Soft Nanostructures Research Articles

Michael Addition Inducing Self-Assembly to Construct Mechanochromic BP Film.

Liquid crystalline blue phase (BP) with 3D cubic nanostructure has attracted much interest in the fields of photonic crystals due to their unique optical properties and the ability to control the flow of light. However, there remains a challenge for simultaneously achieving self-assembly and mechanochromic response of soft 3D cubic nanostructures. Herein, a scalable strategy for the preparation of soft 3D cubic nanostructured films using oligomerization of the Michael addition reaction, which can induce the assembly of double-twisted cylinders for collective replication, remodeling, recombination, and growth, with a phase transition from BPII to BPI, and to chiral nematic phase, is presented. The prepared BP patterns can be obtained by Michael addition oligomerization reaction and composite mask photopolymerization, which present distinct mechanochromic sensitive due to patterns derived from different BP state, and the pattern can be reversibly erased and recurred by mechanical force and temperature. The average domain size of BPII prepared using this strategy can achieve 96µm, which is 2.5 times larger than that obtained using the conventional cooling approach. This work provides new insights into the self-assembly and selective chemochromism of functional materials and devices.

Polymeric Toroids Derived from the Fusion-Induced Particle Assembly of Anisotropic Bowl-Shaped Nanoparticles.

Polymeric toroids are fascinating soft nanostructures due to their unique geometry and properties, which have shown potential applications in the fields of nanoreactors, drug delivery, cancer therapy, etc. However, facile preparation of polymeric toroids is still challenging. Herein, we propose a fusion-induced particle assembly (FIPA) strategy to prepare polymeric toroids using anisotropic bowl-shaped nanoparticles (BNPs) as a building block. The BNPs are prepared in ethanol by the self-assembly of an amphiphilic homopolymer, poly(N-(2,2'-bipyridyl)-4-acrylamide) (PBPyAA), synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Upon incubation in ethanol above the glass transition temperature (Tg) of PBPyAA, the BNPs gradually aggregate to form trimers and tetramers due to the disturbance of the colloidal stability. With the increase in incubation time, the aggregated BNPs fuse with each other and then form toroids. Notably, we find that only anisotropic BNPs can aggregate and fuse to form toroids rather than spherical compound micelles due to high surface free energy and curvature at the edge of the BNPs. Besides, mathematical calculations further confirm the formation of trimers and tetramers during the FIPA process and the driving force for the formation of toroids. Overall, we propose a fresh insight for the facile preparation of polymeric toroids by the FIPA of anisotropic BNPs.

Responsive Magnetic Nanocomposites for Intelligent Shape-Morphing Microrobots

With the development of advanced biomedical theragnosis and bioengineering tools, smart and soft responsive microstructures and nanostructures have emerged. These structures can transform their body shape on demand and convert external power into mechanical actions. Here, we survey the key advances in the design of responsive polymer-particle nanocomposites that led to the development of smart shape-morphing microscale robotic devices. We overview the technological roadmap of the field and highlight the emerging opportunities in programming magnetically responsive nanomaterials in polymeric matrixes, as magnetic materials offer a rich spectrum of properties that can be encoded with various magnetization information. The use of magnetic fields as a tether-free control can easily penetrate biological tissues. With the advances in nanotechnology and manufacturing techniques, microrobotic devices can be realized with the desired magnetic reconfigurability. We emphasize that future fabrication techniques will be the key to bridging the gaps between integrating sophisticated functionalities of nanoscale materials and reducing the complexity and footprints of microscale intelligent robots.

Status and Future Scope of Soft Nanoparticles-Based Hydrogel in Wound Healing.

