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Two-dimensional colloidal crystals assembled from polystyrene nanospheres have emerged as a pivotal foundation for fabricating large-area nano-functional surfaces. These assemblies, defined by their hexagonal close-packed configuration and interlaced with grain boundaries, have garnered significant attention for applications in plasmonic structures, catalysts, photonic crystals, and inverse opals. Nonetheless, achieving consistent large-scale regularity has proven challenging due to unpredictable crystal growth and the introduction of defects. Utilizing acoustic waves excited from the airside, our experiments demonstrate the significant effects of such waves on the self-assembly process, leading to larger crystal domains and reduced defects. In comparison to the extensively studied water-end excitation techniques, our air-end excitation method introduces a novel dynamic in regulating colloidal monolayer crystallization and presents a comprehensive analysis of varying acoustic parameters, frequency, amplitude, and waveform. These findings reveal the potential of airside acoustic annealing in refining the structure of two-dimensional colloidal arrays. To elucidate our experimental observations, we delve into the theoretical underpinnings of particle dynamics, driven by classical hydromechanical constraints like surface tension and gravity. Using a qualitative estimate, we shed light on the resonant excitations and their potential role in optimizing the self-assembly process, especially focusing on resonances pertinent for enhancing cluster enlargements. Conclusively, our research, steeped in robust theoretical frameworks and groundbreaking experimental techniques, offers a multifaceted solution for perfecting two-dimensional colloidal arrays. This combined approach not only broadens the scope of acoustically induced crystallization but also charts a path for its adoption across diverse environments, signaling transformative prospects for nanomanufacturing and optical research. [ABSTRACT FROM AUTHOR]

This article discusses a new fabrication process for colloidal silicon quantum dots (SiQDs) that allows for the tuning of their luminescence color from red to green. The process involves low-temperature thermal cracking of electrochemically prepared meso-porous silicon flakes in a mixture of 10-undecen-1-ol and aqueous hydrogen fluoride solution. The size of the SiQDs and their luminescence color can be controlled by adjusting the content of hydrogen fluoride. The article also explores the properties and potential applications of SiQDs in various fields, such as photovoltaic devices, light emitting devices, bio-imaging, and sensing. The document discusses the size-dependent radiative recombination processes of SiQDs, including factors that can affect their photoluminescence properties. It also explains the formation mechanisms of SiQDs and how they can result in different photoluminescence colors and peak wavelengths. The document concludes by discussing the relationship between the size of SiQDs and their photoluminescence peak energies, as well as the effect of surface passivation on quantum confinement. The article presents a novel method for producing SiQDs with tunable emission colors and suggests potential applications for SiQD devices. [Extracted from the article]

The interplay between crystal nucleation and the structure of the metastable fluid has been a topic of significant debate over recent years. In particular, it has been suggested that even in simple model systems such as hard or charged colloids, crystal nucleation might be foreshadowed by significant fluctuations in local structure around the location where the nucleus first arises. We investigate this using computer simulations of spontaneous nucleation events in both hard and charged colloidal systems. To detect local structural variations, we use both standard and unsupervised machine learning methods capable of finding hidden structures in the metastable fluid phase. We track numerous nucleation events for the face-centered cubic and body-centered cubic crystals on a local level and demonstrate that all signs of crystallinity emerge simultaneously from the very start of the nucleation process. We thus conclude that we observe no precursor for the crystal nucleation of hard and charged colloids. [ABSTRACT FROM AUTHOR]

We investigate quasi-two-dimensional buckled colloidal monolayers on a triangular lattice with tunable depletion interactions. Without depletion attraction, the experimental system provides a colloidal analog of the well-known geometrically frustrated Ising antiferromagnet [Y. Han et al., Nature 456, 898–903 (2008)]. In this contribution, we show that the added depletion attraction can influence both the magnitude and sign of an Ising spin coupling constant. As a result, the nearest-neighbor Ising "spin" interactions can be made to vary from antiferromagnetic to para- and ferromagnetic. Using a simple theory, we compute an effective Ising nearest-neighbor coupling constant, and we show how competition between entropic effects permits for the modification of the coupling constant. We then experimentally demonstrate depletion-induced modification of the coupling constant, including its sign, and other behaviors. Depletion interactions are induced by rod-like surfactant micelles that change length with temperature and thus offer means for tuning the depletion attraction in situ. Buckled colloidal suspensions exhibit a crossover from an Ising antiferromagnetic to paramagnetic phase as a function of increasing depletion attraction. Additional dynamical experiments reveal structural arrest in various regimes of the coupling-constant, driven by different mechanisms. In total, this work introduces novel colloidal matter with "magnetic" features and complex dynamics rarely observed in traditional spin systems. [ABSTRACT FROM AUTHOR]

We investigate and compare the difference in the dynamics of two arrested states: colloidal glass and colloidal gel. Real-space experiments reveal two distinct nonergodicity origins for their slow dynamics, namely, cage effects for the glass and attractive bondings for the gel. Such distinct origins lead to a faster decay of the correlation function and a smaller nonergodicity parameter of the glass than those of the gel. We also find that the gel exhibits stronger dynamical heterogeneity compared with the glass due to the greater correlated motions in the gel. Moreover, a logarithmic decay in the correlation function is observed as the two nonergodicity origins merge, consistent with the mode coupling theory. [ABSTRACT FROM AUTHOR]

In this contribution, gravitational effects in gel-forming patchy colloidal systems are studied. We focus on how the gel structure is modified by gravity. Through Monte Carlo computer simulations of gel-like states recently identified by the rigidity percolation criterion [J. A. S. Gallegos et al., Phys. Rev. E 104, 064606 (2021)], the influence of the gravitational field, characterized by the gravitational Péclet number, Pe, on patchy colloids is studied in terms of the patchy coverage, χ. Our findings point out that there exists a threshold Péclet number, Peg, that depends on χ above which the gravitational field enhances the particle bonding and, in consequence, promotes the aggregation or clustering of particles; the smaller the χ value, the higher the Peg. Interestingly, when χ ∼ 1 (near the isotropic limit), our results are consistent with an experimentally determined threshold Pe value where gravity affects the gel formation in short-range attractive colloids. In addition, our results show that the cluster size distribution and the density profile undergo variations that lead to changes in the percolating cluster, i.e., gravity is able to modify the structure of the gel-like states. These changes have an important impact on the structural rigidity of the patchy colloidal dispersion; the percolating cluster goes from a uniform spatially network to a heterogeneous percolated structure, where an interesting structural scenario emerges, namely, depending on the Pe value, the new heterogeneous gel-like states can coexist with both diluted and dense phases or they simply reach a crystalline-like state. In the isotropic case, the increase in the Pe number can shift the critical temperature to higher temperatures; however, when Pe > 0.01, the binodal disappears and the particles fully sediment at the bottom of the sample cell. Furthermore, gravity moves the rigidity percolation threshold to lower densities. Finally, we also note that within the values of the Péclet number here explored, the cluster morphology is barely altered. [ABSTRACT FROM AUTHOR]

