Thermally induced gelling systems, or thermogels, represent an important class of injectable biomaterials that remain liquid prior to administration but undergo a sol - gel transition upon heating to body temperature, thereby providing a minimally invasive alternative to conventional hydrogels. These materials are typically composed of amphiphilic block copolymer micelles that assemble into macroscopic hydrogel networks. This review highlights the design principles and gelation mechanisms of micelle‑derived thermogels, including mesophase transitions, aggregation mediated by thermosensitive outer shells, and percolated network formation through controlled assembly of patchy micelles with multiple thermosensitive-binding domains. We discuss how polymer composition, block length, and end‑group chemistry dictate critical gelation temperature and concentration, mechanical properties, and long‑term stability. Recent advances in biomedical applications are then introduced, spanning localized drug delivery, vascular embolization, tissue engineering, and cell transplantation. Finally, we outline key challenges for clinical translation, emphasizing the needs for rational design strategies and predictive modeling to accelerate the development of next‑generation thermogels. Literature search: PubMed, SciFinder, and Google Scholar, up to November 2025.

Linear-dendritic block copolymers comprising poly(ε-caprolactone) attached to hydrophilic 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) ester dendron via a disulfide and containing a defined number of pendent visible-light-responsive donor-acceptor Stenhouse adduct (DASA) groups are synthesized using click chemistry and postpolymerization modification. Self-assembly in aqueous solution selectively affords rice grain-like ellipsoidal, rod-like, and spherical micelles, governed by the number of DASA groups. Progressive disassembly of the micelles is observed during photoswitching cycles. Release of camptothecin depends on the DASA content under light irradiation and is enhanced by the synergistic effect of two stimuli. Cellular uptake quantified by FACS analysis is demonstrated to be influenced by the shape of the micelles, with ellipsoidal micelles exhibiting higher efficiency than spherical micelles by following clathrin- and caveolae-mediated endocytosis as major pathways for internalization. Both types of micelles were found to maintain the particle size in Dulbecco's modified Eagle's medium containing 10% fetal bovine serum at 37 ̊C. Doxorubicin (DOX)-loaded ellipsoidal micelles under photoirradiation show significantly higher apoptosis than free DOX.

Soft and deformable objects are widespread in natural and synthetic systems, including micellar domains, microgel particles, foams, and biological cells. Understanding their phase behavior at high concentrations is crucial for controlling long-range order. Here, we employ a Voronoi-based model to study the packing of deformable particles in two dimensions under thermal fluctuations. Particles are represented as interconnected polygons, with the system energy comprising penalties for deviations in area and perimeter from preferred values. The strengths of these penalties capture two key features of packing: dynamic size dispersity, mimicking chain exchange in block copolymer micelles or solvent exchange in microgels, and particle line tension, reflecting the energy cost of shape changes. The model exhibits an order-disorder transition (ODT): low perimeter penalties yield disordered states, while higher penalties produce a hexagonal crystal lattice. Large dynamic size dispersity shifts the ODT to higher perimeter penalties. We explain this by analyzing particle sizes, defect formation barriers, and Voronoi entropy, which show that defect formation is easier when the area penalty term is smaller, providing a mechanistic basis for the ODT trends. In regimes far from ODT, deviations from the hexagonal lattice are accurately described by normal mode displacement fields, confirming that thermal fluctuations rather than defects govern the structure.

Block copolymer micelles based on TMZ conjugate for controlled drug delivery of doxorubicin

Cell migration relies on balancing focal adhesion (FA) stability-necessary for traction generation-and turnover-essential for forward translocation. Here, we dissect how integrin binding frequency and force-dependent bond duration jointly regulate this balance in fibroblasts. Using block copolymer micelle nanolithography, we create gold nanoparticle (Au NP) arrays with controlled spacings to vary integrin-ligand binding frequency. In parallel, tension gauge tethers (TGTs) with defined force threshold limit bond lifetime of high-force integrins under cellular traction. We find that intermediate ligand spacing coupled with a moderate rupture threshold dramatically accelerates fibroblast migration-up to twelvefold faster than on denser or sparser substrates. These conditions foster rapid FA turnover and support a dendritic actin architecture driven by lamellipodia, challenging the longstanding view of fibroblasts as inherently slow, mesenchymal movers. Knockout and blocking experiments further identify α5β1 as the mechanically dominant integrin subtype that plays a pivotal role in supporting this rapid migration. Mechanistically, FAs remain sufficiently stable to generate traction but also disassemble quickly, fostering continuous protrusion-retraction cycles essential for high-speed migration. These findings refine the classic biphasic model of cell migration into a two-dimensional framework that considers ligand spacing (binding frequency) and TGT force thresholds (binding duration). Beyond expanding fundamental understanding of integrin mechanobiology, our results provide broad avenues for tissue engineering and therapeutic applications, where finely tuned adhesion mechanics can markedly modulate cell speed and phenotype.

