MXenes, a class of two-dimensional titanium carbide materials, have emerged as promising materials for film-based applications due to their exceptional properties. However, their densely layered structures hinder ion diffusion, metal-ion mobility, and nanoscale particle transfer, limiting their potential in energy-related applications. Expanding and controlling interlayer spacing is essential for overcoming these limitations and optimizing MXene performance. In this study, silver nanoparticles (AgNPs) measuring 20 and 55 nm in size were incorporated into dense MXene structures to control and expand their pathways. X-ray diffraction confirmed the lamellar structure of pristine MXene, and detailed analyses using electron microscopy and small-angle neutron scattering demonstrated that the size and concentration of AgNPs directly influenced pathway expansion. The interlayer spacing increased significantly, with widths growing from 2.4 nm to ∼25 nm as the AgNP parameters varied. Electrochemical impedance spectroscopy results revealed that the densely packed structure of pristine MXene was unsuitable for use as an anode-current collector coating in batteries. In contrast, the MXene/AgNP composite demonstrated effective functionality due to the expanded pathways, which improved ion transfer and conductivity. These findings underscore the importance of pathway engineering and the use of additive insertion methods in advancing MXene-based materials for energy storage and other functional applications.

Complex coacervation is an associative phase separation process of oppositely charged polyelectrolyte solutions, resulting in a coacervate phase enriched with charged polymers and a polymer-lean phase. To date, studies on the phase behavior of complex coacervation have been largely restricted to aqueous systems with relatively high dielectric constants due to the limited solubility of most polyelectrolytes, hindering the exploration of the effects of electrostatic interactions from differences in solvent permittivity. Herein, we prepare two symmetric but oppositely charged polymerized ionic liquids (PILs), consisting of poly[1-[2-acryloyloxyethyl]-3-butylimidazolium bis(trifluoromethane)sulfonimide] (PAT) and poly[1-ethyl-3-methylimidazolium 3-[[[(trifluoromethyl)sulfonyl]amino]sulfonyl]propyl acrylate] (PEA). Due to the delocalized ionic charges and their chemical structure similarity, both PAT and PEA are soluble in various organic solvents with a wide range of dielectric constants, ranging from 16.7 (hexafluoro-2-propanol (HFIP)) to 66.1 (propylene carbonate (PC)). Notably, no significant correlation is observed between the solvent dielectric constant and the phase diagram of the complex coacervation of PILs. Most organic solvents lead to similar phase diagrams and salt resistances regardless of their dielectric constants, except two protic solvents (HFIP and 2,2,2-trifluoroethanol (TFE)) showing significantly low salt resistances compared to the others. The low salt resistance in these protic solvents primarily arises from strong hydrogen bonding between PILs and solvents as evidenced by 1H NMR and small-angle neutron scattering (SANS) experiments. Our finding suggests that for the coacervation of PILs, particularly those with delocalized and weak charge interactions, entropy from the counterion release and polymer-solvent interaction chi parameter play a more important role than the electrostatic interactions of charged molecules, rendered by the dielectric constant of the solvent medium.

This study presents a nanohybrid that simultaneously improves both photothermal (PT) and photodynamic (PD) effects for cancer therapy. The conjugated polymer nanoparticle (CPN) comprises of p-type conjugated polymer as a photosensitizer, charge donor, and PT agent, n-type conjugated polymer as a charge acceptor and PD agent, and Au nanoparticles (NPs) as a PT agent. This nanohybrid is assembled through a film dispersion process using a hydrophobically modified phospholipid, producing a high yield of uniform hybrid NPs in a short timeframe, and displays exceptional photothermal and photodynamic effects, when activated at a single near-infrared wavelength. Photophysical analysis indicates that the inclusion of Au NPs enhances nonradiative exciton relaxation, while the incorporation of a n-type conjugated polymer boosts photoinduced charge transfer and potentially contributes to the charge-recombination mediated triplet-state formation for an enhanced generation of reactive oxygen species. During phototherapy, the nanohybrid demonstrates the most effective suppression of primary tumor growth and significantly boosts anti-tumor immune responses owing to its simultaneous photothermal and photodynamic effects. Furthermore, when combined with immune checkpoint inhibitors, nanohybrid treatment minimizes tumor sizes while maximizing survival rates in mice. Thus, the nanohybrid represents a promising nanoplatform for combination phototherapy in cancer treatment.