Polymorphism and co-crystallization have gradually gained attention as new tools in the development of modern crystalline functional materials. However, the study on the selective self-assembly of metal clusters into multicomponent crystals is still in its infancy. Herein, we present the synthesis and characterization of two new heteroleptic hydroxido-acetato and acetato Co(II) clusters [Co6(OH)2(OAc)4(pyret)6] (1) and [Co6(OAc)6(pyret)6] (2) incorporating auxiliary 2-pyrrolidinoethoxylate (pyret) ligands. On this occasion, we revealed that the commonly used thermal procedure for dehydration of cobalt(II) acetate leads to a reagent comprising substantial contamination by cobalt hydroxido moieties. Comprehensive structural analysis of new compounds demonstrated intriguing crystal structure diversity of hydroxido-acetato cluster 1, which represents a rare example of both conformational and packing polymorphism in one compound, originating from the flexibility of organic O,N-ligands in the secondary coordination sphere. Furthermore, both clusters exhibit an interesting propensity for the selective formation of co-crystals 1·2 driven mainly by van der Waals forces and specific shape complementarity between co-formers. [ABSTRACT FROM AUTHOR]

Bacteriophages have a well‐defined nanoscale size, shape, and surface chemistry, making them promising candidates for creating advanced biomaterials for applications including biocatalysis, drug delivery, and biosensing. This study demonstrates the self‐assembly of the ≈29 nm diameter bacteriophage Qbeta (Qubevirus durum) with the synthetic polycation, poly [2‐(methacryloyloxy)ethyl] trimethylammonium chloride (pMETAC), into compartmentalized colloidal crystals. The pH and the polymer chain length tune their self‐assembly and the resulting structure, with the potential for further chemical modification or loading with bioactive molecules. Small angle X‐ray scattering (SAXS), multi‐angle dynamic light scattering (DLS), and atomic force microscopy (AFM) are used for studying the Qbeta self‐assembly into the geometrically ordered aggregates. The suprastructures form at pH > 7.0 and disassemble at pH < 7.0. Zeta potential measurements and X‐ray photoelectron spectroscopy (XPS) show pMETAC adsorption onto the negatively charged Qbeta surface. The colloidal crystal formation is achieved without chemically modifying the Qbeta surface. Additionally, the Qbeta/pMETAC suprastructures can be easily separated from the suspension as macroscopic aggregate, maintaining their activity. Their simple preparation allows for large‐scale production of advanced materials in food and health science applications and nanotechnology. The insights from this study will further advance the tailored design and production of novel colloidal materials. [ABSTRACT FROM AUTHOR]

We give details and derivations for the Noether invariance theory that characterizes the spatial equilibrium structure of inhomogeneous classical many-body systems, as recently proposed and investigated for bulk systems (Sammüller et al 2023 Phys. Rev. Lett. 130 268203). Thereby an intrinsic thermal symmetry against a local shifting transformation on phase space is exploited on the basis of the Noether theorem for invariant variations. We consider the consequences of the shifting that emerge at second order in the displacement field that parameterizes the transformation. In a natural way the standard two-body density distribution is generated. Its second spatial derivative is thereby balanced by two further and different two-body correlation functions, which respectively introduce thermally averaged force correlations and force gradients in a systematic and microscopically sharp way into the framework. Separate exact self and distinct sum rules express this balance. We exemplify the validity of the theory on the basis of computer simulations for the Lennard–Jones gas, liquid, and crystal, the Weeks–Chandler–Andersen fluid, monatomic Molinero–Moore water at ambient conditions, a three-body-interacting colloidal gel former, the Yukawa and soft-sphere dipolar fluids, and for isotropic and nematic phases of Gay–Berne particles. We describe explicitly the derivation of the sum rules based on Noether's theorem and also give more elementary proofs based on partial phase space integration following Yvon's theorem. [ABSTRACT FROM AUTHOR]

Tin halide perovskites (THPs) have demonstrated exceptional potential for various applications owing to their low toxicity and excellent optoelectronic properties. However, the crystallization kinetics of THPs are less controllable than its lead counterpart because of the higher Lewis acidity of Sn2+, leading to THP films with poor morphology and rampant defects. Here, a colloidal zeta potential modulation approach is developed to improve the crystallization kinetics of THP films inspired by the classical Derjaguin‐Landau‐Verwey‐Overbeek (DLVO) theory. After adding 3‐aminopyrrolidine dihydro iodate (APDI2) in the precursor solution to change the zeta potential of the pristine colloids, the total interaction potential energy between colloidal particles with APDI2 could be controllably reduced, resulting in a higher coagulation probability and a lower critical nuclei concentration. In situ laser light scattering measurements confirmed the increased nucleation rate of the THP colloids with APDI2. The resulting film with APDI2 shows a pinhole‐free morphology with fewer defects, achieving an impressive efficiency of 15.13 %. [ABSTRACT FROM AUTHOR]

The rapid development of optoelectronic devices with biomimetic synaptic behavior holds significant potential for neuromorphic visual applications. However, considerable challenges remain including convenient device fabrication and low toxicity materials innovation. Here, a heterojunction phototransistor is constructed using low‐toxic CuZnInSSe (CIZS) colloidal quantum dots and amorphous InGaZnO (IGZO), which demonstrates high specific detectivity of 3.4 × 1015 Jones in visible light spectrum. Moreover, it is found that the photoresponse speed can be controlled via a ligand exchange treatment, through that the response speed can be adjusted from 0.3 to 11 s. This enables the device to operate in two distinct modes: a typical fast sensing mode and a neuromorphic visual mode. In the neuromorphic visual mode, the device's synaptic behavior can be tuned by manipulating light pulse intensity, frequency, wavelength, and gate voltage. As a demonstration, a phototransistor array effectively implements image pre‐processing functions, including color recognition, visual memorizing, and forgetting. [ABSTRACT FROM AUTHOR]

Free‐standing zinc oxide in the forms of films and fibrous materials are expected to be used as functional devices such as piezoelectric devices and catalyst filters without being limited by the growth substrate. Herein, a synthetic morphology‐control method for 2D and 1D free‐standing ZnO materials with ordered and nanoporous structures by conversion of liquid‐crystalline (LC) zinc hydroxide carbonate (ZHC) nanoplates is reported. As a new colloidal liquid crystal, the LC ZHC nanoplate precursors are obtained by a biomineralization‐inspired method. The approach is to control the morphology and crystallographic orientation of ZHC crystals by using acidic macromolecules. Their nano‐scale and oriented structures are examined. The LC oriented ZHC nanoplates have led to the synthesis of free‐standing films and microfibers of ZHC in centimeter‐level lengths, with the successful thermal conversion into free‐standing films and microfibers of ZnO. The resultant ZnO films and ZnO microfibers have nanoporous structures and preferential crystallographic orientations that preserve the alignment of ZHC nanoplates before conversion. [ABSTRACT FROM AUTHOR]