Block copolymer (BCP) self-assembly – neat, or in a homopolymer/second BCP containing molecular blend – enables complex nanostructures including spherical micelles, co-continuous cubic gyroids and Frank-Kasper phases. Emergent properties in metallic and high entropy alloys inspire a paradigm shift: treating chemically distinct BCP micelles as functional building blocks to pave a path for multicomponent assemblies with molecularly engineered property profiles. Slowing current progress are challenges associated with the structural characterization of such BCP assemblies with poor atomic contrast. Here, we demonstrate how film surface self-assemblies of binary and ternary BCP micelle alloys can be phase inverted to generate porosity. This, combined with machine-learning assisted image segmentation, allows component classification via routine scanning electron microscopy. Results are supported by mechanistic insights from Voronoi analysis, cluster analysis and Monte Carlo/Brownian Dynamics simulations, revealing rich and controllable non-equilibrium surface structural behavior. Such multicomponent materials are expected to enable emergent properties for a range of applications.

Abstract Tandem reactions have received considerable attention in the past as an economic and ecological advantageous approach to carry out multi‐step reactions. The use of non‐compatible catalysts and which methods can be used to spatially separate them remains a major challenge. Here, we present a simplified approach to facilitate tandem reactions based on diblock copolymer micelles where the hydrophilic shell is functionalized with sulfonic acid groups and the micellar core contains l ‐proline as a second organo catalyst. Self‐assembly in water leads to block copolymer micelles that support a tandem reaction of a sulfonic acid catalyzed acetal cleavage in the micellar shell followed by a l ‐proline catalyzed aldol reaction in the micellar core. Three block copolymers were prepared with different ratios of SO 3 H and l ‐Proline groups within one block copolymer. Conversion of more than 95% for each reaction step and a syn / anti ratio of >3/97 with high enantiomeric excess (>95% ee) for the aldol product were achieved for the best block copolymer micelle. Moreover, the polymer micelles could be recycled in four consecutive runs and gave conversions of up to 98% for the acetal cleavage and 57% for the aldol reaction and proceeded with good enantio‐ (79% ee) and diastereoselectivity ( syn/anti = 4:96) in the 4 th run.

The thin films of nanoporous materials, including zeolites, metal-organic frameworks (MOFs), and mesoporous materials, are promising for applications in electrodes, separations, catalysis, and sensing. While microporous materials offer high surface areas that expose numerous active sites, their limited diffusion pathways for reactants and products constrain performance. Hierarchically structured mesoporous-microporous materials offer an ideal solution by combining extensive surface areas with enhanced diffusion; however, the complexity of creating and integrating dual pore systems has hindered progress in this area, and reports on these materials remain scarce. Here, evaporation-induced methods (spin-coating and spray-coating) are introduced for the rapid synthesis of continuous mesoporous amorphous MOF thin films on solid substrates, achieved through the cooperative self-assembly of block copolymer micelles and MOF precursors (metal ions and organic linkers). The resulting mesoporous amorphous MOF films exhibit uniform pore distribution with low surface roughness. Furthermore, these films exhibit great potential for application on various substrates, benefiting from the versatility of this synthesis approach.

Abstract Packing of soft spheres, such as micelles, polymer‐grafted particles, and microgels, enables the creation of diverse functional materials. Despite the importance of achieving precise structural control, understanding the kinetics of non‐equilibrium packing in a large‐scale deposition process remains challenging. This study investigates the kinetics of the precursor‐assisted close packing of soft spheres using block copolymer micelles as the sphere model. Adding the inorganic precursor SnCl4 is crucial for achieving the close packing, which is versatile and provides a robust platform for tailoring mesoporous materials with tunable pore sizes. The kinetics of the close‐packing process are explored by in situ grazing‐incidence small‐angle X‐ray scattering measurements during slot‐die coating. The soft crystallization process shows six distinct stages: dilute dispersion, concentrated dispersion, wet film, structuring wet film, gel film, and glassy film. The close packing develops first in the in‐plane direction with rapid domain growth and then advances in the out‐of‐plane direction. Precursors in the interstitial voids play a key role by mitigating packing frustration and favoring face‐centered cubic (FCC) ordering. The structure finally stabilizes into a well‐ordered FCC structure with large domain sizes. The derived mesoporous SnO2 features semiconducting properties and enhanced pore connectivity, thus showing superior gas sensing performance toward ethanol.

