Role of surface ligands in the nanoparticle assemblies: a case study of regularly shaped colloidal crystals composed of sodium rare earth fluoride

Assembly of nanoparticles is a promising route to fabricate devices from nanomaterials. Colloidal crystals are well-defined three-dimensional assemblies of nanoparticles with long-range ordered structures and crystalline symmetries. Here, we use a solvent evaporation induced assembly method to obtain colloidal crystals composed of polyhedral sodium rare earth fluoride nanoparticles. The building blocks exhibit the same crystalline orientation in each colloidal crystal as indicated in electron diffraction patterns. The driving force of the oriented assembly is ascribed to the facet-selected capping of oleic acid molecules on {110} facets of the nanoparticles, and the favorable coordination behavior of OA molecules is explained by the steric hindrance determined adsorption based on the studies of the surface atomic structure of nanocrystals and molecular mechanics simulation of OA molecules. The capping ligands also provide hydrophobic interactions between nanoparticles and further direct the oriented assembly process to construct a face-centered cubic structure. These results not only provide a new type of building block for colloidal crystals, but also clarify the important role of surface ligands, which determine the packed structure and orientations of nanoparticles in the assemblies.     

Co‐assembly of Patchy Polymeric Micelles and Protein Molecules

The development in the synthesis and self‐assembly of patchy nanoparticles has resulted in the creation of complex hierarchical structures. Co‐assembly of polymeric nanoparticles and protein molecules combines the advantages of polymeric materials and biomolecules, and will produce new functional materials. Co‐assembly of positively charged patchy micelles and negatively charged bovine serum albumin (BSA) molecules is investigated. The patchy micelles, which were synthesized using block copolymer brushes as templates, leads to co‐assembly with protein molecules into vesicular structures. The average size of the assembled structures can be controlled by the molar ratio of BSA to patchy micelles. The assembled structures are dissociated in the presence of trypsin. The protein–polymer hybrid vesicles could find potential applications in medicine.     

Fabrication of Polyhedral Particles from Spherical Colloids and Their Self‐Assembly into Rotator Phases

Particle shape is a critical parameter that plays an important role in self‐assembly, for example, in designing targeted complex structures with desired properties. Over the last decades, an unprecedented range of monodisperse nanoparticle systems with control over the shape of the particles have become available. In contrast, the choice of micrometer‐sized colloidal building blocks of particles with flat facets, that is, particles with polygonal shapes, is significantly more limited. This can be attributed to the fact that in contrast to nanoparticles, the larger colloids are significantly harder to synthesize as single crystals. It is now shown that a very simple building block, such as a micrometer‐sized polymeric spherical colloidal particle, is already enough to fabricate particles with regularly placed flat facets, including completely polygonal shapes with sharp edges. As an illustration that the yields are high enough for further self‐assembly studies, the formation of three‐dimensional rotator phases of fluorescently labelled, micrometer‐sized, and charged rhombic dodecahedron particles was demonstrated. This method for fabricating polyhedral particles opens a new avenue for designing new materials.     

Assembly of Gold Nanoparticles on a Molecular Ultrathin Film: Tuning the Surface Plasmon Resonance

A number of methodologies for immobilizing metal nanoparticles in 2‐dimensional aggregate structures on various substrates, some with concomitant tuning of the surface plasmon resonance (SPR), have been reported. Many of them involve special functionalization of the nanoparticles, multiple fabrication steps or lengthy procedures. The present study demonstrates that monolayer Langmuir–Blodgett (LB) film of a hemicyanine‐based amphiphile with cationic headgroup is an easily fabricated platform for harnessing citrate‐stabilized gold nanoparticles. It is shown that a single immersion step can be used to immobilize the nanoparticles uniformly on large area films and that systematic variation of the immersion time from 10 min to 6 h leads to controlled assembly of the particles and tuning of the SPR band over ～100 nm. A model for the structural reorganization in the LB film that facilitates the assembly of nanoparticles is presented and the advantages of the current methodology over earlier protocols are pointed out. The versatility of LB films in terms of the molecular level control of fabrication it enables and the variety of film structures that can be realized, point to the wide scope for future explorations, expanding upon the present observations.     

