Propagation rate coefficients of the high green carbon content monomer, tetrahydrofurfuryl methacrylate (THFMA, ), are measured by pulsed-laser polymerization (PLP) in combination with size-exclusion chromatography (PLP-SEC) over an extended temperature range (10-160 degrees C), allowing the observation of propagation and depropagation behavior. Arrhenius parameters are determined for bulk () and for different concentrations of monomer in solution. Lauryl methacrylate (LMA, , ) is investigated in bulk as control system. In extension to the experiments, kinetic simulations performed via PREDICI, are able to prove the molecular weight distributions (MWD) of the experiments and can be used to predict kinetic behavior for different experimental conditions.

Symmetric and asymmetric structures are generally taken as contradictory structures. Developing novel hierarchical self-assembled structures by harmonically combining both symmetry and asymmetry, which we termed "heterosymmetric structures", along with quantitative analysis of their formation process, remains underexplored but is crucial for advancing science and applications. Herein, we create novel heterosymmetric architectures using sustainable colloidal nanoparticles, cellulose nanocrystals (CNC), and hydrophilic nanolignin (NL), by modulating their evaporation kinetics and deposition behaviors to fabricate heterosymmetric films with tunable polarized optical properties for time-dependent reversible matrix encryption. During drying, the increased concentration within CNC/NL colloidal droplets and the liquid crystal phase separation induced by CNC regulate the dynamic competition between Marangoni and capillary flows. Erickson number quantifies the influence of liquid crystal elasticity and viscous forces at the triple-phase contact line in heterosymmetric structure formation. The unique heterosymmetric nature of the resulting films imparts a cross-extinction pattern accompanied by strong birefringence, circular dichroism, circularly polarized luminescence with high luminescence asymmetry factor up to 0.6 and dynamic solvent responsiveness, enabling successful multilevel encryption applications. The insights in this study not only expand the knowledge of symmetric/asymmetric structures but also enhance understanding of collective behaviors in non-equilibrium systems for self-assembling various hierarchical structures with promising properties.

ABSTRACT The synthesis of chiral unsubstituted poly(para‐phenylene) (PPP) chains has remained elusive for decades, with the production of high‐molecular‐weight PPP still inaccessible to date. Drawing inspiration from the intrinsic structural chirality of cellulose nanocrystals (CNCs), which plays a crucial role in their self‐assembly, we propose a novel strategy to address this synthetic obstacle by effectively immobilizing PPP on individual CNCs. This approach leverages intermolecular forces between CNC and PPP, including the CH–π interaction between the CH group of the pyranose ring and the aromatic ring of the PPP building block, as well as hydrogen bonds formed between the boronic acid groups of the PPP oligomers and the hydroxyl groups of the glucose units within the CNC structure, thereby facilitating the chirality transfer from CNCs to PPP chains. PPP immobilized on the CNC surface exhibits right‐handed intrachain helical self‐assembly and interchain helical π‐stacking, with the degree of polymerization reaching up to 80.2. This helical organization of PPP further laterally demonstrates the right‐handedness of individual CNCs in their undried state. Furthermore, suspensions, powders, and films composed of chiral CNC–PPP clusters exhibit pronounced fluorescence, structural coloration, chirality, and circularly polarized luminescence. This work opens novel insights and strategies for inducing chirality into polymer chains via transferring chirality from the nanoobject surface to prepare various chiral assemblies of nanoparticles or conjugated polymers.

Nonconventional luminophores devoid of traditional, large π-conjugates often suffer from low solid-state fluorescence quantum yields (FLQYs). In parallel, self-assembled bowl-shaped and helical architectures at the micro- and macroscale are unusual (mostly reported at the nanoscale). Here, we report that surface-stearoylated cellulose nanocrystals and cellulose stearoyl esters co-assemble into macroscale helices (FLQY: 86%) with diameters of 32−104 μm. Meanwhile, surface-lauroylated cellulose nanocrystals and cellulose lauroyl esters co-assemble into porous bowl-shaped microparticles (FLQY: 91%) with diameters of 8−19 μm. The high FLQYs are ascribed to the synergism of the dense oxygen clusters and abundant van der Waals interactions and hydrogen bonds between side stearoyl or lauroyl groups, which can promote through-space electron delocalization, ultimately improving fluorescence performance. These results were rationalized by theoretical calculations. Such superstructures exhibit great potential for stable anti-counterfeiting materials due to the excellent regeneration ability as well as structural stability of the oxygen clusters.