2D gibbsite nanoplatelets, [γ‐Al(OH)3], are widely used as an inorganic mineral platform for 2D lyotropic liquid crystal (LC) colloids. These particles are synthesized and enlarged using an improved hydrolysis method, resulting in highly crystalline (96.5%), low polydispersity (15.1%), and readily dispersible colloids in water. The aqueous mesomorphic system is characterized for the isotropic‐to‐nematic phase transition by analyzing number density and shear viscosity. Thermal stability is assessed through thermogravimetric analysis. Additionally, kinetic and thermodynamic parameters for 2D gibbsite nanoparticles are determined for the first time using three models (Coats‐Redfern, Friedman, and Kissinger). In particular, the activation and Gibbs free energies for the first dehydration stage of gibbsite yield ranges of 98‒128 kJ mol−1 and 135‒161 kJ mol−1, respectively. To investigate the confinement effect of colloidal gibbsite‐LCs, an isotropic gibbsite dispersion is introduced into a tube, leading to the uniform formation of gibbsite‐LC layers along two distinct pathways: tangential to the liquid‐air interface and as concentric circles along the tube walls. These findings offer valuable insights into potential applications, particularly in the domain of gas barrier inorganic films across various specialized fields. [ABSTRACT FROM AUTHOR]

Mechanical metamaterials, whose unique mechanical properties stem from their structural design rather than material constituents, are gaining popularity in engineering applications. In particular, recent advances in self-assembly techniques offer the potential to fabricate load-bearing mechanical metamaterials with unparalleled feature size control and scalability compared to those produced by additive manufacturing (AM). Yet, the field is still in its early stages. In this perspective, we first provide an overview of the state-of-the-art self-assembly techniques, with a focus on the copolymer and colloid crystal self-assembly processes. We then discuss current challenges and future opportunities in this research area, focusing on novel fabrication approaches, the need for high-throughput characterization methods, and the integration of Machine Learning (ML) and lab automation for inverse design. Given recent progress in all these areas, we foresee mechanical metamaterials fabricated from self-assembly techniques impacting a variety of applications relying on lightweight, strong, and tough materials. [ABSTRACT FROM AUTHOR]

A self‐confined solid‐state dewetting mechanism is reported that can fundamentally reduce the use of sophisticated nanofabrication techniques, enabling efficient wafer‐scale patterning of non‐closely packed (ncp) gold nanoparticle arrays. When combined with a soft lithography process, this approach can address the reproducibility challenges associated with colloidal crystal self‐assembly, allowing for the batch fabrication of ncp gold arrays with consistent ordering and even optical properties. The resulting dewetted ncp gold nanoparticle arrays exhibit strong surface lattice resonance properties when excited in inhomogeneous environments under normal white‐light incidence. With these SLR properties, the sensitive plasmonic sensing of molecular interactions is achieved using a simple transmission setup. This study will advance the development of miniaturized and portable devices. [ABSTRACT FROM AUTHOR]

The pair-interaction force profiles for two non-magnetic colloids immersed in a suspension of ferromagnetic colloidal polymers are investigated via Langevin simulations. A quasi-two-dimensional approach is taken to study the interface case and a range of colloidal size ratios (non-magnetic:magnetic) from 6:1 up to 20:1 have been considered in this work. Simulations show that when compared with non-magnetic suspensions, the magnetic polymers strongly modify the depletion force profiles leading to strongly oscillatory behavior. Larger polymer densities and size ratios increase the range of the depletion forces, and in general, also their strength; the force barrier peaks at short distances show more complex behavior. As the length of the ferromagnetic polymers increases, the force profiles become more regular, and stable points with their corresponding attraction basins develop. The number of stable points and the distance at which they occur can be tuned through the modification of the field strength H and the angle θ formed by the field and the imaginary axis joining the centers of the two non-magnetic colloids. When not constrained, the net forces acting on the two colloids tend to align them with the field till θ = 0 ∘ . At this angle, the force profiles turn out to be purely attractive, and therefore, these systems could be used as a funneling tool to form long linear arrays of non-magnetic particles. Torsional forces peak at θ = 45 ∘ and have minimums at θ = 0 ∘ as well as θ = 90 ∘ which is an unstable orientation as slight deviations will evolve towards θ → 0 ∘ . Nonetheless, results suggest that the θ = 90 ∘ orientation could be easily stabilized in several ways. In such a case, the stable points that the radial force profiles exhibit for this orthogonal orientation to the field could be used to control the distance between the two large colloids: their position and number can be controlled via H. Therefore, suspensions made of ferromagnetic colloidal polymers can be also useful in the creation of magnetic colloidal tweezers or ratchets. A qualitative explanation of all the observed phenomena can be provided in terms of how the geometrical constraints and the external field modify the conformations of the ferromagnetic polymers near the two large particles, and in turn, how both factors combine to create unbalanced Kelvin forces that oscillate in strength with the distance between the two non-magnetic colloids. [ABSTRACT FROM AUTHOR]

The atomically dispersed Ni–P 3 species on BP nanosheets own the electron-rich feature that can improve the photogenerated charge separation efficiency and lower the activation barrier of CO 2 conversion, thus realizing highly efficient visible-light-driven CO 2 reduction. [Display omitted] • A conceptionally new single-atom catalyst BP-Ni is synthesized. • BP-Ni exhibits excellent activity as a cocatalyst in the photocatalytic CO 2 reduction. • The Ni–P 3 species on BP nanosheets own the electron-rich feature. • The Ni–P 3 species can improve the photogenerated charge separation efficiency. • The Ni–P 3 species can lower the activation barrier of CO 2 conversion. The development of unique single-atom catalysts with electron-rich feature is essential to promoting the photocatalytic CO 2 reduction, yet remains a big challenge. Here, a conceptionally new single-atom catalyst constructed from atomically dispersed Ni–P 3 species on black phosphorus (BP) nanosheets (BP-Ni) is synthesized for realizing highly efficient visible-light-driven CO 2 reduction when trapping photogenerated electrons from homogeneous light absorbers in the presence of triethanolamine as the sacrificial agent. Both the experimental and theoretical calculation data reveal that the Ni–P 3 species on BP nanosheets own the electron-rich feature that can improve the photogenerated charge separation efficiency and lower the activation barrier of CO 2 conversion. This unique feature makes BP-Ni exhibit the much higher activity as cocatalyst in the photocatalytic CO 2 reduction than BP nanosheets. The BP-Ni can also be applied as a cocatalyst for enhanced photocatalytic CO 2 reduction after combining with CdSe/S colloidal crystal photocatalyst. The present study offers valuable inspirations for the design and construction of effective catalytic sites toward photocatalytic CO 2 reduction reactions. [ABSTRACT FROM AUTHOR]

The development of innovative methods for real-time surveillance of enzymatic activity determination processes is essential, particularly for insoluble substrate enzymatic assessments. In this work, a novel method for enzymatic activity determination was devised by assembling a 190 nm silica colloidal crystal (SCC) film onto a glass slide, coupled with Ordered Porous Layer Interferometry (OPLI) technology. By fixing the substrate of the enzyme on the surface of the silica sphere, a solid–liquid interface can be formed for monitoring enzymatic activity. The enzymatic activity is gauged by the change in the SCC film's thickness caused by the digestion of the loaded substrate. The procedure of chymotrypsin-mediated casein digestion was documented in real time, facilitating the examination of chymotrypsin's activity and kinetics. The newly-developed enzymatic activity determination method demonstrated exceptional sensitivity towards chymotrypsin activity, with a linear range spanning 0.0505–2.02 units per mg. Additionally, the method was extended to the assessment of fibrinolysis enzyme activity and kinetic analysis, yielding promising results. Therefore, this technique can serve as a real-time, user-friendly, cost-effective novel approach for enzymatic activity determination, providing fresh perspectives for enzymatic activity determination studies. [ABSTRACT FROM AUTHOR]