Wounds are alterations in skin integrity resulting from any type of trauma. The healing process is complex, involving inflammation and reactive oxygen species formation. Therapeutic approaches for the wound healing process are diverse, associating dressings and topical pharmacological agents with antiseptics, anti-inflammatory, and antibacterial actions. Effective treatment must maintain occlusion and moisture in the wound site, suitable capacity for the absorption of exudates, gas exchange, and the release of bioactives, thus stimulating healing. However, conventional treatments have some limitations regarding the technological properties of formulations, such as sensory characteristics, ease of application, residence time, and low active penetration in the skin. Particularly, the available treatments may have low efficacy, unsatisfactory hemostatic performance, prolonged duration, and adverse effects. In this sense, there is significant growth in research focusing on improving the treatment of wounds. Thus, soft nanoparticles-based hydrogels emerge as promising alternatives to accelerate the healing process due to their improved rheological characteristics, increased occlusion and bioadhesiveness, greater skin permeation, controlled drug release, and a more pleasant sensory aspect in comparison to conventional forms. Soft nanoparticles are based on organic material from a natural or synthetic source and include liposomes, micelles, nanoemulsions, and polymeric nanoparticles. This scoping review describes and discusses the main advantages of soft nanoparticle-based hydrogels in the wound healing process. Herein, a state-of-the-art is presented by addressing general aspects of the healing process, current status and limitations of non-encapsulated drug-based hydrogels, and hydrogels formed by different polymers containing soft nanostructures for wound healing. Collectively, the presence of soft nanoparticles improved the performance of natural and synthetic bioactive compounds in hydrogels employed for wound healing, demonstrating the scientific advances obtained so far.

Soft nanostructures out of star-shaped triazines with flexible amide spacers: liquid crystals with a cubic to columnar transition with memory effect, gels and supramolecular chirality

This work reports the synthesis and characterization of a new family of star-shaped tricarboxamides with C3-symmetry that have flexible amide spacers linking a tris(triazolyl)triazine core with three trialkoxyphenyl groups. The presence of amide groups allows the formation of intermolecular hydrogen bonds that reinforce π-stacking and van der Waals interactions, promoting liquid crystalline behavior, and self-assembly in solvents leading to organogels. As determined by polarized optical microscopy, differential scanning calorimetry and X-ray diffraction on powder samples, all the three reported molecules present a hexagonal columnar (Colh) phase stable at room temperature. Interestingly, they show a transition to a cubic micellar mesophase (BCC) at high temperatures. A mechanism for this transition, which is consistent with the fragmentation of columns to form supramolecular spheres, was elucidated from X-ray studies on aligned samples. Moreover, on cooling from the BCC to the columnar phase a preferential orientation of columns occurs, according to which each cubic domain gives rise to four hexagonal domains. The ability of the synthesized structures to aggregate in solvent media was studied in a variety of organic solvents, and all of them were able to gel 1-octanol at low concentrations. X-ray studies of gels and xerogels were carried out and showed a molecular organization consistent with Colh order. FTIR studies were carried out to analyze the formation of hydrogen bonds and the influence of the length of the flexible spacer in the liquid crystalline state and in the organogels. Furthermore, the presence of a stereogenic center in the flexible amide spacer leads to macroscopic chirality in the liquid crystal state and the organogels in 1-octanol as demonstrated by circular dichroism spectroscopy.

Theoretical treatment of complex coacervate core micelles: structure and pH-induced disassembly.

Complex coacervate core micelles (C3Ms) are supramolecular soft nanostructures formed by the assembly of a block copolymer and an oppositely charged homopolymer. The coacervation of the charged segments in both macromolecules drives the formation of the core of the C3M, while the neutral block of the copolymer forms the corona. This work introduces a molecular theory (MOLT) that predicts the internal structure and stimuli-responsive properties of C3Ms and explicitly considers the chemical architecture of the polyelectrolytes, their acid-based equilibria and electrostatic and non-electrostatic interactions. In order to accurately predict complex coacervation, the correlations between charged species are incorporated into MOLT as ion-pairing processes, which are modeled using a coupled chemical equilibrium formalism. Very good agreement was observed between the experimental results in the literature and MOLT predictions for the scaling relationships that relate the dimensions of the micelle (aggregation number and sizes of the micelle and the core) to the lengths of the different blocks. MOLT was used to study the disassembly of the micelles when the solution pH is driven away from the value that guarantees the charge stoichiometry of the core. This study reveals that very sharp disassembly transitions can be obtained by tuning the length or architecture of the copolymer component, thereby suggesting potential routes to design C3Ms capable of releasing their components at very precise pH values.