Quantum dots (QDs) exhibit size-dependent optical properties, where both the absorption and fluorescence energy levels vary with QD size. However, this dependence results in a discontinuity of intrinsically accessible energy levels for the bandgap, posing challenges in achieving precise energy tuning within a specific range. Herein, we demonstrate emission energy control of QDs with identical absorption energy levels by manipulating the spatial arrangement of QDs within QD-polymer complexes through hydrophobic interactions. The phase behavior of the QD-polymer complexes was modulated by adjusting the mass fraction of hydrophilic and hydrophobic blocks in the block copolymer, utilizing two types of amphiphilic block copolymers and varying temperatures. The QDs were spontaneously trapped within the hydrophobic region of the polymer template in water, resulting in spherical, cylindrical, and vesicle structures of QD-polymer complexes, corresponding to spherical, cylindrical, and layered assemblies of QDs, respectively. Depending on the QDs' location within the QD-polymer complex, the surface area in contact with water varied, leading to different degrees of oxidation and, consequently, a change in the fluorescence energy level of QDs. This study introduces a novel method to fine tune the emission energy (<15 eV) of QDs by adjusting the polymer form factor without complicated procedures.

The advancement of flexible and wearable electronics relies on semiconducting polymers that can endure mechanical deformation while maintaining high electrical performance under strain. In this study, we demonstrate that fine-tuning backbone rigidity through the molecular design of donor moieties significantly enhances both the mechanical and charge transport properties of diketopyrrolopyrrole (DPP)-based polymers. Specifically, the flexible DPP-4T (quaterthiophene) exhibited a persistence length of 20.4 nm in solution, while DPP-DTT (dithienothiophene) showed a longer persistence length of 32.8 nm due to its stiff backbone, as confirmed by small-angle neutron scattering and Monte Carlo simulations. This flexibility enabled DPP-4T to achieve a crack-onset strain exceeding 100% via the film-on-elastomer method and a fracture strain of over 30% in quasi-free-standing films. Additionally, DPP-4T demonstrated a 180% increase in hole mobility at 80% strain, driven by strain-induced chain alignment and backbone planarization. Utilizing a range of characterization techniques, including ultraviolet-visible (UV-vis) spectroscopy, grazing incidence X-ray diffraction (XRD), and Raman spectroscopy, we characterized structural changes at multiple length scales under applied tensile strain. Notably, strain induced a transformation in chain conformation from a twisted to a flat structure, reducing the hopping energy barrier and enhancing charge transport. These structural rearrangements are crucial for sustaining efficient charge transport and ensuring the reliability of electronic performance under mechanical stress.

Ni‐rich layered oxides are envisioned as the most promising cathode materials for next‐generation lithium‐ion batteries; however, their practical adoption is plagued by fast capacity decay originating from chemo‐mechanical degradation. The intrinsic chemical–mechanical instability, inherited from atomic‐ and nanoscale defects generated during synthesis, is not yet resolved. Here, atomic‐ and nanoscale structural evolution during solid‐state synthesis of Ni‐rich layered cathode, Li[Ni 0.92 Co 0.03 Mn 0.05 ]O 2 , is investigated using combined X‐ray/neutron scattering and electron/X‐ray microscopy. The multiscale analyses demonstrate the intertwined correlation between phase transition and microstructural evolution, with atomic‐scale defects derived from the decomposition of precursors leading to the creation of intra/inter‐granular pores. The nucleation and coalescence mechanism of pore defects during the synthesis of Ni‐rich layered cathodes are quantitatively revealed. Furthermore, a modified synthetic route is proposed to effectively circumvent the formation of nanoscale defects in Ni‐rich layered cathodes by facilitating uniform synthetic reactions, resulting in superior electrochemical and microstructural stability.