The early stages of the molecular self‐assembly pathway leading to crystal nucleation have a significant influence on the properties and purity of organic materials. This mini review collates the work on organic mesoscale clusters and discusses their importance in nucleation processes, with a particular focus on their critical properties and susceptibility to sample treatment parameters. This is accomplished by a review of detection methods, including dynamic light scattering, nanoparticle tracking analysis, small angle X‐ray scattering, and transmission electron microscopy. Considering the challenges associated with crystallisation of flexible and large‐molecule active pharmaceutical ingredients, the dynamic nature of mesoscale clusters has the potential to expand the discovery of novel crystal forms. By collating literature on mesoscale clusters for organic molecules, a more comprehensive understanding of their role in nucleation will evolve and can guide further research efforts. [ABSTRACT FROM AUTHOR]

Designing of innovative technologies for the development of functional materials remain crucial for achieving sustainable technological advancements. In this regard, nanoparticles (NPs) possessing enormous potential properties can be obtained using various facile methods for several applications. Adopting NPs as primitive building blocks can initiate the formation of complex entities named supraparticle (SP) to create several advanced functional materials. Additionally, SPs enable entirely new material characteristics to the system, owing to their individual entities, intrinsic properties such as coupling, spatial arrangement, and co‐localization. Indeed, methods such as template‐induced evaporation‐based assembly of NPs direct the shape, size, and morphology of SPs from their respective colloidal dispersions on a solvent‐repellant solid surface. Therefore, it is important to comprehend the formation of SPs and their structure‐property relationship with respect to practical application. This review presents a brief overview of SPs assembly by outlining the templated‐assisted evaporation‐based methodologies for synthesizing SPs. Further, the effect of various factors on the interaction between colloidal entities, solvent, and substrate, leading to the genesis of SPs is elaborated. Conclusively, specific properties are described and applications of SPs for energy storage, generation, and environmental remediation are reported, which collectively brings many interdisciplinary research fields to the same podium. [ABSTRACT FROM AUTHOR]

The application of organic crystal in different photoelectric device has different demand on the crystal structure and morphology, while the self‐assembly of different materials into crystals with a desired morphology remains a challenge. Herein, using three binary halogen‐bonded cocrystals involving a nonplanar halogen accepter molecule tetra(4‐pyridyl)‐tetrathiafulvalene (TTF(py)4), co‐crystallized with halogen donor aryl iodides C6F6‐xIx (x = 2,3, 1,3,5‐trifluoro‐2,4,6‐triiodobenzene (IFB), meta‐1,3‐diiodotetrafluorobenzene (mdIFB) or para‐1,3‐diiodotetrafluorobenzene (pdIFB)), are reported. TTF(py)4‐IFB cocrystals are formed primarily via N···I halogen bonds and F···H hydrogen bonds, while TTF(py)4‐mdIFB cocrystals and TTF(py)4‐pdIFB cocrystals are formed primarily via π–π Interactions, N···I halogen bonds and F···H hydrogen bonds, homogeneous π–π interactions are dominant in TTF(py)4‐mdIFB, while heterogeneous π–π interactions are dominant in TTF(py)4‐pdIFB. Through predicted morphology based on the attachment energy (Eatt) theory, especially π–π interaction, the influence of intermolecular interactions on crystal morphology is analyzed. The study demonstrates that the π–π interaction plays an important role in regulating the crystal structure and morphology, the work provides a deeper understanding of π–π interactions in nonplanar binary halogen‐bonded cocrystals. [ABSTRACT FROM AUTHOR]

Summary: In this study, the oleogel was produced by Pickering emulsion‐based method by using citrus fibre (CF)‐whey protein isolate (WPI) colloidal complex. The obtained oleogels were characterised by rheological and textural properties, and then the oleogels were used in cookies as an alternative to palm oil. The four oleogels (1% to 5%) were fabricated using a CF‐10% WPI complex. Shear thinning rheological behaviour was observed in all emulsion and oleogel samples. The G values were greater than the G values, indicating that solid‐like behaviour dominated in all emulsion and oleogel samples. All oleogel samples had a higher than 90% oil‐holding capacity. The visual appearance of 3% CF‐10% WPI and 5% CF‐10% WPI showed no surface oil, and more integrity structure means that could well trap oil in a gel matrix. Increasing CF% concentration reduced oil droplets and created a more compact structure, particularly at 3% and 5% CF‐10% WPI. An increase in CF concentration from 2% to 5% led to an increase in the hardness value of the dried products and cookies that CF formed a 3D network structure with binds liquid oil. The oxidative stability showed that no significant changes were found between the 3% CF‐10% WPI and palm cookies (P < 0.05). Cookies containing oleogels with a 3% CF content exhibited a visual resemblance to this trait, suggesting a colour appearance that closely resembled cookies made with palm oil. The incorporation of oleogels into the cookie recipe proved to be an effective substitute for palm oil. CF‐10% WPI oleogels show promise for use in cookie preparation as a replacement for palm oil, offering potential as substitutes for saturated and trans fats in food products. [ABSTRACT FROM AUTHOR]

SERS has been of interest as an influential analytical characterization method for scientific studies to detect chemical and biological molecules. The selection of suitable SERS substrates is a major challenge for specific detection of molecules. Here, two different types of graphene-based SERS substrates were prepared and their SERS activities were compared. Our chemical vapor-deposited graphene (CVDG) SERS substrates showed an excellent limit of detection of 10−13 M. 10−13 M is the lowest concentration achieved so far in the as grown graphene-based SERS substrates without the use of noble metal or other materials for R6G molecules. When a flexible and transparent SERS substrate with a large surface area is desired, substrates made of CVDG SERS substrates are more suitable, while modified graphene oxide (MGO) may be preferred in powder, colloid and thin film SERS applications. MGO showed better signal enhancement compared to CVDG and SiO2 reference substrates in high concentration R6G solution. The differences between the SERS activities of the substrates were discussed in detail in terms of the differences in the chemical, electrical, optical, and surface properties of CVDG and MGO. Understanding the enhancement activities of non-resonant graphene-based SERS materials is critical for the next generation of Raman spectrometer instruments. [ABSTRACT FROM AUTHOR]

The self-assembly of colloidal nanoparticles into ordered superlattices typically uses dynamic interactions to govern particle crystallization, as these non-permanent bonds prevent the formation of kinetically trapped, disordered aggregates. However, while the use of reversible bonding is critical in the formation of highly ordered particle arrangements, dynamic interactions also inherently make the structures more prone to disassembly or disruption when subjected to different environmental stimuli. Thus, there is typically a trade-off between the ability to initially form an ordered colloidal material and the ability of that material to retain its order under different conditions. Here, we present a method for embedding colloidal nanoparticle superlattices into a polymer gel matrix. This encapsulation strategy physically prevents the nanoparticles from dissociating upon heating, drying, or the introduction of chemicals that would normally disrupt the lattice. However, the use of a gel as the embedding medium still permits further modification of the colloidal nanoparticle lattice by introducing stimuli that deform the gel network (as this deformation in turn alters the nanoparticle lattice structure in a predictable manner). Moreover, encapsulation of the lattice within a gel permits further stabilization into fully solid materials by removing the solvent from the gel or by replacing the solvent with a liquid monomer that can be photopolymerized. This embedding method therefore makes it possible to incorporate ordered colloidal arrays into a polymer matrix as either dynamic or static structures, expanding their potential for use in responsive materials. [ABSTRACT FROM AUTHOR]