Controlling the spatial arrangement of nanodots is pivotal for functional nanomaterials and biointerfaces, and the spontaneous self-assembly of block copolymer micelles has been widely used to fabricate ordered nanostructures. However, achieving tunable disorder remains a fundamental challenge. Here, we demonstrate how successive spin coating dynamically modulates both density and disorder in micellar arrays, revealing an unexpected non-monotonic evolution of structural order. By using the Voronoi tessellation and Alpha shapes filtering algorithm, we found that initial coatings produce hexagonal order (interparticle distance: 126 nm, σd/d̅ = 0.12) and intermediate cycles induce maximal disorder (interparticle distance: 95 nm, σd/d̅ = 0.26), while further deposition partially restores order driven by steric hindrance (interparticle distance: 73 nm, σd/d̅ = 0.20). Our successive spin-coating approach achieves tunable disorder equivalent to conventional polymer-blending methods but without additives, offering a versatile strategy for engineering nanoscale surface patterns with potential applications for biomaterials and optical device design.

Hierarchical assembly of nanosized building blocks has emerged as an effective strategy for the bottom-up fabrication of functional materials with a wide range of potential applications, but large-scale production of well-defined hierarchical colloidal materials still remains challenging. In this study, cross-linked block copolymer micelles with reversible addition-fragmentation chain transfer (RAFT) groups at the interface were prepared by orthogonal RAFT-mediated polymerization-induced self-assembly (PISA) of hydroxypropyl methacrylate (HPMA) in water. These micelles were then used as building blocks for the polymerization-induced hierarchical self-assembly (PIHSA) of N-isopropylacrylamide (NIPAM) in water. We demonstrated that the presence of RAFT groups at the interface of micelles could promote the PIHSA process that enables the preparation of hierarchical colloidal materials with higher-order structures (e.g., vesicles). Careful monitoring the PIHSA process revealed some intermediate structures that provide mechanistic insights into the formation of hierarchical colloidal materials. This study provides a scalable and environmentally benign approach to prepare hierarchical colloidal materials with a diverse set of complex structures.

Abstract Nanostructured epoxy composite resins have broad usage in adhesives, coatings, composites, and 3D printing. With these materials, careful control of the rheological properties is critical to ensuring that the properties meet their required performance targets. However, it can be difficult to accurately measure the rheological properties. In this work, we establish a method to develop a reliable pre-shear (PS) procedure to repeatably measure the apparent yield stress of the resins, which is critical to ensure the accurate understanding of the material behavior. The resins in this study consisted of an epoxy resin with nanoclay as a shear thinning agent, ionic liquid (1-ethyl-3-methylimidazolium dicyanamide) as a latent curing agent, and poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymer (BCP) as a nanostructured component. We establish a methodology to evaluate the effectiveness of a pre-shear protocol and evaluate several methods to identify a pre-shear procedure that resulted in repeatable transient creep results on a rheometer. We identified that large amplitude oscillatory shear was the most effective method for these materials, and the optimal magnitude of the shear was dependent on the composition of the epoxy resins. Through the consistent application of this approach, we were able to use transient creep testing to identify the phase boundaries in the epoxy/BCP resins when the BCP micelles undergo an order-order transition from spherical to hexagonal micelles through changes in the yield stress of the material. This work adds to the new growing body of literature demonstrating the importance of establishing rigorous pre-shear conditions to improve the accuracy of structured yield stress fluids.