Drying in confined systems is a critical process with broad implications, spanning applications from materials science to water management in microscale technologies. Nevertheless, the coupled dynamics of transport and gelation in confined drying of colloidal suspensions remains poorly understood. Here cellulose nanocrystals (CNCs) are employed as a model system to systematically investigate the temporal dynamics, kinetic behavior, and structural transformation of nanocrystal suspensions during capillary drying. We report a mechanism whereby CNC suspensions, upon exceeding a critical concentration (∼1 wt%), undergo a transition from a fluid-like state to a kinetically arrested gel state at the evaporation front. This transition is accompanied by pinning of the evaporation interface at the capillary opening and leads to the formation of a gel-film heterostructure, consisting of a CNC gel layer with a water concentration gradient and a thin surface film formed via interfacial slip. This heterostructure promotes directional water transport from the capillary interior to the interface and significantly enhances the effective evaporative area, thereby accelerating the overall drying process. These findings offer insights into confinement-driven drying behavior and establish a framework for regulating evaporation kinetics in colloidal systems.

Bending-to-straightening behavior is vital for both natural processes and advanced materials design. Nonclassical crystallization pathways, particularly amorphous-crystalline transformations, offer opportunities to achieve such dynamic actuation. This study reveals that sugar azides are capable of undergoing spontaneous bending-to-straightening behavior, accompanied by helical deformation, driven by an amorphous-crystalline transformation during anisotropic self-assembly. The process is initiated with bending amorphous nanowires, which evolve into locally crystallized twisted nanoribbons and ultimately straighten into crystalline rectangular hollow tubes through screw dislocation. This transformation is governed by the interplay between the stereostructure of the sugar backbone and the collinear dipole arrangement of the azide group, which together regulates initial helical aggregation and subsequent directional growth. These findings not only clarify the molecular origins of bending-to-straightening crystallization but also provide a strategy for designing responsive materials capable of adapting to unstructured environments.

Reversible self-assembly of nanoparticles remains challenging due to limited molecular mobility. Moreover, reported successful examples typically rely on inorganic-core nanoparticles that require surface pre-functionalization with specific stimuli-responsive ligands. Here, we demonstrate reversible self-assembly of organic nanoparticles through the selective self-modulation of aliphatic chains, without the need for prior modification with external stimuli-responsive ligands. D-glucose 11-octadecylthioundecanoate (D-Glc-C11S18E) self-assembles into microspheres (3-6 mu m) comprising nanospheres (100-300 nm). Within these nanospheres, octadecylthioundecanoyl (C29) groups form interior crystalline domains (C29 lamella) while octadecyl (C18) chains organize at nanosphere interfaces (C18 lamella). Thermal triggering enables selective reversibility: at 50 degrees C, the C18 lamella dissociates into disordered structures while the C29 lamella remains intact; cooling to 20 degrees C regenerates the C18 lamella. In methanol, this process drives reversible microsphere-nanosphere morphological transitions (validated by scanning electron microscopy/dynamic light scattering), accompanied by a reversible fluorescence modulation. Both structural and optical modulations exhibit no apparent fatigue over 10 consecutive cycles. Energy decomposition analysis reveals stronger C29 binding energy (Delta Eint = -29.80 kcal/mol vs. C18's -19.90 kcal/mol), explaining selective reversibility. Density functional theory calculations confirm the distinct highest occupied molecular orbital-lowest unoccupied molecular orbital gaps correlating with emission wavelengths. Leveraging the temperature/wavelength-dependent fluorescence, we constructed a multi-input logic gate. This work establishes a new insight for reversible assembly and enables smart and fatigue-resistant optoelectronic applications.

Spherulites are generally fabricated from cooling polymer melts, while their fabrication under mild conditions or from small molecule materials has been barely reported. Besides, organic luminescent molecules typically suffer from low quantum yields in a solid state. Moreover, preparing material with interconnected and simultaneous changes in structural and fluorescent colors is challenging. Here, we present the first solution-derived spherulites with unique interconnected structural and fluorescent colors, self-assembled from stearoylated monosaccharides at room temperature. D-galactose stearoyl ester self-assembled into banded spherulites, containing twisted nanoplates and interconnected simultaneously changing structural and fluorescent colors. In comparison, D-mannose stearoyl ester can only form non-banded spherulites, which contain oriented nanoplates and uniform structural and fluorescent colors. Such materials revealed a novel negative correlation between fluorescence and birefringence, termed alignment-promoted quenching propensity. Remarkably, the solid-state fluorescence quantum yields of galactose and mannose-derived spherulites are as high as 49 +/- 2% and 51 +/- 2% respectively, approximately ten times higher than those of unmodified monosaccharides. These quantum yield values are among the highest of reported organic nonconventional fluorophores and even comparable to those of conventional aromatic chromophores. Moreover, these spherulites manifested an unexpected excitation-dependent multicolor photoluminescence with a broad-spectrum emission (410-620 nm). They show multiple peaks in the photoluminescent emission spectra and broad fluorescence lifetime distributions, which should be attributed to the clustering of a variety of oxygen-containing functional groups as emissive moieties.