This paper presents a theoretical investigation of the design of a new actuator type made of anisotropic colloidal particles grafted with stimuli-responsive polymer chains. These artificial muscles combine the osmotic actuation principle of stimuli-responsive hydrogels with the structural alignment of colloidal liquid crystals to achieve directional motion. The solubility of the stimuli-responsive polymer in the neutral state, its degree of polymerization, the salt concentration, and the grafting density of the polymer chains on the surface of the colloidal particles are investigated and identified as important for actuator performance and tunability. The computational results suggest that the proposed mechanically active material matches or exceeds the performances of natural muscles and provide the guidelines for the realization of artificial muscles with predetermined actuation properties. [ABSTRACT FROM AUTHOR]

Yielding of the particulate network in colloidal gels under applied deformation is accompanied by various microstructural changes, including rearrangement, bond rupture, anisotropy, and reformation of secondary structures. While much work has been done to understand the physical underpinnings of yielding in colloidal gels, its topological origins remain poorly understood. Here, employing a series of tools from network science, we characterize the bonds using their orientation and network centrality. We find that bonds with higher centralities in the network are ruptured the most at all applied deformation rates. This suggests that a network analysis of the particulate structure can be used to predict the failure points in colloidal gels a priori. [ABSTRACT FROM AUTHOR]

Shear history plays an important role in determining the linear and nonlinear rheological response of colloidal gels and can be used for tuning their structure and flow properties. Increasing the colloidal particle aspect ratio lowers the critical volume fraction for gelation due to an increase in the particle excluded volume. Using a combination of rheology and confocal microscopy, we investigate the effect of steady and oscillatory preshear history on the structure and rheology of colloidal gels formed by silica spheres and rods of length L and diameter D (L/D = 10) dispersed in 11 M CsCl solution. We use a non-dimensional Mason number, Mn (=Fvisc./Fattr.), to compare the effect of steady and oscillatory preshear on gel viscoelasticity. We show that after preshearing at intermediate Mn, attractive sphere gel exhibits strengthening, whereas attractive rod gel exhibits weakening. Rheo-imaging of gels of attractive rods shows that at intermediate Mn, oscillatory preshear induces large compact rod clusters in the gel microstructure, compared to steady preshear. Our study highlights the impact of particle shape on gel structuring under flow and viscoelasticity after shear cessation. [ABSTRACT FROM AUTHOR]

We study the crystallization of colloidal dispersions under capillary-action-induced shear as the dispersion is drawn into flat walled capillaries. Using confocal microscopy and small angle x-ray scattering, we find that the shear near the capillary walls influences the crystallization to result in large random hexagonal close-packed (RHCP) crystals with long-range orientational order over tens of thousands of colloidal particles. We investigate the crystallization mechanism and find partial crystallization under shear, initiating with hexagonal planes at the capillary walls, where shear is highest, followed by epitaxial crystal growth from these hexagonal layers after the shear is stopped. We then characterize the three-dimensional crystal structure finding that the shear-induced crystallization leads to larger particle separations parallel to the shear and vorticity directions as compared to the equilibrium RHCP structure. Confocal microscopy reveals that competing shear directions, where the capillary walls meet at a corner, create differently oriented hexagonal planes of particles. The single-orientation RHCP colloidal crystals remain stable after formation and are produced without the need of complex shear cell arrangements. [ABSTRACT FROM AUTHOR]

Migration of colloidal particles induced by temperature gradients is commonly referred to as thermodiffusion, thermal diffusion, or the (Ludwig-)Soret effect. The thermophoretic force experienced by a colloidal particle that drives thermodiffusion consists of two distinct contributions: a contribution resulting from internal degrees of freedom of single colloidal particles, and a contribution due to the interactions between the colloids. We present an irreversible thermodynamics based theory for the latter collective contribution to the thermophoretic force. The present theory leads to a novel "thermophoretic interaction force" (for uncharged colloids), which has not been identified in earlier approaches. In addition, an N -particle Smoluchowski equation including temperature gradients is proposed, which complies with the irreversible thermodynamics approach. A comparison with experiments on colloids with a temperature dependent attractive interaction potential over a large concentration and temperature range is presented. The comparison shows that the novel thermophoretic interaction force is essential to describe data on the Soret coefficient and the thermodiffusion coefficient. • An irreversible thermodynamics based theory is presented leading to a novel "thermophoretic interaction force" on colloidal particles that originates from their mutual interactions. • Explicit microscopic expressions are found for the Soret coefficient and the thermodiffusion coefficient in terms of the (equilibrium) pair-correlation function. • The novel thermophoretic interaction force is essential to be able to describe the experimental data. [ABSTRACT FROM AUTHOR]

[Display omitted] We hypothesize that pre-assembled lithographic Brownian seven-fold quasi-crystals (QCs) of colloidal tiles at high densities can exhibit a heptatic liquid quasi-crystal (LQC) phase upon release; such heptatic LQCs can undergo heterogeneous dynamics at different length scales, reflecting the underlying symmetry, corrugation, and hierarchy of local sets of tiles. We design, fabricate, and release a seven-fold QC composed of three differently shaped rhombic tiles using the method of lithographically pre-assembled monolayers (litho-PAMs). High resolution optical microscopy enables spatio-temporal particle tracking of Brownian fluctuations of many tiles in a large area over a long time. We develop an edge-proximity tessellation method for analyzing nearest neighboring particles that can be applied to assemblies and dense systems of complex shapes. A fluctuating heptatic LQC phase is identified at high tile area fractions. Heterogenous dynamics and order at different length scales indicate diverse, hierarchical motif structures. We show that certain motifs can collectively rotate without any cage breaking, leading to alterations of the local tile-structure reminiscent of phason-flips in atomic QCs; this rotation causes a slow decline in the system's spatial order. We anticipate that edge-proximity tessellation will help elucidate phase transitions of other systems made of diverse building blocks having significant geometrical complexity at multiple length scales. [ABSTRACT FROM AUTHOR]

