We quantify these interactions through evaluation of capillary energy variation as a function of the separation distance between the particles. Depending on the relative orientations of neighboring particles, attractive or repulsive forces appear between Janus spheres. The interactions are found to be dipolar in nature, with a pair potential inversely proportional to the third power of the inter-particle distance. We find that Janus spheres with similar orientations undergo a relative realignment in the interface plane in order to minimize the capillary energy. We also evaluate the dependence of capillary forces on the size and degree of amphiphilicity between two sides of the particle. This study can provide new insight into understanding the interactions and assembly of Janus particles of random orientations at liquid–fluid interfaces.

Behaviour of iron oxide (Fe3O4) Janus particles in overlapping external AC electric and static magnetic fields

The assembly behaviour of Fe3O4-capped Janus particles with magnetically and electrically anisotropic properties is investigated in overlapping external AC electric and static magnetic fields. Generally, Fe3O4 Janus particles have been shown to form double and staggered chains in external static magnetic and AC electric fields, respectively. Here, the reaction of Fe3O4 Janus particles to sequentially applied AC electric and static magnetic fields in parallel and perpendicular field geometry is studied in order to elucidate to what extend the asymmetric nature of the Janus particle can be addressed independently by each field during assembly. A parallel field geometry leads to contraction of the Janus particle chains, whereas a perpendicular field geometry leads first to the rotation of the Janus particle chains towards the more dominant field followed by rhombohedral stacking of the chains into two-dimensional, two-particle thick sheets as a result of the weaker field. The Janus particle assembly behaviour in each field geometry tested is parameterized by the characteristic angle, θ, and the inter-particle distance, d. The observed response of the Fe3O4 Janus particles is shown to be driven by the interaction of electric and magnetic dipoles generated in the caps by the external AC electric and static magnetic fields, respectively, as well as the polarization of the polystyrene particle. Reversibility of the assembly behaviour correlates strongly with the fact that the electric dipoles disappear immediately after the AC electric field is turned off, whereas the magnetic dipoles remain permanently in the Fe3O4 caps even after the static magnetic field is removed. As a result, the Fe3O4 Janus particle assembly behaviour is responsive to both the electric and the magnetic fields and their behaviour can be manipulated by the sequence and relative orientation of the external fields.

Directed Assembly of Janus Particles under High Frequency ac-Electric Fields: Effects of Medium Conductivity and Colloidal Surface Chemistry

The manipulation and assembly of polystyrene-based Janus particles of varied surface chemistry on one hemispherical particle surface under high frequency nonuniform ac-electric fields is examined experimentally by in situ microscopic observation. Strong effects of ac-field frequency, medium conductivity, and particle surface chemistry on the structure of Janus colloidal assembly are observed. At low medium conductivity, σ(m) from 0.0007 S/m to 0.0153 S/m, pearl chains of Janus particles are observed over the ac-frequency range from 25 kHz to 20 MHz, indicating the dielectrophoresis (DEP)-directed assembly. In contrast, the chaining of Janus particles is disrupted in a certain frequency range at high σ(m) from 0.0153 S/m to 0.116 S/m, suggesting the combining effects of both induced-charge electrophoresis (ICEP) and DEP. The critical transition frequency for the onset of the fractal aggregation at high σ(m) from 0.0153 S/m to 0.116 S/m is experimentally determined, showing a good agreement with the theoretically predicted upper ICEP frequency limit. Additionally, it is demonstrated that by using zwitterionic Janus particles, the assembled structure of Janus particles under ac-fields can be modified by the chemical coatings on each hemispherical surface of Janus particles.