Modeling curvature-resisting material surfaces with isogeometric analysis

Improved understanding of solid surface energy and its role in the overall mechanical properties is of great interest due to the emerging manufacturing techniques of nanostructures, coatings, and synthetic/biological bilayer–polymer hybrids. Continuum numerical modeling of surface stresses efficiently incorporates a zero-thickness membrane bonded to a bulk, intrinsically accounting for surface tension and surface elasticity. Compressive surface stresses are not possible in a purely membrane formulation, ignoring the surface flexural resistance. The extension of material surfaces to account for flexural resistance, i.e., the Steigmann–Ogden model, requires spatial derivatives of second order, posing significant challenges to standard discretization techniques. Hence, the effect of surface curvature resistance on the overall mechanical behavior of complex geometries remains elusive. Here, we develop a three-dimensional computational formulation of curvature-dependent surface energetics at finite strains using surface-enriched isogeometric analysis. Coupled with a hyperelastic bulk, bending-resistance of material surfaces furnishes a new physical length scale, i.e., the elastobending length. We quantify the effect of elastobending deformations for several numerical examples involving soft materials with thin coatings and liquid-shell surfaces, capturing budding-like behavior observed at cell membranes. Our results demonstrate a stiffer overall mechanical behavior when material surfaces resist bending deformations and illustrate how curvature effects lead to complex budding deformations at non-zero initial curvature states. The proposed methodology provides a robust computational foundation to help improve our understanding and mechanical characterization of soft solids, nanostructures, and biological membranes at small scales.

Fingerprinting soft material nanostructure response to complex flow histories

Understanding the complex connection between flow-processing history, fluid structure, and fluid properties represents a grand challenge for the engineering and fundamental study of nanostructured soft materials. To address this challenge, we report measurements using scanning small-angle x-ray scattering in a fluidic four-roll mill (FFoRM), which enables rapid nanostructural characterization of complex fluids under an unprecedentedly diverse range of flow histories. Combining this technique with analysis of the Lagrangian deformation history of fluid elements, we demonstrate rapid mapping of orientational ordering of fluids' nanostructure along diverse deformation trajectories that emulate those encountered in flow processing. Using demonstrative experiments on model rodlike nanoparticle dispersions, we show that differences in rod flexibility and rod-rod interactions play a significant role in determining the fluid's anisotropic structural response to similar flow histories. An analysis of the coupling between measured particle alignment and interparticle correlations reveals these differences to arise from the nature and strength of interparticle interactions in flow. These measurement and analysis techniques produce large datasets that hold promise toward advancing process-structure-property models and inverse design processes of flows that are tailored to produce targeted nanostructures.

3D quasi-skyrmions in thick cylindrical and dome-shape soft nanodots

Magnetic skyrmions are widely attracting researchers due to fascinating physics and novel applications related to their non-trivial topology. Néel skyrmions have been extensively investigated in magnetic systems with Dzyaloshinskii–Moriya interaction (DMI) and/or perpendicular magnetic anisotropy. Here, by means of micromagnetic simulations and analytical calculations, we show that 3D quasi-skyrmions of Néel type, with topological charge close to 1, can exist as metastable states in soft magnetic nanostructures with no DMI, such as in Permalloy thick cylindrical and dome-shaped nanodots. The key factor responsible for the stabilization of DMI-free is the interplay of the exchange and magnetostatic energies in the nanodots. The range of geometrical parameters where the skyrmions are found is wider in magnetic dome-shape nanodots than in their cylindrical counterparts. Our results open the door for a new research line related to the nucleation and stabilization of magnetic skyrmions in a broad class of nanostructured soft magnetic materials.