Confined crystallization of PVDF and a PVDF‐TFE copolymer in nanolayered films

Layer‐multiplying coextrusion was used in conjunction with isothermal recrystallization to study the confined crystallization of polyvinylidene fluoride (PVDF) and polyvinylidene fluoride‐tetrafluoroethylene (PVDF‐TFE) using polycarbonate (PC) and polysulfone (PSF) as confining materials. Three layered systems were produced (PC/PVDF, PSF/PVDF, and PC/PVDF‐TFE) with layer thicknesses ranging from 525 to 28 nm. The crystal morphology was affected by both layer thickness and recrystallization temperature. Specifically, increased recrystallization temperature and decreased layer thickness facilitated the formation of high aspect ratio in‐plane crystals in both PVDF based polymers. On the other side of the spectrum, thicker layers and lower recrystallization temperatures produced on‐edge PVDF crystals and isotropic PVDF‐TFE crystals. The morphology was correlated with oxygen permeability, which decreased by almost two orders of magnitude compared with the bulk. A variety of crystal structures were obtained and explained with nucleation and diffusion theory. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Hydrogen‐Bonded Liquid Crystalline Materials: Supramolecular Polymeric Assembly and the Induction of Dynamic Function

Liquid crystals are molecular materials that combine anisotropy with dynamic nature. Recently, the use of hydrogen bonding for the design of functional liquid crystalline materials has been shown to be a versatile approach toward the control of simple molecularly assembled structures and the induction of dynamic function. A variety of hydrogen‐bonded liquid crystals has been prepared by molecular self‐assembly processes via hydrogen bond formation. Rod‐like and disk‐like low‐molecular weight complexes and polymers with side‐chain, main‐chain, network, and guest‐host structures have been built by the complexation of complimentary and identical hydrogen‐bonded molecules. These materials consist of closed‐type hydrogen bondings. Another type of hydrogen‐bonded liquid crystals consists of open‐type hydrogen bonding. In this case, the introduction of hydrogen bonding moieties, such as hydroxyl groups, induces microphase segregation leading to liquid crystalline molecular order. Moreover, liquid crystalline physical gels have been prepared by the molecular aggregation of hydrogen‐bonded molecules in non‐hydrogen‐bonded liquid crystals. They show significant electrooptical properties. An anisotropic gel is a new type of anisotropic materials forming heterogeneous structures.     

Roles of amorphous calcium phosphate and biological additives in the assembly of hydroxyapatite nanoparticles

Potential mechanisms for formation of highly organized biomineralized structures include oriented crystal growth on templates, the aggregation of nanocrystals by oriented attachment, and the assembly of inorganic nanoparticles mediated by organic molecules into aggregated structures. In the present study, the potential role of amorphous calcium phosphate (ACP) in facilitating the assembly of hydroxyapatite (HAP) nanoparticles into highly ordered structures was evaluated. The physical characteristics of HAP nanoparticles prepared by three different methods were analyzed after extended exposure to additives in solution. Higher order HAP architecture was detected only when the starting particles were aggregates of nanospheres with HAP cores and ACP shells. Enamel-like HAP architecture was produced when the biologic additive was 10 mM glycine or 1.25 microM amelogenin. Large platelike crystals of the type present in bone were induced when the additive was 10 mM glutamic acid. Surface ACP initially links the HAP nanoparticles in a way that allows parallel orientation of the HAP nanoparticles and then is incorporated into HAP by phase transformation to produce a more highly ordered architecture with features that are characteristic for HAP in biologic structures. These studies provide evidence for a new mechanism for assembly of biominerals in which ACP functions by linking HAP nanocrystals while they assume parallel orientations and then is incorporated by phase transformation into HAP molecules that rigidly link HAP nanocrystals in larger fused crystallites. Biologic molecules present during this process of biomineral assembly specifically regulate the assembly kinetics and determine the structural characteristics of the final HAP architecture.     

Frame‐Guided Assembly of Vesicles with Programmed Geometry and Dimensions

In molecular self‐assembly molecules form organized structures or patterns. The control of the self‐assembly process is an important and challenging topic. Inspired by the cytoskeletal‐membrane protein lipid bilayer system that determines the shape of eukaryotic cells, we developed a frame‐guided assembly process as a general strategy to prepare heterovesicles with programmed geometry and dimensions. This method offers greater control over self‐assembly which may benefit the understanding of the formation mechanism as well as the functions of the cell membrane.     