[Display omitted] • 2D GnP/MoS 2 and 3D (GnP/MoS 2)/MWNT composites are prepared by a facile, robust and ecofriendly method. • Effects of N-doping of GnPs and mass fraction of MWNTs on ORR activity are explored and rationalized. • Best synergistic ORR activity is obtained for N-doped catalyst with 3:1 2D-to-1D ratio. • Catalysts exhibit excellent stability and methanol resistance in alkaline medium. • Promising route to develop bifunctional ORR/OER catalysts. Nanocomposites have garnered attention for their potential as catalysts in electrochemical reactions vital for technologies like fuel cells, water splitting, and metal-air batteries. This work focuses on developing three-dimensional (3D) nanocomposites through aqueous phase exfoliation, non-covalent functionalization of building blocks with surfactants and polymers, and electrostatic interactions in solution leading to the nanocomposites assembly and organization. By combining molybdenum disulfide (MoS 2) layers with graphene nanoplatelets (GnPs) to form a binary 2D composite (MoS 2 /GnP), and subsequently incorporating multiwalled carbon nanotubes (MWNTs) to create ternary 3D composites, we explore their potential as catalysts for the oxygen reduction reaction (ORR) critical in fuel cells. Characterization techniques such as X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction elucidate material composition and structure. Our electrochemical studies reveal insights into the kinetics of the reactions and structure–activity relationships. Both the (MoS 2 /GnP)-to-MWNT mass ratio and nitrogen-doping of GnPs (N -GnPs) play a key role on the electrocatalytic ORR performance. Notably, the (MoS 2 / N -GnP)/MWNT material, with a 3:1 mass ratio, exhibits the most effective ORR activity. All catalysts demonstrate good long-term stability and methanol crossover tolerance. This facile fabrication method and observed trends offer avenues for optimizing composite electrocatalysts further. [ABSTRACT FROM AUTHOR]

Abstract Nanostructured materials that mimic structural coloration in nature can be synthetically created by colloidal self‐assembly. To maximize optical effects, the natural world integrates melanin as a broadband absorber to remove incoherently scattered light. Polydopamine (PDA) is used as a synthetic analog of natural melanin to systematically investigate the influence of absorber quantity and distribution on color saturation in colloidal photonic crystals. The absorbing PDA is integrated into two distinct ways: homogenous colloidal crystals are produced from core–shell particles with incrementally increasing polydopamine shells, and heterogeneous colloidal crystals are formed by co‐assembly of varying ratios of polystyrene (PS) and absorbing PS@PDA particles. The chromaticity is quantified by converting the measured spectra to reconstructed colors in the L*a*b* color sphere to identify structures with optimal color saturation. Simulations based on the discrete dipole approximation (DDA) indicate that a homogeneous absorber distribution is most efficient in creating saturated structural coloration. Experiments, however, demonstrate that the heterogeneous absorber incorporation outperforms the homogeneous strategies, as it allows for a more precise adjustment of the absorber content in the required concentration range. These results underline the importance of incorporating absorbers and indicate efficient ways in which colloidal photonic crystals with saturated structural colors can be prepared.

Abstract Colloidal crystals are materials self‐assembled from the colloidal nanoparticles. Due to the ordered microstructure, they exhibit significant optical properties and have shown huge potential in the field of biosensing. Besides, the unique macroscopic shapes can also play a critical role in the sensing process. Here, we present a comprehensive discussion on the colloidal crystal‐based biosensors with different topological shapes, including the development strategies of currently reported colloidal crystal particles, films, and fibers, and their recent progress in biosensing. In addition, the faced challenges and the possible solutions are also concluded and discussed. We expect this review can enrich the knowledge and encourage the communication of interdisciplinary researchers, thus promoting the further development and practical applications of colloidal crystal‐based biosensors.

The response of soft colloids to crowding depends sensitively on the particles' compressibility. Nanogel suspensions provide model systems that are often studied to better understand the properties of soft materials and complex fluids from the formation of colloidal crystals to the flow of viruses, blood, or platelet cells in the body. Large spherical nanogels, when embedded in a matrix of smaller nanogels, have the unique ability to spontaneously deswell to match their size to that of the nanogel composing the matrix. In contrast to hard colloids, this self-healing mechanism allows for crystal formation without giving rise to point defects or dislocations. Here, we show that anisotropic ellipsoidal nanogels adapt both their size and their shape depending on the nature of the particles composing the matrix in which they are embedded. Using small-angle neutron scattering with contrast variation, we show that ellipsoidal nanogels become spherical when embedded in a matrix of spherical nanogels. In contrast, the anisotropy of the ellipsoid is enhanced when they are embedded in a matrix of anisotropic nanogels. Our experimental data are supported by Monte Carlo simulations that reproduce the trend of decreasing aspect ratio of ellipsoidal nanogels with increasing crowding by a matrix of spherical nanogels. [ABSTRACT FROM AUTHOR]

We study the nucleation of nearly hard charged colloidal particles. We use Monte Carlo simulations in combination with free-energy calculations to accurately predict the phase diagrams of these particles and map them via the freezing density to hard spheres, then we use umbrella sampling to explore the nucleation process. Surprisingly, we find that even very small amounts of charge repulsion can have a significant effect on the phase behavior. Specifically, we find that phase boundaries and nucleation barriers are mostly dependent on the Debye screening length and that even screening lengths as small as 2% of the particle diameter are sufficient to show marked differences in both. This work demonstrates clearly that even mildly charged colloids are not effectively hard spheres. [ABSTRACT FROM AUTHOR]

Colloidal systems possess unique features to investigate the governing principles behind liquid-to-solid transitions. The phase diagram and crystallization landscape of colloidal particles can be finely tuned by the range, number, and angular distribution of attractive interactions between the constituent particles. In this work, we present a computational study of colloidal patchy particles with high-symmetry bonding—six patches displaying octahedral symmetry—that can crystallize into distinct competing ordered phases: a cubic simple (CS) lattice, a body-centered cubic phase, and two face-centered cubic solids (orientationally ordered and disordered). We investigate the underlying mechanisms by which these competing crystals emerge from a disordered fluid at different pressures. Strikingly, we identify instances where the structure of the crystalline embryo corresponds to the stable solid, while in others, it corresponds to a metastable crystal whose nucleation is enabled by its lower interfacial free energy with the liquid. Moreover, we find the exceptional phenomenon that, due to a subtle balance between volumetric enthalpy and interfacial free energy, the CS phase nucleates via crystalline cubic nuclei rather than through spherical clusters, as the majority of crystal solids in nature. Finally, by examining growth beyond the nucleation stage, we uncover a series of alternating one-phase and two-phase crystallization mechanisms depending on whether or not the same phase that nucleates keeps growing. Taken together, we show that an octahedral distribution of attractive sites in colloidal particles results in an extremely rich crystallization landscape where subtle differences in pressure crucially determine the crystallizing polymorph. [ABSTRACT FROM AUTHOR]

Self-assembly of Zn(NO3)2 with tris(2-(isoquinolin-5-yloxy)ethyl)amine (L) as a C3-symmetric tridentate N-donor in a mixture of dioxane and acetonitrile gives rise to [NO3@Zn3(NO3)5L2]·2CH3CN in the form of crystals of sandwich-shaped cages encapsulating a nitrate, whereas the same self-assembly reaction in a different mixture, benzene and ethanol, produces [Zn(NO3)L(H2O)]NO3·H2O in the form of crystals of 3D networks with cml {4,62}2{42,610,83} topology. The most interesting feature is the transformation of [NO3@Zn3(NO3)5L2]·2CH3CN crystals into [Zn(NO3)L(H2O)]NO3·H2O crystals in ethanol. A significant difference in heterogeneous transesterification catalysis between the two species is observed. On the other hand, self-assembly of Co(NO3)2 with L gives rise to 3D networks, [Co(NO3)L(H2O)]NO3·H2O, whereas self-assembly of Ni(NO3)2 and Cu(NO3)2 with L produces sandwich-type cages, [NO3@Ni3(NO3)3L2(H2O)6]2NO3·C2H5OH·C6H6 and [NO3@Cu3(NO3)5L2(C2H5OH)]·C2H5OH·2C6H6, respectively, with the latter notably showing heterogeneous catechol oxidation catalytic effects. [ABSTRACT FROM AUTHOR]