Soft Surface Nanostructure with Semi-Free Polyionic Components for Sustainable Antimicrobial Plastic.

Surface antimicrobial materials are of interest as they can combat the critical threat of microbial contamination without contributing to issues of environmental contamination and the development drug resistance. Most nanostructured surfaces are prepared by post fabrication modifications and actively release antimicrobial agents. These properties limit the potential applications of nanostructured materials on flexible surfaces. Here, we report on an easily synthesized plastic material with inherent antimicrobial activity, demonstrating excellent microbicidal properties against common bacteria and fungus. The plastic material did not release antimicrobial components as they were anchored to the polymer chains via strong covalent bonds. Time-kill kinetics studies have shown that bactericidal effects take place when bacteria come into contact with a material for a prolonged period, resulting in the deformation and rupture of bacteria cells. A scanning probe microscopy analysis revealed soft nanostructures on the submicron scale, for which the formation is thought to occur via surface phase separation. These soft nanostructures allow for polyionic antimicrobial components to be present on the surface, where they freely interact with and kill microbes. Overall, the new green and sustainable plastic is easily synthesized and demonstrates inherent and long-lasting activity without toxic chemical leaching.

Advanced Electron Microscopy of Nanophased Synthetic Polymers and Soft Complexes for Energy and Medicine Applications.

After decades of developments, electron microscopy has become a powerful and irreplaceable tool in understanding the ionic, electrical, mechanical, chemical, and other functional performances of next-generation polymers and soft complexes. The recent progress in electron microscopy of nanostructured polymers and soft assemblies is important for applications in many different fields, including, but not limited to, mesoporous and nanoporous materials, absorbents, membranes, solid electrolytes, battery electrodes, ion- and electron-transporting materials, organic semiconductors, soft robotics, optoelectronic devices, biomass, soft magnetic materials, and pharmaceutical drug design. For synthetic polymers and soft complexes, there are four main characteristics that differentiate them from their inorganic or biomacromolecular counterparts in electron microscopy studies: (1) lower contrast, (2) abundance of light elements, (3) polydispersity or nanomorphological variations, and (4) large changes induced by electron beams. Since 2011, the Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory has been working with numerous facility users on nanostructured polymer composites, block copolymers, polymer brushes, conjugated molecules, organic–inorganic hybrid nanomaterials, organic–inorganic interfaces, organic crystals, and other soft complexes. This review crystalizes some of the essential challenges, successes, failures, and techniques during the process in the past ten years. It also presents some outlooks and future expectations on the basis of these works at the intersection of electron microscopy, soft matter, and artificial intelligence. Machine learning is expected to automate and facilitate image processing and information extraction of polymer and soft hybrid nanostructures in aspects such as dose-controlled imaging and structure analysis.

Transition molecular structures between block copolymers and hyperbranched copolymers suitable for toughening epoxy thermosets

Various toughening agents had been explored to overcome the intrinsic brittleness of epoxy thermosets. While they effectively toughened epoxy thermosets, however, usually produced plasticizing effect, leading to compromised thermal stability, modulus and glass transition temperature (Tg). Herein dumbbell-shaped SEBS-g-PEG copolymers, owning transitional molecular structures between block copolymers and hyperbranched copolymers, were synthesized via grafting methoxypolyethylene glycol (PEG) onto both end blocks of polystyrene-b-poly(ethylene-ran-butylene)-b-polystyrene (SEBS). They not only had good compatibility with epoxy thermosets without plasticizing effect, but also could form micro-phase separation morphology suitable for toughening epoxy thermosets via combining the advantages of block copolymers and hyperbranched copolymers. At higher branching density, their 10% load could increase ~230% KIC and impact strength without sacrificing thermal stability, Tg, flexural strength and modulus. The morphology results showed that their soft nanostructures’ size increased and the phase interfaces became blurred as increasing the branching density in SEBS-g-PEG. Thus, the toughening mechanism was attributed to the strengthened bonding between the interphases and the enlarged size of soft nanostructures.