Morphosynthesis of alanine mesocrystals by pH control

Crystallization of DL-alanine is studied as a single polymorph model case to analyze the different modes of crystallization of polar organic molecules in absence of any structure directing additives. Depending on supersaturation, which is controlled either by temperature or by pH, and in the absence of additives, crystallization by mesoscale assembly of nanoparticles is found over a wide range of conditions, leading to so-called mesocrystals. This supplements the classical molecule-based crystallization mechanism, which is identified at lower supersaturations and at pH values away from the isoelectric point (IEP). The resulting alanine crystals are characterized by SEM, XRD, and single-crystal analysis. Time-resolved conductivity measurements and dynamic light scattering of the reaction solutions reveal information about precursor structures and reaction kinetics. A formation mechanism is proposed for the alanine mesocrystals.     

Self‐Assembled Fluorescent Organic Nanoparticles for Live‐Cell Imaging

Fluorescent, cell‐permeable, organic nanoparticles based on self‐assembled π‐conjugated oligomers with high absorption cross‐sections and high quantum yields have been developed. The nanoparticles are generated with a tuneable density of amino groups for charge‐mediated cellular uptake by a straightforward self‐assembly protocol, which allows for control over size and toxicity. The results show that a single amino group per ten oligomers is sufficient to achieve cellular uptake. The non‐toxic nanoparticles are suitable for both one‐ and two‐photon cellular imaging and flow cytometry, and undergo very efficient cellular uptake.     

Chirality Induction through Nano‐Phase Separation: Alternating Network Gyroid Phase by Thermotropic Self‐Assembly of X‐Shaped Bolapolyphiles

The single gyroid phase as well as the alternating double network gyroid, composed of two alternating single gyroid networks, hold a significant place in ordered nanoscale morphologies for their potential applications as photonic crystals, metamaterials and templates for porous ceramics and metals. Here, we report the first alternating network cubic liquid crystals. They form through self‐assembly of X‐shaped polyphiles, where glycerol‐capped terphenyl rods lie on the gyroid surface while semiperfluorinated and aliphatic side‐chains fill their respective separate channel networks. This new self‐assembly mode can be considered as a two‐color symmetry‐broken double gyroid morphology, providing a tailored way to fabricate novel chiral structures with sub‐10 nm periodicities using achiral compounds.     

Dual‐Input Regulation and Positional Control in Hybrid Oligonucleotide/Discotic Supramolecular Wires

The combination of oligonucleotides and synthetic supramolecular systems allows for novel and long‐needed modes of regulation of the self‐assembly of both molecular elements. Discotic molecules were conjugated with short oligonucleotides and their assembly into responsive supramolecular wires studied. The self‐assembly of the discotic molecules provides additional stability for DNA‐duplex formation owing to a cooperative effect. The appended oligonucleotides allow for positional control of the discotic elements within the supramolecular wire. The programmed assembly of these hybrid architectures can be modulated through the DNA, for example, by changing the number of base pairs or salt concentration, and through the discotic platform by the addition of discotic elements without oligonucleotide handles. These hybrid supramolecular‐DNA structures allow for advanced levels of control over 1D dynamic platforms with responsive regulatory elements at the interface with biological systems.     

Oriented assembly of Fe3O4 nanoparticles into monodisperse hollow single-crystal microspheres

Magnetite nanoparticles of Fe3O4 were found to assemble into monodisperse hollow Fe3O4 microspheres with tunable diameters ranging from 200 to 400 nm and open pores on the shells in ethylene glycol in the presence of dodecylamine (DDA). The oriented assembly of nanoparticles conferred the individual hollow Fe3O4 microspheres a remarkable feature of single crystals. The morphologies of the products could be easily manipulated by varying the synthesis parameters. Increasing the concentration of DDA led to an obvious shape evolution of the products from rhombic nanoparticles to hollow microspheres, solid microspheres, and finally irregular nanoparticles, which were mainly attributed to the special self-assembly phenomenon of Fe3O4 nanoparticles in the solvothermal process.     

Precisely Assembled Cyclic Gold Nanoparticle Frames by 2D Polymer Single‐Crystal Templating

In recent decades, extensive studies have been devoted to assembling nanoparticles (NPs) into various ordered structures to achieve novel optical properties. However, it still remains a challenging task to assemble NPs into cyclic one‐dimensional (1D) shapes, such as rings and frames. Herein, we report a directed assembly method to precisely assemble NPs into well‐defined, free‐standing frames using polymer single crystals (PSCs) as the template. Preformed poly(ethylene oxide) (PEO) single crystals were used as the template to direct the crystallization of block copolymer (BCP) poly(ethylene oxide)‐b‐poly(4‐vinylpyridine) (PEO‐b‐P4VP), which directs the gold NPs (AuNPs) to form AuNP frames. By controlling the PSC growth, we were able to, for the first time, precisely tune both the size and width of the AuNP frame. These novel AuNP frames topologically resemble NP nanorings and cyclic polymer chains, and show unique surface plasmon resonance (SPR) behaviors.     

