Colloidal Molecules Research Articles

Spontaneous Formation of π-Conjugated Polymeric Colloidal Molecules Through Stepwise Coacervation and Symmetric Compartmentalization.

Coacervation, the phase separation of liquid induced by polymeric solutes, sometimes results in the formation of oligomeric clusters of droplets. The morphology of the clusters is non-uniform because the clustering is a consequence of the random collisions of the drifting droplets. Herewereportdistinctively organized coacervation, yielding colloidal molecules with monodisperse size, morphological symmetry, and compositional heterogeneity.Weinvestigate the coacervation of a mixture of two types of synthetic polymers and find that one of the polymers coacervates first and serves as a core droplet, on which the other polymer coacervates subsequently to form satellite droplets. The satellite droplets arrange themselves symmetrically around the core and solidify without losing the morphology. The number of satellites and their symmetry are modulable depending on the chemical affinity and the diameter of the droplets. This finding highlights the capability of coacervation as a non-templated and non-covalent pathway to form aspherical colloidal materials with structural and functional complexity.

Impact of non-reciprocal interactions on colloidal self-assembly with tunable anisotropy.

Non-reciprocal (NR) effective interactions violating Newton's third law occur in many biological systems, but can also be engineered in synthetic, colloidal systems. Recent research has shown that such NR interactions can have tremendous effects on the overall collective behavior and pattern formation, but can also influence aggregation processes on the particle scale. Here, we focus on the impact of non-reciprocity on the self-assembly of a colloidal system (originally passive) with anisotropic interactions whose character is tunable by external fields. In the absence of non-reciprocity, that is, under equilibrium conditions, the colloids form square-like and hexagonal aggregates with extremely long lifetimes yet no large-scale phase separation [Kogler et al., Soft Matter 11, 7356 (2015)], indicating kinetic trapping. Here, we study, based on Brownian dynamics simulations in 2D, an NR version of this model consisting of two species with reciprocal isotropic, but NR anisotropic interactions. We find that NR induces an effective propulsion of particle pairs and small aggregates ("active colloidal molecules") forming at the initial stages of self-assembly, an indication of the NR-induced non-equilibrium. The shape and stability of these initial clusters strongly depend on the degree of anisotropy. At longer times, we find, for weak NR interactions, large (even system-spanning) clusters where single particles can escape and enter at the boundaries, in stark contrast to the small rigid aggregates appearing at the same time in the passive case. In this sense, weak NR shortcuts the aggregation. Increasing the degree of NR (and thus, propulsion), we even observe large-scale phase separation if the interactions are weakly anisotropic. In contrast, systems with strong NR and anisotropy remain essentially disordered. Overall, the NR interactions are shown to destabilize the rigid aggregates interrupting self-assembly and phase separation in the passive case, thereby helping the system to overcome kinetic barriers.

Rigid flocks, undulatory gaits, and chiral foldamers in a chemically active polymer

Active matter systems—such as a collection of active colloidal particles—operate far from equilibrium with complex inter-particle interactions that govern their collective dynamics. Predicting the collective dynamics of such systems may aid the design of self-shaping structures comprised of active colloidal units with a prescribed dynamical function. Here, using simulations and theory, we study the collective dynamics of a chain consisting of active Brownian particles with internal interactions via trail-mediated chemicals, connected by harmonic springs in two dimensions to obtain design principles for active colloidal molecules. We show that two-dimensional confinement and chemo-repulsive interactions between the freely-jointed particles lead to an emergent rigidity of the chain in the steady-state dynamics. In the chemo-attractive regime, the chain collapses into crystals that abruptly halt their motion. Further, in a chain consisting of a binary mixture of monomers, we show that non-reciprocal chemical affinities between distinct species give rise to novel phenomena, such as chiral molecules with tunable dynamics, sustained undulatory gaits and reversal of the direction of motion. Our results suggest a novel interpretation of the role of trail-mediated interactions, in addition to providing active self-assembly principles arising due to non-reciprocal interactions.