Energy transduction through FRET in self-assembled soft nanostructures based on surfactants/polymers: current scenario and prospects.

The self-assembled systems of surfactants/polymers, which are capable of supporting energy funneling between fluorophores, have recently gained significant attraction. Surfactant and polymeric micelles form nanoscale structures spanning a radius of 2-10 nm are generally suitable for the transduction of energy among fluorophores. These systems have shown great potential in Förster resonance energy transfer (FRET) due to their unique characteristics of being aqueous based, tendency to remain self-assembled, spontaneous formation, tunable nature, and responsiveness to different external stimuli. This review presents current developments in the field of energy transfer, particularly the multi-step FRET processes in the self-assembled nanostructures of surfactants/polymers. The part one of this review presents a background and brief overview of soft systems and discusses certain aspects of the self-assemblies of surfactants/polymers and their co-solubilization property to bring fluorophores to close proximity to transduce energy. The second part of this review deals with single-step and multi-step FRET in the self-assemblies of surfactants/polymers and links FRET systems with advanced smart technologies including multicolor formation, data encryption, and artificial antenna systems. This review also discusses the diverse examples in the literature to present the emerging applications of FRET. Finally, the prospects regarding further improvement of FRET in self-assembled soft systems are outlined.

Geometric effects in cylindrical core/shell hard–soft exchange-coupled magnetic nanostructures

We explore the optimal condition for cylindrical core/shell hard-soft exchange-coupled magnetic nanostructures by obtaining full hysteresis loops for various geometries by obtaining full hysteresis loops for various geometrical variables, including the dimensional scale and soft/hard-magnetic phase volume ratio through micromagnetic simulations. For achieving maximum energy product (BH), it is essential to increase the demagnetizing field by increasing the volume fraction of the soft magnet while maintaining a positive nucleation field and, which can be possible by the scaling-down. To scale up the nanostructure to a bulk magnet having high BH can be achieved by forming an array of needle-shaped exchange-coupled cylinders. These findings could lead to the flexible design and scalable fabrication of exchange-coupled permanent magnets.

Multivalent Clustering of Adhesion Ligands in Nanofiber-Nanoparticle Composites

Because the positioning and clustering of biomolecules within the extracellular matrix dictates cell behaviors, the engineering of biomaterials incorporating bioactive epitopes with spatial organization tunable at the nanoscale is of primary importance. Here we used a highly modular composite approach combining peptide amphiphile (PA) nanofibers and silica nanoparticles, which are both easily functionalized with one or several bioactive signals. We show that the surface of silica nanoparticles allows the clustering of RGDS bioactive signals leading to improved adhesion and spreading of fibroblast cells on composite hydrogels at an epitope concentration much lower than in PA-only based matrices. Most importantly, by combining the two integrin-binding sequences RGDS and PHSRN on nanoparticle surfaces, we improved cell adhesion on the PA nanofiber/particle composite hydrogels, which is attributed to synergistic interactions known to be effective only for peptide intermolecular distance of ca. 5 nm. Such composites with soft and hard nanostructures offer a strategy for the design of advanced scaffolds to display multiple signals and control cell behavior.

Design of cationic amphiphiles for generating self-assembled soft nanostructures, micelles and hydrogels