Metal halide perovskite nanocrystals (PNCs) have attracted significant research interest owing to their exceptional photovoltaic properties and their potential applications in photovoltaics and light-emitting devices. However, stabilizing individual PNCs while maintaining their intrinsic properties remains a great challenge. In this study, a facile yet robust approach is introduced by utilizing polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) block copolymer micelles as templates to precisely control the formation, size, and stability of CsPbBr3 PNCs. Interestingly, the reaction kinetics of PNC precursors in the micelles can be modulated by stacking of polymer chains via crosslinking of P4VP cores or collapsing of micelle templates, enabling facile control over the geometry of PNCs inside the micelles. By tuning the molecular weight of P4VP, precise size control of the CsPbBr3 PNCs can be achieved. Most importantly, the hydrophobic PS shell enhances the stability of PNCs against moisture and polar solvents (e.g., methanol, ethanol, dichloromethane, etc.) without interference in ion exchange processes. The approach enables the in situ growth of monodisperse CsPbBr3 PNCs, offering a straightforward and scalable method for fabricating highly stable, size-controlled PNCs suitable for optoelectronic applications.

Delivering of hydrophobic drugs by polymeric nanoparticles is an intensively investigated research and development field worldwide due to the insufficient solubility of many existing and potential new drugs in aqueous media. Among polymeric nanoparticles, micelles of biocompatible amphiphilic block copolymers are among the most promising candidates for solubilization, encapsulation, and delivery of hydrophobic drugs to improve the water solubility and thus the bioavailability of such drugs. In this study, amphiphilic ABA triblock copolymers containing biocompatible hydrophilic hyperbranched (dendritic) polyglycerol (HbPG) outer and hydrophobic poly(tetrahydrofuran) (PTHF) inner segments were synthesized using amine-telechelic PTHF as a macroinitiator for glycidol polymerization. These hyperbranched-linear-hyperbranched block copolymers form nanosized micelles with 15-20 nm diameter above the critical micelle concentration. Coagulation experiments proved high colloidal stability of the aqueous micellar solutions of these block copolymers against temperature changes. The applicability of block copolymers as drug delivery systems was investigated using curcumin, a highly hydrophobic, water-insoluble, natural anti-cancer agent. High and efficient drug solubilization up to more than 3 orders of magnitude to that of the water solubility of curcumin (>1500-fold) is achieved with the HbPG-PTHF-HbPG block copolymer nanomicelles, locating the drug in amorphous form in the inner PTHF core. Outstanding stability of and sustained curcumin release from the drug-loaded block copolymer micelles were observed. The in vitro bioactivity of the curcumin-loaded nanomicelles was investigated on U-87 glioblastoma cell line, and an optimal triblock copolymer composition was found, which showed highly effective cellular uptake and no toxicity. These findings indicate that the HbPG-PTHF-HbPG triblock copolymers are promising candidates for advanced drug solubilization and delivery systems.

Self‐assembly of block copolymers in solution provides access to different nanostructures depending on block composition and processing conditions. However, more complex hierarchical nanostructures as found in nature remain challenging to achieve. In this study, the influence of a β‐sheet forming tetrapeptide sequence (GFFG) is investigated at the interface of an amphiphilic block copolymer based on poly(butyl acrylate) (PBA) and poly(ethylene oxide) (PEO). Using atomic force microscopy (AFM) and tip‐enhanced Raman spectroscopy (TERS), nanoscale insights are provided into the structural organisation and mechanical properties of these hybrid materials. Both the tetrapeptide‐containing block copolymer and a control block copolymer without the peptide linker form wormlike micelles in water. However, the incorporation of the peptide linker alters the micelle morphology by increasing the contour length sixfold compared to the control polymer and by altering the mechanical properties of the wormlike micelles. TERS analysis confirms the presence of ordered β‐sheet structures at the hydrophilic/hydrophobic interface, which increase the bending stiffness of the micelles. The introduction of additional secondary interactions, such as those induced by the peptide linker, therefore appears as an interesting lever to manipulate the structure formation and mechanical properties block copolymer micelles, opening up interesting design strategies for tailor‐made hierarchically structured nanomaterials.

All-optical neuromorphic devices based on adaptive two-dimensional (2D) materials have the potential for mimicking the complex processing and memory capabilities of biological synapses. Recent research demonstrated synaptic plasticity and visual memory in WS2 monolayer-based 2D memitters (i.e., an emitter with memory). However, improving their optical performances is crucial for extending their scalability. Since the neuromorphic functionalities of 2D memitters relies on O2 and H2O desorption/absorption on WS2, a careful balance between photoluminescence intensity and surface preservation is critical. Here, we investigate the enhancement of time-dependent photoluminescence response, achieved through coupling WS2 flakes with plasmonic nanoparticles obtained by liquid phase infiltration of gold in self-assembled block copolymer micelles. The localized surface plasmon resonance of gold nanoparticles amplifies the electric field and improves light-matter interactions. This method enhances the 2D memitter optical properties while preserving its adaptive photoluminescence response, thus enabling neuromorphic behavior under optical stimuli.