Local detection of hydrogen concentration in metals is of central importance for many areas of hydrogen technology, such as hydrogen storage, detection, catalysis, and hydrogen embrittlement. A novel approach to measure the hydrogen concentration in a model system consisting of cubic palladium nanoparticles (Pd NPs), with a lateral resolution down to 4 nm is demonstrated. By measuring the shift of the Pd bulk plasmon peak with scanning transmission electron microscopy (STEM) combined with energy electron loss spectroscopy (EELS) during in situ hydrogen gas loading and unloading, local detection of the hydrogen concentration is achieved in TEM. With this method, concentration changes inside the NPs at various stages of hydrogenation/dehydrogenation are observed with nanometer resolution. The versatility of in situ TEM allows to link together microstructure, hydrogen concentration, and local strain, opening up a new chapter in hydrogen research.

The dehydration process is widely recognized as a significant phenomenon in nature. Hydrogels, which are important functional materials with high water content and crosslinked networks, encounter the issue of dehydration in their practical applications. Here, we report the distinctive anisotropic dehydration modality of dynamic hydrogels, which is fundamentally different from the more commonly observed isotropic dehydration of covalent hydrogels. Xerogels derived from dynamic hydrogel dehydration will fully cover a curved substrate surface and exhibit hollow structures with internal knots, in contrast to the bulk xerogels produced by covalent hydrogel dehydration. Depending on the competing cohesion of polymer chains and the adhesion at the hydrogel-substrate interface, the previously overlooked reorganization of polymer networks within dynamic hydrogels, triggered by dehydration-induced stress, has been discovered to regulate such macroscopic structural reconstruction for dynamic hydrogel dehydration. With the attached hydrogel-substrate interface, the surface microstructures of substrates can also be engraved onto xerogels with high resolution and on a large scale. This work will greatly enhance our understanding of the soft matter dehydration process and broaden the applications of dehydration technologies using water-containing materials. Hydrogels have attracted much attention due to their intrinsic viscoelastic properties, porous structures, and processability but dehydration of hydrogels often limits the application of these materials. Here, the authors report the distinctive anisotropic dehydration modality of dynamic hydrogels, which is fundamentally different from the more commonly observed isotropic dehydration of covalent hydrogels.

Plasmonic molecules (PMs) composed of polymer-capped nanoparticles represent an emerging material class with precise optical functionalities. However, achieving controlled structural changes in metallic nanoparticle aggregation at the nanoscale, similar to the modification of atomic structures, remains challenging. This study demonstrates the 2D/3D isomerization of such plasmonic molecules induced by a controlled ultrasound process. We used two types of gold nanoparticles, each functionalized with hydrogen bonding (HB) donor or acceptor polymers, to self-assemble into different ABN-type complexes via interparticle polymer bundles acting as molecular bonds. Post-ultrasonication treatment significantly shortens these bonds from approximately 14 to 2 nm by enhancing HB cross-linking within the bundles. This drastic change in the bond length increases the stiffness of the resulting clusters, facilitating the transition from 2D to 3D configurations in 100% yield during drop-casting onto substrates. Our results advance the precise control of PMs' nanoarchitectures and provide insights for their broad applications in sensing, optoelectronics, and metamaterials.

2D plasmonic molecules are constructed by hydrogen bond interaction between a donor–acceptor pair of polymer-grafted gold nanoparticles. As demonstrated in the Research Article (e202309798) by Yingying Cai and Philipp Vana, the weak yet multidentate hydrogen bonding allows a structural rearrangement from 3D to 2D when cast onto a substrate. Precise control of the coordination number is enabled by fine-tuning the interparticle interaction.

The propagation step is one of the key reactions in radical polymerization and knowledge about its kinetics is often vital for understanding and designing polymerization processes leading to new materials or optimizing technical processes. Arrhenius expressions for the propagation step in free-radical polymerization of diethyl itaconate (DEI) as well as di-n-propyl itaconate (DnPI) in bulk, for which propagation kinetics was yet unexplored, were thus determined via pulsed-laser polymerization in conjunction with size-exclusion chromatography (PLP-SEC) experiments in the temperature range of 20 to 70 °C. For DEI, the experimental data was complemented by quantum chemical calculation. The obtained Arrhenius parameters are A = 1.1 L·mol–1·s–1 and Ea = 17.5 kJ·mol−1 for DEI and A = 1.0 L·mol–1·s–1 and Ea = 17.5 kJ·mol−1 for DnPI.