Interparticle ligand exchange can occur during the formation of nanoparticle superlattices (NPSLs), affecting the symmetry of the NPSLs. Here, we report time-resolved small-angle neutron scattering (TR-SANS) measurements of the interparticle exchange kinetics of thiolate ligands among gold nanoparticles (AuNPs) at different temperatures. To track the ligand exchange among AuNPs, two groups of AuNPs were functionalized with hydrogenated and deuterated dodecanethiol, respectively, and then mixed in a solvent mixture of toluene and deuterated toluene for shell contrast. The interparticle ligand exchange barely occurred at 25 °C even after 40 h, but 11%, 34%, and 74% occurred at 50, 60, and 70 °C, respectively. At 80 °C, the exchange saturated after 20 h. The exchange process follows first-order kinetics, and its activation energy is estimated to be 29.1 kcal/mol, supporting that ligand desorption is a rate-determining step. These findings can be used as valuable reference data, aiding in the design and understanding of NPSLs.

Binary nanoparticle superlattices (BNSLs) are one of the important classes of nanomaterial architectures for a wide range of potential applications because they can provide synergistically enhanced properties depending on the morphology and spatial arrangement of nanoparticles (NPs). However, although many studies have been conducted on the fabrication of BNSLs, there are still several challenges in achieving BNSLs with a three-dimensional lattice due to their complicated synthesis, hindering their practical applications. Herein, we report the fabrication of temperature-sensitive BNSLs in complexes of gold nanoparticles (AuNPs), Brij 58 surfactant, and water via a two-step evaporation method. The surfactant was utilized for two different purposes, i.e., surface modification of the AuNPs to control their interfacial energy and as a template material for the formation of the superlattice. Depending on the size and concentration of the AuNPs, the mixture of AuNPs and surfactant self-assembled into three types of BNSLs, including CaF2, AlB2, and NaZn13, which were sensitive to temperature. This study is the first demonstration of the temperature- and particle size-dependent control of BNSLs in the bulk state without the covalent functionalization of NPs via a simple two-step solvent evaporation method.

The two-dimensional (2D) assembly of gold nanoparticles (AuNPs) in a confined geometry is a rare phenomenon that has not been experimentally verified for complex systems. In this study, this process was investigated in detail using two types of block copolymers with hydrophobic and hydrophilic blocks and a series of AuNPs of three different sizes protected by hydrophobic ligands. In aqueous solutions, the selected block copolymers self-assembled into vesicular nanostructures with a hydrophobic domain in the wall, which functions as a confined geometrical space for hydrophobic AuNPs (i.e., it exerts a confinement effect and restricts the movement of AuNPs). Small-angle X-ray scattering studies revealed that AuNPs of different sizes assembled differently in the same confined geometry of the vesicular wall. In addition, optimal conditions for the formation of a regular NP array in the hydrophobic domain were determined. The AuNPs successfully self-assembled into a regular 2D lattice structure, forming a shell around the vesicle, when their size matched the thickness of the hydrophobic domain of the vesicular nanostructure. This study provides guidelines for the fabrication of nanoparticle arrays with controlled structures, which could enhance the functionality of materials and their physical properties.

Block copolymer blend systems have been of great interest for a wide range of potential applications, such as nanobuilding blocks or guidance materials, because they can provide a rich phase behavior according to external conditions. However, a new and unique phase behavior of block copolymers, which can give us their more extended potential applications, has not yet been reported. Herein, we report the unusual self-assembly of two different types of Pluronic P65 and PE6200 triblock copolymer blends dependent on temperature and PE6200 concentration, which is unique for the block copolymer blends in aqueous solution. As the temperature and concentration of PE6200 (as an additive) increased, the Pluronic P65/PE6200 copolymer blends sequentially self-assembled into an isotropic micellar-hexagonal-isotropic micellar or isotropic micellar- hexagonal-isotropic micellar-lamellar phase, which is a discontinuous ordered phase (called a closed looplike phase transition), and their phase transition temperature could be controlled. To the best of our knowledge, this is the first report of a closed looplike phase transition of Pluronic block copolymer blends in aqueous solution, which can be easily applied to nanosized templates for temperature-selective highly ordered structures and optical devices such as optoelectronics or optical sensors.