Materials with the same chemical composition can exhibit distinct properties depending on their crystal phases. Here, the synthesis of two types of mesoporous Bi2Se3 films at different reduction potentials is reported and their application in electrochemical glucose sensing. Mesoporous Bi2Se3 is synthesized by incorporating block copolymer micelle assemblies into the deposition solution and applying a reduction potential. To characterize the crystal phases accurately, Bi2Se3 films are heat‐treated at 200 °C for 1 h in a nitrogen atmosphere. The results reveal that the Bi2Se3 films synthesized under different conditions exhibit clearly distinct phases: rhombohedral (R‐Bi2Se3) and orthorhombic (O‐Bi2Se3). The R‐Bi2Se3‐8 nm, featuring 8 nm pores and synthesized at a more negative reduction potential, outperforms its nonporous counterpart, achieving a glucose sensing sensitivity of 0.143 µA cm−2 µM−1 and a detection limit of 6.2 µM at pH 7.4 in 0.1 M phosphate‐buffered saline solution. In contrast, the O‐Bi2Se3, prepared at a relatively positive potential, exhibits no glucose‐sensing activity. The inactivity of O‐Bi2Se3 for glucose oxidation is likely due to the energetically unfavorable intermediates, as predicted by density functional theory calculations. These findings underscore the critical role of crystal phase control in porous nanomaterials and pave the way for developing innovative porous systems.

Drug-delivery systems have attracted considerable attentiondueto their potential to increase the bioavailability of certain drugsand mitigate side effects by enabling targeted drug release. Reversiblycore-cross-linked block copolymer micelles providing a hydrophilicand potentially nonimmunogenic shell and a hydrophobic core suitablefor the uptake of hydrophobic drugs are frequently considered becauseof their high stability against environmental changes and dilution.Ultimately, triggering core-de-cross-linking enables the implementationof strategies for targeted drug release, which requests insights intothe impact of varying nanomechanical properties on the stability ofindividual micelles. Here, atomic force microscopy nanoindentationin aqueous media is applied to intact α-allyl-PEG80-b-P(tBGE52-co-FGE12) micelles to quantify changes in theirnanomechanical properties induced by dithiobismaleimidoethane (DTME)-mediatedDiels–Alder cross-linking of furfuryl moieties and sequentialde-cross-linking by reduction of its disulfide bond by tris(2-carboxyethyl)phosphine.As a result of crosslinking by DTME, the apparent Young’s modulusof the micelles roughly doubles to 1.18 GPa. Changes to the Young’smodulus can be largely reversed by de-cross-linking. Cross-linkedand de-cross-linked micelles maintain their structural integrity evenin diluted aqueous media below the critical micelle concentration,in contrast to the micelles prior to crosslinking. Understandingthe structure–property relationships associated with the observedaugmented mechanical stability in native environments is crucial forimproving the efficiency of drug encapsulation and introducing refinedtemporal and spatially controlled drug-release mechanisms.

The hexagonal close-packed layers (HCPLs) in the hexagonal close-packed (HCP) lattice of the spherical micelles in block copolymer (BCP)/homopolymer blends were previously shown to contain a significant fraction of stacking faults, which increased in a thermally reversible manner as the temperature decreased. In this study, we further observed that the interlayer distance of the HCPLs expanded more significantly than the lateral dimension during cooling, resulting in a distorted HCP phase, with the unit cell aspect ratio (c/a) exceeding the ideal value of 1.633. The concurrent emergence of unit cell distortion and stacking faults suggested a strong correlation between these two defects. Furthermore, their thermally reversible behavior pointed to a thermodynamic origin. We propose that when the lateral size of the HCPL is small, the entropy gain from mixing HCPLs with different stacking sequences competes with the bulk free energy that favors the ideal HCP packing, leading to the introduction of stacking faults. In BCP/homopolymer blends, a fraction of the homopolymer, initially solubilized in the micelle corona, may be expelled into the interlayer regions to alleviate the bulk free energy penalty associated with stacking faults, thereby increasing the aspect ratio of the unit cell. This study reveals a thermally activated distortion of the close-packed structure in BCP blends, highlighting the complexity and tunability of the spherical phase in BCP systems.

Investigating the Block Copolymer Deposition on Au Nanoparticle Surface via Graphene Liquid Cell