self-assembly of nanoparticles

 

  • Typically, nanoparticles will self-assemble for one or both of two reasons: molecular interactions and external direction.

  • [19] Hard nanoparticles[edit] For hard particles, Pauling’s rules are useful in understanding the structure of ionic compounds in the early days, and the later entropy maximization
    principle shows favor of dense packing in the system.

  • In self-assembly, regular structural arrangements are frequently observed, therefore there must be a balance of attractive and repulsive between molecules otherwise an equilibrium
    distance will not exist between the particles.

  • [6] To do so correctly, an extremely high level of direction and control is required and developing a simple, efficient method to organize molecules and molecular clusters
    into precise, predetermined structures is crucial.

  • [citation needed] Design nanoparticle self-assembly structure Self-assembly of nanoparticles is driven by either maximization of packing density or minimization of the contact
    area between particles according to hard or soft nanoparticles.

  • Definition Self-assembly is defined as a process in which individual units of material associate with themselves spontaneously into a defined and organized structure or larger
    units with minimal external direction.

  • [4] This definition allows one to account for mass and energy fluxes taking place in the self-assembly processes.

  • This process occurs at all size scales, in the form of either static or dynamic self-assembly.

  • This so-called bridging will enable fabrication of materials with the fine resolution of bottom-up methods and the larger range and arbitrary structure of top-down processes.

  • Furthermore, in some cases components are too small for top-down synthesis, so self-assembly principles are required to realize these novel structures.

  • Often, they also provide a defect-correcting platform and thus, liquid/liquid interfaces are ideal for self-assembly.

  • [11] By controlling local intermolecular forces to find the lowest-energy configuration, self-assembly can be guided by templates to generate similar structures to those currently
    fabricated by top-down approaches.

  • Concepts related to thermal motion and capillary action influence equilibrium timescales and kinetic rates that are not well defined in self-assembling systems.

  • By size Among the more sophisticated and structurally complex nanostructures currently available are organic macromolecules, wherein their assembly relies on the placement
    of atoms into molecular or extended structures with atomic-level precision.

  • He imagined a world in which “we could arrange atoms one by one, just as we want them.” This idea set the stage for the bottom-up synthesis approach in which constituent components
    interact to form higher-ordered structures in a controllable manner.

  • The decrease in total free energy for microscopic particles is much larger than that of thermal energy, resulting in an effective confinement of large colloids to the interface.

  • [17] In order for a self-assembling system to reach the minimum free energy configuration, there has to be enough thermal energy to allow the mass transport of the self-assembling
    molecules.

  • Static self-assembly is significantly slower compared to dynamic self-assembly as it depends on the random chemical interactions between particles.

  • Self-assembly of nanoscale structures from functional nanoparticles has provided a powerful path to developing small and powerful electronic components.

  • For defect formation, the free energy of single defect formation is given by: The enthalpy term, does not necessarily reflect the intermolecular forces between the molecules,
    it is the energy cost associated with disrupting the pattern and may be thought of as a region where optimum arrangement does not occur and the reduction of enthalpy associated with ideal self-assembly did not occur.

  • The necessity of the self-assembly to be an equilibrium process is defined by the organization of the structure which requires non-ideal arrangements to be formed before the
    lowest energy configuration is found.

  • Self-assembled materials with desired structures are often obtained through thermodynamic control.

  • Each colloid particle has the ability to store information as known as binary number 0 and 1 after applying it to a strong magnetic field.

  • [17] In addition, the flexibility and the lower free energy conformation is usually a result of a weaker intermolecular force between self-assembled moieties and is essentially
    enthalpic in nature.

  • Combinations of fields allow the benefits of self-assembly, such as scalability and simplicity, to be maintained while being able to control orientation and structure formation.

  • [23] Nanoparticles can be programmed to self-assemble by changing the functionality of their side groups, taking advantage of weak and specific intermolecular forces to spontaneously
    order the particles.

  • In block copolymers, covalent bonds frustrate the natural tendency of each individual polymer to remain separate (in general, different polymers, do not like to mix), so the
    material assembles into a nano-pattern instead.

  • While Hamaker theory generally describes a macroscopic system, the vast number of nanoparticles in a self-assembling system allows the term to be applicable.

  • Cell imaging Nanoparticles have good biological labeling and sensing because of brightness and photostability; thus, certain self-assembled nanoparticles can be used as imaging
    contrast in various systems.