Engineering the Electrostatic Interactions between Oppositely Charged Polymer-Grafted Nanoparticles for Constructing Colloid Molecules on Substrates.

Arrays of nanoparticle (NP) clusters with controlled architectures show broad applications in nanolasers, sensors, and photocatalysis, but the fabrication of these arrays on substrates remains a grand challenge. This review presents a highly effective polymer-based strategy for the process-directed self-assembly of binary polyelectrolyte-grafted NPs (PGNPs) bearing opposite charges into stable colloidal molecules (CMs) on substrates via electrostatic interactions. The coordination number (x) of ABx CMs can be tuned by adjusting the pH or ionic strength of the solution or by employing different combinations of PGNPs with varying charge densities. Large-area CMs with diverse structures ranging from AB to AB7 can be constructed on substrates in high yields. This approach is applicable to PGNPs with different cores of NPs. This assembly strategy offers a useful tool for the fabrication of structurally precise assemblies on substrates with broad applications.

Mechanisms for electric field induced color change in coupled colloidal quantum dot molecules revealed by low temperatures single particle spectroscopy

Mechanisms for electric field induced color change in coupled colloidal quantum dot molecules revealed by low temperatures single particle spectroscopy

The Valence-Dependent Activity of Colloidal Molecules as Ice Recrystallization Inhibitors.

Inspired by advances in cryopreservation techniques, which are essential for modern biomedical applications, there is a special interest in the ice recrystallization inhibition (IRI) of the antifreeze protein (AFPs) mimics. There are in-depth studies on synthetic materials mimicking AFPs, from simple molecular structure levels to complex self-assemblies. Herein, we report the valence-dependent IRI activity of colloidal organic molecules (CMs). The CMs were prepared through polymerization-induced particle-assembly (PIPA) of the ABC-type triblock terpolymer of poly(acryloxyethyl trimethylammonium chloride)-b-poly(benzyl acrylate)-b-poly(diacetone acrylamide) (PATAC-b-PBzA-b-PDAAM) at high monomer conversions. Stabilized by the cationic block of PATAC, the strong intermolecular H-bonding and incompatibility of the PDAAM block with PBzA contributed to the in situ formation of Janus particles (AX1) beyond the initial spherical seed particles (AX0), as well as the high valency clusters of linear AX2 and trigonal AX3. Their distribution was controlled mainly by the polymerization degrees (DPs) of PATAC and PDAAM blocks. IRI activity results of the CMs suggest that the higher fraction of AX1 results in the better IRI activity. Increasing the fraction of AX1 from 27% to 65% led to a decrease of the mean grain size from 39.8% to 10.9% and a depressed growth rate of ice crystals by 58%. Moreover, by replacing the PDAAM block with the temperature-responsive one of poly(N-isopropylacrylamide) (PNIPAM), temperature-adjustable IRI activity was observed, which is well related to the reversible transition of AX0 to AX1, providing a new idea for the molecular design of amphiphilic polymer nanoparticle-based IRI activity materials.

Symmetry-Breaking of Nanoparticle Surface Function Via Conformal DNA Design.

Asymmetric surface functionalization of complex nanoparticles to control their directional self-assembly remains a considerable challenge. Here, we demonstrated a conformal DNA design strategy for flexible remodeling of the surface of complex nanoparticles, taking Au nanobipyramids (AuNBPs) as a model. We sheathed one or both tips of AuNBPs into conformal DNA origami with an exceptionally accurate orientation control. Such asymmetrically and symmetrically distributed surface patches possess regioselective, sequence, and site-specific DNA binding capabilities. As a result, we realized a series of prototypical multicomponent "colloidal molecules" made of AuNBPs and Au nanospheres (AuNSs) with defined directionality and number of "bonding valence" as well as 1D and 3D hierarchical assemblies, e.g., inverse core-satellites of AuNBPs and AuNSs, side-by-side and tip-to-tip linear assemblies of AuNBPs, and 3D helical superstructures of AuNBPs with tunable twists. These findings inspire new opportunities for nanoparticle surface engineering and the high-order self-assembly of nanoarchitectures with higher complexity and broadened functionalities.