AbstractDie Nutzung makromolekularer Gestaltungsmittel zur Regulierung von nicht‐kovalenten Bindungen im Nanoskalenbereich ist eine junge und emporkommende Herstellungsmethode für fortgeschrittene Nanostrukturen. Zum ersten Mal beschreiben wir eine Methode der Selbstorganisation, um eine Serie 2D‐plasmonischer Moleküle (PM) herzustellen, die Wasserstoffbrückenwechselwirkungen zwischen Paaren polymerbeschichteter Goldnanopartikel ausnutzen (Wasserstoff‐brückendonator und ‐akzeptor). Wir fanden heraus, dass aufgrund der Natur von Wasserstoffbrückenwechselwirkungen die Polymerinteraktion und die Solvatisierung während des Selbstorganisationsprozesses miteinander konkurrieren. Dies erwies sich als die wichtigste Bedingung, um die Koordinationszahl der PM zu kontrollieren. Wir führten eine umfassende Studie hinsichtlich des Lösungsmitteleffekts durch, die uns half, eine Serie präziser PM mit hoher Symetrie zu entwerfen und herzustellen.

The use of macromolecular design features to regulate non-covalent bonding on the nanoscale is a young and emerging fabrication strategy for advanced nanostructures. For the first time, we describe a self-assembly method to create a series of 2D plasmonic molecules (PMs) using hydrogen-bond interaction between a pair of polymer-capped gold nanoparticles (hydrogen-bond donor and acceptor). Due to the nature of hydrogen-bond interaction, we found that polymer interaction and solvation compete with each other during the self-assembly process, which turns out to be the most important condition for controlling the coordination number of PMs. We have conducted an extensive study on the solvent effect, which has helped us to design and fabricate a series of precise PMs with high symmetry.

Thermoresponsive hydrogels based on ionic cellulose/chitosan are widely used various fields, such as smart windows and tissue engineering, while the effect of carbohydrate backbones of cellulose/chitosan on the thermal response and mechanical properties of hydrogels has received less attention so far. Herein, poly(2(dimethylamino)ethyl methacrylate) (PDMAEMA)-grafted cellulose sulfate (P-CS) and PDMAEMA-grafted chitosan sulfate (P-CHS) as research models are successfully synthesized through multi-step reactions. The P-CS and P-CHS polymers are further applied in crosslinked polyacrylamide networks, resulting in the P-CS and P-CHS hydrogels. Compared to P-CS hydrogels, P-CHS hydrogels could obviously block the transmission of visible light when the temperature is changed from 25 to 42 °C. In contrast to P-CHS hydrogels, the P-CS hydrogels change easily from soft and weak state to stiff and strong state according to their mechanical behaviors. These results indicate that different carbohydrate backbones of cellulose and chitosan should have caused distinct aggregation behaviors of corresponding P-CS and P-CHS hydrogels, which are accompanied by different light transmittance and mechanical properties. Graphical abstract Thermoresponsive hydrogels using PDMAEMA-grafted ionic cellulose sulfate (P-CS) and chitosan sulfate (P-CHS) are successfully prepared. Distinct carbohydrate backbone displayed different effects on the thermoresponsive and mechanical properties of hydrogels.

New block co-polymer enable wide pore structures, suitable for biomolecule infiltration. These new porous thin films were compared to standard Pluronic based mesoporous layers, both, steric and charge effects on inflitration were assessed.

2D plasmonic molecules are constructed by hydrogen bond interaction between a donor–acceptor pair of polymer-grafted gold nanoparticles. As demonstrated in the Research Article (e202309798) by Yingying Cai and Philipp Vana, the weak yet multidentate hydrogen bonding allows a structural rearrangement from 3D to 2D when cast onto a substrate. Precise control of the coordination number is enabled by fine-tuning the interparticle interaction.

Polyethylene glycol-grafted gold nanoparticles are attached to silica nanoparticle cores via hydrogen bonding in a controlled fashion, forming well-defined core-satellite structures in colloidal solution. For separating these complex structures effectively from the parental nanoparticles, a straightforward and easy protocol using glass beads has been developed. The attached gold nanoparticles show unique surface mobility on the silica core surface, which allows for nanoparticle rearrangement into a 2D ring pattern surrounding the silica nanoparticle template when the core-satellite structures are cast to a planar surface. When etching away the silica core under conditions in which the polymer shell fixes the satellites to the substrate, highly ordered ring-shaped patterns of gold nanoparticles are formed. By variation of the size of the parental particles - 13 to 28 nm for gold nanoparticles and 39 to 62 nm for silica nanoparticles - a great library of different ring-structures regarding size and particle number is accessible with relative ease. The proposed protocol is low-cost and can easily be scaled up. It moreover demonstrates the power of hydrogen bonds in polymers as a dynamic anchoring tool for creating nanoclusters with rearrangement ability. We believe that this concept constitutes a powerful strategy for the development of new and innovative nanostructures.