Tuning the lattice spacing or stop bands holds great significance in the design and application of materials with colloidal crystals. Typically, particle surface modifications or the application of external physical fields are needed. In this study, we demonstrated the ability to expand or compress the lattice of colloidal crystals simply by utilizing a salt solution, without the need for any special treatments to the colloidal particles. We found that by only considering the diffusiophoresis effect we cannot explain the reversion of lattice expansion to lattice compression with the increase in the salt concentration and that the diffusioosmotic flow originating from the container wall must be taken into account. Further analysis revealed that variations in the salt concentration altered the relative amplitudes between diffusiophoresis and diffusioosmosis through changing the zeta potentials of the particles and the wall, and the competition between the particle diffusiophoresis and wall diffusioosmosis lay at the center of the underlying mechanism. [ABSTRACT FROM AUTHOR]

Existing strategies designed to produce ordered arrangements of colloidal particles on solid supports are of great interest for their wide range of applications, from colloidal lithography, plasmonic and biomimetic surfaces to tags for anti‐counterfeiting, but they all share various degrees of complexity hampering their facile implementation. Here, a drastically simplified methodology is presented to achieve ordered particle deposition, consisting in adding micromolar amounts of cationic surfactant to a colloidal suspension drop and let it evaporate in an upside‐down configuration. Confinement at the air/water interface enables particle assembly into monolayers, which are then transferred on the substrate producing highly ordered structures displaying vivid, orientation‐dependent structural colors. The method is compatible with many particle types and substrates, while controlling system parameters allows tuning the deposit size and morphology, from monocrystals to polycrystalline disks and "irises", from single‐component to crystal alloys with Moiré patterns, demonstrating its practicality for a variety of processes. [ABSTRACT FROM AUTHOR]

[Display omitted] Hetero-aggregation of oppositely charged colloidal particles with controlled architectural and interactional asymmetry allows modifying gel nanostructure and properties. We hypothesize the relative size ratio between cationic nanospheres and varied-size anionic two-dimensional nanoclays will influence the gel formation mechanisms and resulting rheological performance. Hybrid colloidal gels formed via hetero-aggregation of cationic gelatin nanospheres (∼400 nm diameter) and five types of nanoclays with similar 1 nm thickness but different lateral sizes ranging from ∼ 30 nm to ∼ 3000 nm. Structure-property relationships were elucidated using a suite of techniques. Microscopy and scattering probed gel nanostructure and particle configuration. Rheology quantified linear and non-linear viscoelastic properties and yielding behavior. Birefringence and polarized imaging assessed size-dependent nanoclay alignment during shear flow. Nanoclay size ratio relative to nanospheres affected the gelation process, network structure, elasticity, yielding, and shear response. Gels with comparably sized components showed maximum elasticity, while yield stress depended on nanoclay rotational mobility. Shear-induced nanoclay alignment was quantified by birefringence, which is more pronounced for larger nanoclay. Varying nanoclay size and interactions with nanospheres controlled dispersion, aggregation, and nematic ordering. These findings indicate that architectural and interactional asymmetry enables more control over gel properties through controlled assembly of anisotropic building blocks. [ABSTRACT FROM AUTHOR]

Electrostatic forces in solutions are highly relevant to a variety of fields, ranging from electrochemical energy storage to biology. However, their manifestation in concentrated electrolytes is not fully understood, as exemplified by counterintuitive observations of colloidal stability and long-ranged repulsions in molten salts. Highly charged biomolecules, such as DNA, respond sensitively to ions in dilute solutions. Here, we use non-base-pairing DNA-coated nanoparticles (DNA-NP) to analyze electrostatic interactions in concentrated salt solutions. Despite their negative charge, these conjugates form colloidal crystals in solutions of sufficient divalent cation concentration. We utilize small-angle X-ray scattering (SAXS) to study such DNA-NP assemblies across the full accessible concentration ranges of aqueous CaCl2, MgCl2, and SrCl2 solutions. SAXS shows that the crystallinity and phases of the assembled structures vary with cation type. For all tested salts, the aggregates contract with added ions at low salinities and then begin expanding above a cation-dependent threshold salt concentration. Wide-angle X-ray scattering (WAXS) reveals enhanced positional correlations between ions in the solution at high salt concentrations. Complementary molecular dynamics simulations show that these ion-ion interactions reduce the favorability of dense ion configurations within the DNA brushes below that of the bulk solution. Measurements in solutions with lowered permittivity demonstrate a simultaneous increase in ion coupling and decrease in the concentration at which aggregate expansion begins, thus confirming the connection between these phenomena. Our work demonstrates that interactions between charged objects continue to evolve considerably into the high-concentration regime, where classical theories project electrostatics to be of negligible consequence. [ABSTRACT FROM AUTHOR]

The fabrication of high quality nanophotonic surfaces for integration in optoelectronic devices remains a challenge because of the complexity and cost of top–down nanofabrication strategies. Combining colloidal synthesis with templated self‐assembly emerged as an appealing low‐cost solution. However, it still faces several obstacles before integration in devices can become a reality. This is mostly due to the difficulty in assembling small nanoparticles (<50 nm) in complex nanopatterns with a high yield. In this study, a reliable methodology is proposed to fabricate printable nanopatterns with an aspect ratio varying from 1 to 10 and a lateral resolution of 30 nm via nanocube assembly and epitaxy. Investigating templated assembly via capillary forces, a new regime was identified that was used to assemble 30–40 nm nanocubes in a patterned polydimethylsiloxane template with a high yield for both Au and Ag with multiple particles per trap. This new method relies on the generation and control of an accumulation zone at the contact line that is thin as opposed to dense, displaying higher versatility. This is in contrast with conventional wisdom, identifying a dense accumulation zone as a requirement for high‐yield assembly. In addition, different formulations are proposed that can be used for the colloidal dispersion, showing that the standard water‐surfactant solutions can be replaced by surfactant‐free ethanol solutions, with good assembly yield. This allows to minimize the presence of surfactants that can affect electronic properties. Finally, it is shown that the obtained nanocube arrays can be transformed into continuous monocrystalline nanopatterns via nanocube epitaxy at near ambient temperature, and transferred to different substrates via contact printing. This approach opens new doors to the templated assembly of small colloids and could find potential applications in various optoelectronic devices ranging from solar cells to light‐emitting diodes and displays. [ABSTRACT FROM AUTHOR]