Engineering colloidal crystals molecule by molecule.

DNA particles are programmed to assemble with precision into complex lattices.

Programmable Colloids with Analogous Hypercoordination Complex Architectures.

Colloidal molecule clusters (CMCs) are promising building blocks with molecule-like symmetry, offering exceptional synergistic properties for applications in plasmonics and catalysis. Traditional CMC fabrication has been limited to simple molecule-like structures utilizing isotropic particles. Here, we employ molecular dynamics simulation to investigate the co-assembly of anisotropic nanorods (NRs) and the stimulus-responsive polymer (SRP) via reversible adsorption. The results of the simulation show that it is possible to fabricate hypercoordination complex structures with high symmetry from the co-assembly of NRs and the SRP, even in analogy to the Th(BH4)4 structure. The coordination number of these CMCs can be precisely programmed by adjusting the shape and size of the ends of the NRs and the SRP cohesion energy. Furthermore, a finite-difference time-domain simulation indicates these hypercoordination structures exhibit significantly enhanced optical activity and plasmonic coupling effects. These findings introduce a new design approach for complex molecule-like structures utilizing anisotropic nanoparticles and may expand the applications of CMCs in photonics.

Synthesis of patchy colloids with different chemical functionalities

Patchy particles are one of the new frontiers in developing novel functional colloids because of their similarity to molecules in terms of their potential ability to form directional bonds and give rise to complex architecture via self-assembly. Considerable challenges remain in developing effective strategies for synthesizing such complex particles. Most current works have focused on controlling the position of patches, which is already tricky. Still, very few works have tackled the problem of preparing particles with patches bearing different functionalities. In this work, we used an activated swelling method developed in our group to prepare Janus polymer particles with variable Janus balance and used them to synthesize bi-patchy particles with different chemical functionalities. We first created polystyrene/polymethyl methacrylate-glycidyl methacrylate (PS/P(MMA-GMA)) Janus particles with a small methacrylate patch. The epoxy groups were then aminated (PS/P-NH2), leading to a change in the hydrophilicity of the patch. We then used two methods to create patchy particles. In the first case, we mixed unmodified PS/P(MMA-GMA) and PS/P-NH2 Janus particles and fused them by adding THF as a plasticizer. This led to the formation of bi-patchy particles with identical patches and two patches bearing different functionalities, as proved by fluorescence microscopy. In the second case, PS/P-NH2 particles were used as seeds for an additional activated swelling polymerization step with MMA as a monomer to obtain pure bi-patchy particles with differently functionalized patches. This was possible thanks to the incompatibility between the NH2-functionalized first patch and the pure PMMA of the second one. The work opens the path to preparing colloidal molecules capable of forming multiple directional bonds through orthogonal chemical functionalization.

Reconfigurable Assembly of Planar Colloidal Molecules via Chemical Reaction and Electric Polarization.

Colloidal molecules, ordered structures assembled from micro- and nanoparticles, serve as a valuable model for understanding the behavior of real molecules and for constructing materials with tunable properties. In this work, we introduce a universal strategy for assembling colloidal molecules consisting of a central active particle surrounded by several passive particles as ligands. During the assembly process, active particles attract the surrounding passive particles through phoresis and osmosis resulting from the chemical reactions on the surface of the active particles, while passive particles repel each other due to the electric polarization induced by an alternating current (AC) electric field. By carefully selecting particles of varying structures and sizes, we have assembled colloidal molecules of symmetric and asymmetric dimers, trimers, and multimers. Furthermore, the coordination number of these colloidal molecules can be regulated in real time and insitu by tuning the interaction forces between the constituent particles. Brownian dynamics simulations reproduced the formation of the colloidal molecules and validated that the self-assembly arises from chemically induced attraction and electrical dipolar repulsion. This strategy for reconfigurable colloidal assemblies poses the potential for designing adaptive micro-nanomachines.