  • [34] The magnetic nanochains possess attractive properties which are significant added value for many potential uses including magneto-mechanical actuation-associated nanomedicines
    in low and super-low frequency alternating magnetic field and magnetic drug delivery.

  • The study of self-assembly of nanoparticles began with recognition that some properties of atoms and molecules enable them to arrange themselves into patterns.

  • [2] The small size of nanoparticles allows them to have unique characteristics which may not be possible on the macro-scale.

  • Static self-assembly utilizes interactions amongst the nano-particles to achieve a free-energy minimum.

  • It is now known that organic compounds can be conductors, semiconductors, and insulators, thus one of the main opportunities in nanomaterials science is to use organic synthesis
    and molecular design to make electronically useful structures.

  • The second is through external manipulation by applying and combining the effects of several kinds of fields to manipulate the building blocks into doing what is intended.

  • Small assemblies are formed because of their increased lifetime as the attractive interactions between the components lower the Gibbs free energy.

  • [25] However, to deliver precise and scalable (programmable) assembly for a desired structure, a careful positioning of ligand molecules onto the nanoparticle counterpart
    should be required at the building block (precursor) level,[26][27][28][29] such as direction, geometry, morphology, affinity, etc.

  • He describes self-assembly as a process where components of the system acquire non-random spatial distribution with respect to each other and the boundaries of the system.

  • Hamaker constants for nanoparticles are calculated using Lifshitz theory, and can often be found in literature.. Externally directed self-assembly[edit] The natural ability
    of nanoparticles to self-assemble can be replicated in systems that do not intrinsically self-assemble.

  • Hamaker interactions take into account the polarization characteristics of a large number of nearby particles and the effects they have on each other.

  • If is negative, there will be a finite number of defects in the system and the concentration will be given by: N is the number of defects in a matrix of N0 self-assembled
    particles or features and is the activation energy of defect formation.

  • [20] Different particle shapes / polyhedra create diverse complex packing structures in order to minimize the entropy of the system.

  • [36] Solid interfaces[edit] Nano-particles can self-assemble on solid surfaces after external forces (like magnetic and electric) are applied.

  • [23] In most cases, the thermodynamic driving force for self-assembly is provided by weak intermolecular interactions and is usually of the same order of magnitude as the
    entropy term.

  • A variety of applications where the self-assembly of nanoparticles might be useful.

  • Classification Nanostructures can be organized into groups based on their size, function, and structure; this organization is useful to define the potential of the field.

  • [17] This equation shows that as the value of approaches the value of and above a critical temperature, the self-assembly process will become progressively less likely to
    occur and spontaneous self-assembly will not happen.

  • Here, we demonstrate that the selection of kinetic pathways can lead to drastically different self-assembled structures, underlining the significance of kinetic control in
    self-assembly.

  • [citation needed] Nanoscale objects have always been difficult to manipulate because they cannot be characterized by molecular techniques and they are too small to observe
    optically.

  • [39] 2D self-assembly monodisperse particle colloids has a strong potential in dense magnetic storage media.

  • The successful design of ligand-building block units can play an essential role in manufacturing a wide-range of new nano systems, such as nanosensor systems,[30] nanomachines/nanobots,
    nanocomputers, and many more uncharted systems.

  • “[8] Another definition by Serge Palacin & Renaud Demadrill is “Self-assembly is a spontaneous and reversible process that brings together in a defined geometry randomly moving
    distinct bodies through selective bonding forces.

  • [15] A bottom-up approach for nano-assembly is a primary research target for nano-fabrication because top down synthesis is expensive (requiring external work) and is not
    selective on very small length scales, but is currently the primary mode of industrial fabrication.

  • In solutions, it is an outcome of random motion of molecules and the affinity of their binding sites for one another.

  • [44] Surface modification with functional groups, can also lead to selective biological labeling.

  • [23] While these aggregations are based on intermolecular forces, external factors such as temperature and pH also play a role in spontaneous self-assembly.

  • The challenges of this application are the difficulty of reproducing or controlling the size of self-assembly nano micelle, preparing predictable size-distribution, and the
    stability of the micelle with high drug load content.

  • • Natural processes that drive self-assembly tend to be highly reproducible.

 

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Photo credit: https://www.flickr.com/photos/morgaine/2675221506/’]