Pluronic amphiphilic block copolymers, well known to have a phase behavior can be controlled by external conditions, have a wide range of potential for applications such as nanotemplates or nanobuilding blocks. However, the phase behaviors of Pluronic block copolymer/additive complexes with highly ordered phases have not been fully investigated. Here, we report the unusual molecular weight-dependent self-assembly of Pluronic block copolymer/additive complexes. Depending on the temperature and additive, Pluronic P65 block copolymer with a lower molecular weight showed the closed loop-like (CLL) phase behavior with the disorder-order-disorder-order phase transition in aqueous solution, whereas Pluronic P105 and P85 block copolymers with higher molecular weights underwent highly ordered continuous phase transitions with face centered cubic (FCC), hexagonal, and lamellar phases. It is expected that the specific phase behavior of the block copolymer/additive complex can be applied in optical devices such as nanotemplates or optical sensors for a highly ordered superlattice. Furthermore, this study provides a new route to control the phase behavior of the block copolymers without a complicated process.

Self-assembly of gold nanoparticles (AuNPs) into highly ordered superstructures provides a promising route toward fabricating materials with new functionalities or enhanced physical properties. Although self-assembly of AuNPs has garnered significant research attention recently, a highly ordered superlattice of AuNPs under a low concentration in a confined geometry formed by nonfunctionalized materials has not been reported. Herein, we investigate the self-assembly of a 2D AuNPs superlattice in a polymer vesicle layer using hydrophobic interactions, which exhibits centered rectangular lattice symmetry. To create the highly ordered AuNPs superlattice, the P(EGx-b-iPGEy) block copolymers that form the thickness of the hydrophobic vesicle layer comparable to the size of the AuNP are used as a template to control the AuNP degree of freedom. To the best of our knowledge, this study provides the first demonstration of a centered rectangular structure formation of AuNPs at the vesicle layer in 2D confined geometry.

We report various self-assembled structures of gold nanoparticles in a block copolymer aggregate template, which are easily driven by hydrophobic interactions.

A self-assembled unilamellar vesicle, which can be used as a drug delivery system, was easily and simply fabricated using a blended system of Pluronic block copolymers. Controlling the hydrophilic mass fraction of block copolymers (by blending the block copolymer with a different hydrophilic mass fraction) and temperature (i.e., the hydrophobic interaction is controlled), a vesicular structure was formed. Small angle neutron scattering measurements showed that the vesicular structure had diameters of empty cores from 13.6 nm to 79.6 nm, and thicknesses of the bilayers from 2.2 nm to 8.7 nm when the hydrophobic interaction was changed. Therefore, considering that the temperature of the vesicle formation is controllable by the concentration of the blended block copolymers, it is possible for them to be applied in a wide range of potential applications, for example, as nanoreactors and nanovehicles.

The phase behavior of amphiphilic Pluronic block copolymers in aqueous solution is of importance for a broad spectrum of practical applications but has not been fully exploited yet. Here, the phase behavior of the mixture of the Pluronic P65 and P105 triblock copolymer, (which have the same composition of PEO and PPO but the different molecular weight) and organic derivative, 5-methyl salicylic acid (5mS), in aqueous solution has been investigated by using small angle neutron scattering (SANS). According to the temperature and the 5mS concentration, SANS measurements showed that the P65-5mS mixtures sequentially transform into a random coil, sphere, vesicle, cylinder, and vesicle again, while the P105-5mS mixtures form spherical particles with two different sizes without any topological phase transition. Upon heating, the formation of two different kinds of the vesicle structure of amphiphilic block copolymer in aqueous solution is very unusual. This phase behavior was explained as the coupled effect of the simultaneous increase of the hydrophobicity of the polymer and the solubility of 5mS molecules upon heating. This result gives fundamental information for the practical use of Pluronic polymers in nano- and bio-science and it provides a simple route for the fabrication of the nanostructure without a complicated procedure.

A new method to easily derive the phase transition of amphiphilic block copolymer in aqueous solution is suggested in this study. Using two kinds of Pluronic triblock copolymers, which have different mass fractions of the hydrophilic part of the block copolymer, the mixed block copolymers in aqueous solution self-assembled into a variety of nanostructures. Small angle neutron scattering revealed that the block copolymer complex formed spheres, cylinders, and vesicles depending on both the concentration of another Pluronic block copolymer (Pluronic PE6200) as an additive and temperature. This phase behavior can be easily explained in terms of the hydrophobicity of the block copolymer by increasing its effective hydrophobic moiety and temperature.