The review summarizes our recent reports on brightly‐emitting materials with varied dimensionality (3D, 2D, 0D) synthesized using "green" chemistry and exhibiting highly efficient photoluminescence (PL) originating from self‐trapped exciton (STE) states. The discussion starts with 0D emitters, in particular, ternary indium‐based colloidal quantum dots, continues with 2D materials, focusing on single‐layer polyheptazine carbon nitride, and further evolves to 3D luminophores, the latter exemplified by lead‐free double halide perovskites. The review shows the broadband STE PL to be an inherent feature of many materials produced in mild conditions by "green" chemistry, outlining PL features general for these STE emitters and differences in their photophysical properties. The review is concluded with an outlook on the challenges in the field of STE PL emission and the most promising venues for future research. [ABSTRACT FROM AUTHOR]

Although droplet microfluidics has been studied for the past two decades, its applications are still limited due to the low productivity of microdroplets resulting from the low integration of planar microchannel structures. In this study, a microfluidic system implementing inverse colloidal crystals (ICCs), a spongious matrix with regularly and densely formed three-dimensional (3D) interconnected micropores, was developed to significantly increase the throughput of microdroplet generation. A new bottom-up microfabrication technique was developed to seamlessly integrate the ICCs into planar microchannels by accumulating non-crosslinked spherical PMMA microparticles as sacrificial porogens in a selective area of a mold and later dissolving them. We have demonstrated that the densely arranged micropores on the spongious ICC of the microchannel function as massively parallel micronozzles, enabling droplet formation on the order of >10 kHz. Droplet size could be adjusted by flow conditions, fluid properties, and micropore size, and biopolymer particles composed of polysaccharides and proteins were produced. By further parallelization of the unit structures, droplet formation on the order of >100 kHz was achieved. The presented approach is an upgrade of the existing droplet microfluidics concept, not only in terms of its high throughput, but also in terms of ease of fabrication and operation. [ABSTRACT FROM AUTHOR]

Generating space-filling arrangements of most discrete polyhedra nanostructures of the same shape is not possible. However, if the appropriate individual building blocks are selected (e.g., cubes), or multiple shapes of the appropriate dimensions are matched (e.g., octahedra and tetrahedra) and their pairing interactions are subsequently forced, space-filled architectures may be possible. With flexible molecular ligands (polyethylene glycol-modified DNA), the shape of a polyhedral nanoparticle can be deliberately altered and used to realize geometries that favor space tessellation. In this work, 10 new colloidal crystals were synthesized from DNA-modified nanocrystal building blocks that differed in shapes and sizes, designed to form space-filling architectures with micron-scale dimensions. The insights and capabilities provided by this new strategy substantially expand the scope of colloidal crystals possible and provide an expanded tool kit for researchers interested in designing metamaterials. [ABSTRACT FROM AUTHOR]

The crystal growth and orientation of two‐dimensional (2D) perovskite films significantly impact solar cell performance. Here, we incorporated robust quadrupole‐quadrupole interactions to govern the crystal growth of 2D Ruddlesden–Popper (RP) perovskites. This was achieved through the development of two unique semiconductor spacers, namely PTMA and 5FPTMA, with different dipole moments. The ((5FPTMA)0.1(PTMA)0.9)2MAn−1PbnI3n+1 (nominal n=5, 5F/PTMA−Pb) film shows a preferred vertical orientation, reduced grain boundaries, and released residual strain compared to (PTMA)2MAn−1PbnI3n+1 (nominal n=5, PTMA−Pb), resulting in a decreased exciton binding energy and reduced electron‐phonon coupling coefficients. In contrast to PTMA−Pb device with an efficiency of 15.66 %, the 5F/PTMA−Pb device achieved a champion efficiency of 18.56 %, making it among the best efficiency for 2D RP perovskite solar cells employing an MA‐based semiconductor spacer. This work offers significant insights into comprehending the crystal growth process of 2D RP perovskite films through the utilization of quadrupole‐quadrupole interactions between semiconductor spacers. [ABSTRACT FROM AUTHOR]

Layered 2D perovskites are solution‐processed quantum‐wells. Their effective band‐gap is determined via the inorganic perovskite layer thickness and exciton quantum confinement effects. Alternatively, by changing the organic moieties, one can tune the dielectric constant and distance between the monolayers modifying the excitonic interactions. In colloidal perovskites, a dynamic equilibrium exists between the free organic moieties in the solution and the surface of the nanocrystal. Colloidal synthesis is used to make single monolayer L2PbBr4 platelets and assemble these into layered 2D stacks. In the experiment, L is an alkylamine surface ligand whose length (4‐18 carbons) determines the interlayer distances between the quantum‐wells. The dynamic equilibrium of ligand mixtures in solution and perovskite surfaces leads to optimal mixing of the molecules. During the self‐assembly of monolayers, the distance between the inorganic layers is thus engineered. The interlayer distance is proportional to the average ligand mixture length. This results in controlled interactions between the 2D‐excitons, enabling red‐shifted absorption and emission and extended lifetimes for longer alkyl chains. Using entropic mixing of ligands for the engineering of 2D excitonic interactions is therefore demonstrated. Formation of layered 2D perovskites from colloidal building blocks allows intermixing of dissimilar materials opening possibilities for new heterostructures and junctions. [ABSTRACT FROM AUTHOR]

Grain rotation is commonly observed during the evolution of microstructures in polycrystalline materials of different kinds, including metals, ceramics, and colloidal crystals. It is widely accepted that interface migration in these systems is mediated by the motion of line defects with step and dislocation character, i.e., disconnections. We propose a crystallography-respecting continuum model for arbitrarily curved grain boundaries or heterophase interfaces, accounting for the disconnections' role in grain rotation. Numerical simulations demonstrate that changes in grain orientations, as well as interface morphology and internal stress field, are associated with disconnection flow. Our predictions agree with molecular dynamics simulation results for pure capillarity-driven evolution of grain boundaries and are interpreted through an extended Cahn-Taylor model. [ABSTRACT FROM AUTHOR]

In situ preparation of bifunctional thiazolo[5,4‐d]thiazole (TTz)‐based fluorophore cross‐linked nanofibers is successfully performed. These multifunctional nanofibers are used as both crystal growth template and antibacterial substrate that makes bacterial detection possible simultaneously. These highly fluorescent nanofibers act as optical sensors toward many analytes. The acid, base, and metal cation‐sensitive nature of the 2,5‐bis(4‐hydroxyphenyl)thiazolo[5,4‐d]thiazole (HPhTT) dye makes the prepared PVA nanofibers sensitive against these chemicals. Metal nanoparticles (MNPs) or metal oxide crystal formation occurs on the surface of nanofibers without any reducing agent. The strong interaction between metal cations and fluorophores results in crystal formation on the surface, which is named for the first time as "complexation‐triggered crystalization." These dye cross‐linked and metal‐interacted nanofibers exhibit antibacterial effect against E. coli (ATCC 25922), S. aureus (ATCC 25923), P. aeruginosa (ATCC 27853), and E. faecalis (ATCC 25922) strains. Also, the emission wavelength change of nanofibers in bacterial contamination makes it possible to use smart nanofiber films for optical bacteria detection. These novel materials pave the way for new applications such as smart wound bands, optical sensors, and one‐step preparation of surface‐enhanced Raman spectroscopy substrate. [ABSTRACT FROM AUTHOR]