Design of amphiphiles to develop robust self-assembled soft nanomaterials, such as micelles and hydrogels is an interesting subject. A series of cationic amphiphilic compounds were synthesized comprising 1-ethoxy (3-pentadecyl) benzene as the hydrophobic tail. The second carbon of ethoxy was linked to quaternary head groups (trimethyl ammonium bromide (PEA), triethyl ammonium bromide (PETE), pyridinium bromide (PEPy), N-methyl morpholino bromide (PENM), N-methyl piperidine bromide (PENP)). Inclusion of benzene ring leads to a significant decrease in critical micellar concentration (CMC) as compared to other cationic surfactants, such as cetyl trimethyl ammonium bromide (CTAB). Interestingly, at higher concentration, these cationic amphiphiles were forming soft hydrogels with critical gelation concentration (CGC) from 3 to 10% (w/v). The small-angle X-ray scattering (SAXS) analysis of xerogel revealed the formation of self-assembled lamellar patterns of molecules. Further, the morphology of xerogels were also seen under a scanning electron microscope (SEM) which correlates with SAXS data. The SAXS and SEM data confirms the formation of worm-like micellar structures and entangle themselves to form a hydrogel. The cytotoxicity assay was done on HDFA, HeLa and HEK cell lines, haemolysis assay showed better haemocompatibility than CTAB. The synthesized surfactants exhibited up to 3-fold higher solubilization capability against hydrophobic molecules than CTAB.

Multivalent Clustering of Adhesion Ligands in Nanofiber-Nanoparticle Composites

Because the positioning and clustering of biomolecules within the extracellular matrix dictates cell behaviors, the engineering of biomaterials incorporating bioactive epitopes with spatial organization tunable at the nanoscale is of primary importance. Here we used a highly modular composite approach combining peptide amphiphile (PA) nanofibers and silica nanoparticles, which are both easily functionalized with one or several bioactive signals. We show that the surface of silica nanoparticles allows the clustering of RGDS bioactive signals leading to improved adhesion and spreading of fibroblast cells on composite hydrogels at an epitope concentration much lower than in PA-only based matrices. Most importantly, by combining the two integrin-binding sequences RGDS and PHSRN on nanoparticle surfaces, we improved cell adhesion on the PA nanofiber/particle composite hydrogels, which is attributed to synergistic interactions known to be effective only for peptide intermolecular distance of ca. 5 nm. Such composites with soft and hard nanostructures offer a strategy for the design of advanced scaffolds to display multiple signals and control cell behavior.

Covalent Post-Assembly Modification: A Synthetic Multipurpose Tool in Supramolecular Chemistry.

The use of covalent post-assembly modification (PAM) in supramolecular chemistry has grown significantly in recent years, to the point where PAM is now a versatile synthesis tool for tuning, modulating, and expanding the functionality of self-assembled complexes and materials. PAM underpins supramolecular template-synthesis strategies, enables modular derivatization of supramolecular assemblies, permits the covalent 'locking' of unstable structures, and can trigger controlled structural transformations between different assembled morphologies. This Review discusses key examples of PAM spanning a range of material classes, including discrete supramolecular complexes, self-assembled soft nanostructures and hierarchically ordered polymeric and framework materials. As such, we hope to highlight how PAM has continued to evolve as a creative and functional addition to the synthetic chemist's toolbox for constructing bespoke self-assembled complexes and materials.

Nanostructural formation kinetics in an Fe86B14 soft magnetic alloy investigated by in situ transport measurements under isothermal conditions

The soft magnetic properties in iron-based nanocrystalline alloys have generally been achieved through the addition of nonmagnetic additives, but this has the unwanted effect of reducing the saturation magnetization. In a recent advance, it was shown that magnetically soft nanostructured alloys could be prepared from a simple, binary Fe-B amorphous precursor by ultrarapid annealing (URA). These materials had a saturation magnetization comparable to that of silicon steel, while a refined grain structure resulted in considerably lower core losses through the exchange averaging effect of the magnetic anisotropy. As yet, the formation mechanism of the soft magnetic nanostructure in this simple binary system has not been identified. We investigated the crystallization process of amorphous ${\mathrm{Fe}}_{86}{\mathrm{B}}_{14}$ using in situ transport measurements. The relationship between the resistivity and the volume fraction of bcc-Fe crystallites was calibrated by $^{57}\mathrm{Fe}$ M\"ossbauer spectroscopy. In this paper, we show that the isothermal crystallization behavior of these Fe-B amorphous alloys is well described by the Johnson-Mehl-Avrami-Kolmogorov kinetic model and that the the Avrami exponent ($n$) shows a tendency to increase with increasing annealing temperature (${T}_{\mathrm{a}}$); the exponent $n$ is approximately 1.5 at ${T}_{\mathrm{a}}<700\phantom{\rule{0.28em}{0ex}}\mathrm{K}$ while $n>2$ at ${T}_{\mathrm{a}}=729\phantom{\rule{0.28em}{0ex}}\mathrm{K}$. This suggests that below 700 K the nucleation rate is governed solely by a limited number of quenched-in nuclei whereas at higher temperatures, homogeneous nucleation starts to dominate. Since the onset of crystallization is increased dramatically by rapid heating, the formation of the refined nanostructure induced by URA can be well understood by an increase in the number density of nuclei due to homogeneous nucleation. The increased homogeneous nucleation at higher annealing temperatures can be linked to enhanced atomic transport due to viscous flow.