Spontaneous size-controllable vesicles that are prepared by a mixture of surfactants with different alkyl chain lengths (n-alkyltrimethylammonium bromide, C(n)TAB) and an organic derivative (5-methyl salicylic acid, 5mS) in aqueous solution have been investigated. When the organic derivative 5mS is mixed with the C(n)TAB surfactants in aqueous solution, the surfactant vesicles are spontaneously formed above a certain 5mS concentration. Small angle neutron scattering reveals that the core radius of surfactant vesicles is clearly increased from ca. 31 nm to ca. 97 nm with the alkyl chain length of surfactants while the bilayer thickness of the vesicles is nearly constant. The structure of surfactant vesicles maintains against temperature change ranging from 30 degrees C to 45 degrees C, showing no structural change. These results can provide thermally stable surfactant vesicles with various sizes and constant bilayer thickness that may possess a different permeability and may allow the surfactant vesicle to be used in gene or drug delivery for a variety of goods.

In the temperature range of 303–333 K, the self-assembled structures of a mixture of Pluronic F127 triblock copolymer [PEO 106 PPO 70 PEO 106 ; PEO is poly(ethylene oxide) and PPO is poly(propylene oxide)] and an organic derivative, 5-methyl salicylic acid (5mS), in aqueous solution have been investigated using small-angle neutron scattering (SANS). Above a 5mS concentration of 1.93 g l −1 , the F127–5mS mixture solution became cloudy with a blue colour arising from the Tyndall effect, indicating that large polymer aggregates had formed in the mixture solution. SANS measurements showed that the self-assembled structure of the F127–5mS mixture transformed from a spherical to a cylindrical micelle with increasing the concentration of 5mS in the temperature range of 303–323 K. When the 5mS concentration was increased to 3.3 g l −1 , the self-assembled structure of the F127–5mS mixture at 333 K underwent an additional phase transition from a cylindrical to a spherical micelle of large size at a 5mS concentration of 2.75 g l −1 , although its self-assembled structure changed from a spherical to a cylindrical micelle at a 5mS concentration of 1.93 g l −1 as well. The phase transitions are explained by the variation of the mass fraction of the hydrophilic part of F127 and the coupled effect of the limited solubility and the strong tendency to bind with amphiphilic molecules of 5mS. Using a simple material balance equation and the structural information obtained from SANS model analyses, the numbers of D 2 O and of 5mS molecules in the core and corona regions are calculated. This result can provide a simple and easy way to prepare various nanostructures using a Pluronic triblock copolymer in aqueous solution and may be very useful for practical applications of a Pluronic polymer such as various nanobuilding blocks or nanotemplates.

A unilamellar polymeric vesicle is a self-assembled structure of a block copolymer that forms a spherical single bilayer structure with a hydrophobic interlayer and a hydrophilic surface. Due to their enhanced colloidal stability and mechanical property, controllable surface functionality, or tunable membrane thickness, polymeric vesicles are useful in nano and bio-science, providing potential applications as nanosized carriers for catalysts, drugs, and enzymes. For fabrication of a unilamellar vesicle, however, preparative procedures with a few steps are inherently required. Herein, without complicated preparative procedures, we report spontaneous unilamellar polymeric vesicles with nanometer sizes (<100 nm), which are prepared by simply mixing a triblock copolymer, Pluronic P85 (PEO26PPO40PEO26), and an organic derivative, 5-methyl salicylic acid (5mS), in aqueous solution. Depending on the 5mS concentration and the temperature, the P85-5mS mixtures presented various self-assembled nanostructures such as spherical and cylindrical micelles or vesicles, which were characterized by small angle neutron scattering and cryo-TEM, resulting in a phase diagram drawn as a function of temperature and the 5mS concentration. Interestingly the critical temperature for the micelle-to-vesicle phase transition was easily controlled by varying the 5mS concentration, i.e. it was decreased with increasing the 5mS concentration.