Four‐Dimensional Deoxyribonucleic Acid–Gold Nanoparticle Assemblies

Organization of gold nanoobjects by oligonucleotides has resulted in many three‐dimensional colloidal assemblies with diverse size, shape, and complexity; nonetheless, autonomous and temporal control during formation remains challenging. In contrast, living systems temporally and spatially self‐regulate formation of functional structures by internally orchestrating assembly and disassembly kinetics of dissipative biomacromolecular networks. We present a novel approach for fabricating four‐dimensional gold nanostructures by adding an additional dimension: time. The dissipative character of our system is achieved using exonuclease III digestion of deoxyribonucleic acid (DNA) fuel as an energy‐dissipating pathway. Temporal control over amorphous clusters composed of spherical gold nanoparticles (AuNPs) and well‐defined core–satellite structures from gold nanorods (AuNRs) and AuNPs is demonstrated. Furthermore, the high specificity of DNA hybridization allowed us to demonstrate selective activation of the evolution of multiple architectures of higher complexity in a single mixture containing small and larger spherical AuNPs and AuNRs.     

Sequence‐Mandated,Distinct Assembly of Giant Molecules

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain‐like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence‐dependent phase structures. Not only compositional variation changed the self‐assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank–Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence‐mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self‐assembly.     

Sequence‐Mandated,Distinct Assembly of Giant Molecules

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain‐like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence‐dependent phase structures. Not only compositional variation changed the self‐assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank–Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence‐mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self‐assembly.     

Patterned Colloidal Photonic Crystals

Colloidal photonic crystals (PCs) have been well developed because they are easy to prepare, cost‐effective, and versatile with regards to modification and functionalization. Patterned colloidal PCs contribute a novel approach to constructing high‐performance PC devices with unique structures and specific functions. In this review, an overview of the strategies for fabricating patterned colloidal PCs, including patterned substrate‐induced assembly, inkjet printing, and selective immobilization and modification, is presented. The advantages of patterned PC devices are also discussed in detail, for example, improved detection sensitivity and response speed of the sensors, control over the flow direction and wicking rate of microfluidic channels, recognition of cross‐reactive molecules through an array‐patterned microchip, fabrication of display devices with tunable patterns, well‐arranged RGB units, and wide viewing‐angles, and the ability to construct anti‐counterfeiting devices with different security strategies. Finally, the perspective of future developments and challenges is presented.     

Light‐Driven Self‐Healing of Nanoparticle‐Based Metamolecules

Metamolecules and crystals consisting of nanoscale building blocks offer rich models to study colloidal chemistry, materials science, and photonics. Herein we demonstrate the self‐assembly of colloidal Ag nanoparticles into quasi‐one‐dimensional metamolecules with an intriguing self‐healing ability in a linearly polarized optical field. By investigating the spatial stability of the metamolecules, we found that the origin of self‐healing is the inhomogeneous interparticle electrodynamic interactions enhanced by the formation of unusual nanoparticle dimers, which minimize the free energy of the whole structure. The equilibrium configuration and self‐healing behavior can be further tuned by modifying the electrical double layers surrounding the nanoparticles. Our results reveal a unique route to build self‐healing colloidal structures assembled from simple metal nanoparticles. This approach could potentially lead to reconfigurable plasmonic devices for photonic and sensing applications.     

Recrystallization‐Induced Self‐Assembly for the Growth of Cu2O Superstructures

The assembly of inorganic nanoparticles (NPs) into 3D superstructures with defined morphologies is of particular interest. A novel strategy that is based on recrystallization‐induced self‐assembly (RISA) for the construction of 3D Cu₂O superstructures and employs Cu₂O mesoporous spheres with diameters of approximately 300 nm as the building blocks has now been developed. Balancing the hydrolysis and recrystallization rates of the CuCl precursors through precisely adjusting the experimental parameters was key to success. Furthermore, the geometry of the superstructures can be tuned to obtain either cubes or tetrahedra and was shown to be dependent on the growth behavior of bulk CuCl. The overall strategy extends the applicability of recrystallization‐based processes for the guided construction of assemblies and offers unique insights for assembling larger particles into complicated 3D superstructures.