Polymer Cubosomes: Infinite Cubic Mazes and Possibilities.

Block copolymers (BCPs) have been indispensable building blocks to create a range of soft nanostructures including discrete particulates (micelles and vesicles) and periodic structures via spontaneous assembly in bulk and in solution. The size, shape, and phase of these structures can be controlled by the rational design of the molecular structure of building blocks based on the structural analogy of BCPs to lipids and small molecule surfactants. Inverse bicontinuous cubic mesophases of polymers, or polymer cubosomes when in colloidal forms, are emerging nanostructures composed of triply periodic minimal surfaces (TPMSs) of block copolymer bilayers. Created by spontaneous assembly of BCPs in solution, polymer cubosomes internalize two nonintersecting nanochannel networks arranged in a cubic crystalline order. As well-defined porous particles with highly ordered internal structures and high surface-area-to-volume ratios, polymer cubosomes can be used for chemical reactors or bioreactors, carriers capable of cargo loading and release, and scaffolds for nanotemplating. However, despite their structural similarity to lipid cubosomes and applicability, polymer cubosomes have been only sporadically observed as an outcome of serendipity until recent studies demonstrated that BCPs could form well-defined polymer cubosomes in solution.In this Account, we describe our recent progress in creating polymer cubic mesophases and their colloidal particles (polymer cubosomes) in dilute solution. BCPs with nonlinear architectures (dendritic-linear, branched-linear, and branched-branched BCPs) preferentially self-assembled to inverse mesophases in solution when the block ratio (f), defined as a molecular weight ratio of the hydrophilic block to that of the hydrophobic block, was small (<10%). The resulting lyotropic structures transformed from flat bilayers to cubic phases of primitive cubic and double diamond lattices and finally to inverted hexagonal phases as f decreased. We proposed that the architecture of a BCP plays an important role in the preferential formation of polymer cubosomes in solution. The presence of the bulky hydrophilic block limited chain stretching of the hydrophobic polymer block, which would increase the packing parameter of the BCP to greater than unity, a prerequisite for inverse mesophase formation. The structural characteristics of polymer cubosomes, such as lattice symmetries, pore sizes, and lattice parameters, could also be controlled by fine-tuning the structural parameters of BCPs. We also suggested nonsynthetic methods to precisely control the phase and internal lattice of inverse mesophases of BCPs by the coassembly of two BCPs with different block ratios (mix-and-match approach) and the modulation of the affinity of the common solvent toward the hydrophobic block of the BCP. To investigate the potential applications of polymer cubosomes, we prepared inorganic photonic crystals using a cubosome-templated synthesis. We also discussed the utilization of cubosomes as chemical reactors by functionalization of the surface and the covalent stabilization of transient self-assembled structures via cross-linking of the hydrophobic domain. This Account reflects the efforts of synthetic chemists to understand the self-assembly behavior of BCPs to form complex morphologies in solution. We hope that our Account inspires efforts from chemists and other scientists to further understand these structures with infinite mazes of complexity and possibility.