Molecular size variations of chromophoric dissolved organic matter (CDOM) along a salinity gradient in the Changjiang River estuary

Molecular size is a critical parameter for characterizing dissolved organic matter in aquatic systems. Four cruises were conducted in October 2018, March 2019, July 2019 (with a normal flood), and August 2020 (with an extreme flood), along a transect from the Changjiang (Yangtze) River freshwater to the shelf area with salinities near or > 30. During each cruise surface water samples at 5–6 stations were collected along the salinity gradient, and absorption spectra (to quantify and qualify chromophoric dissolved organic matter (CDOM)) were measured. In addition, ultrafiltration was conducted so that the size partitions including four factions of <1 kDa, 1–3 kDa, 3–10 kDa and 10 kDa–0.2 μm were obtained. In the different seasons, CDOM molecular sizes always showed decreasing trends from land to sea, which was consistent to most estuaries worldwide. In the freshwaters, those with sizes >1 kDa generally contributed 20%–40% of the bulk CDOM in different seasons, but these large colloidal molecules always disappeared at the offshore stations. The extreme flood in August 2020 brought more waters with lower salinity and higher CDOM concentration into the transects, and the extra CDOM materials were generally of larger molecular sizes. In addition to suspended particulate matter (SPM) resuspension, the flocculation of organic matter could also be another important reason for localised increased CDOM molecular size near the river mouth.

Innenrücktitelbild: Photo‐Induced Self‐assembly of Copolymer‐Capped Nanoparticles into Colloidal Molecules (Angew. Chem. 1/2024)

Innenrücktitelbild: Photo‐Induced Self‐assembly of Copolymer‐Capped Nanoparticles into Colloidal Molecules (Angew. Chem. 1/2024)

Inside Back Cover: Photo‐Induced Self‐assembly of Copolymer‐Capped Nanoparticles into Colloidal Molecules (Angew. Chem. Int. Ed. 1/2024)

Inside Back Cover: Photo‐Induced Self‐assembly of Copolymer‐Capped Nanoparticles into Colloidal Molecules (Angew. Chem. Int. Ed. 1/2024)

Colloidal Self‐Assembly: From Passive to Active Systems

AbstractSelf‐assembly fundamentally implies the organization of small sub‐units into large structures or patterns without the intervention of specific local interactions. This process is commonly observed in nature, occurring at various scales ranging from atomic/molecular assembly to the formation of complex biological structures. Colloidal particles may serve as micrometer‐scale surrogates for studying assembly, particularly for the poorly understood kinetic and dynamic processes at the atomic scale. Recent advances in colloidal self‐assembly have enabled the programmable creation of novel materials with tailored properties. We here provide an overview and comparison of both passive and active colloidal self‐assembly, with a discussion on the energy landscape and interactions governing both types. In the realm of passive colloidal assembly, many impressive and important structures have been realized, including colloidal molecules, one‐dimensional chains, two‐dimensional lattices, and three‐dimensional crystals. In contrast, active colloidal self‐assembly, driven by optical, electric, chemical, or other fields, involves more intricate dynamic processes, offering more flexibility and potential new applications. A comparative analysis underscores the critical distinctions between passive and active colloidal assemblies, highlighting the unique collective behaviors emerging in active systems. These behaviors encompass collective motion, motility‐induced phase segregation, and exotic properties arising from out‐of‐equilibrium thermodynamics. Through this comparison, we aim to identify the future opportunities in active assembly research, which may suggest new application domains.

Colloidal Self-Assembly: From Passive to Active Systems.

Self-assembly fundamentally implies the organization of small sub-units into large structures or patterns without the intervention of specific local interactions. This process is commonly observed in nature, occurring at various scales ranging from atomic/molecular assembly to the formation of complex biological structures. Colloidal particles may serve as micrometer-scale surrogates for studying assembly, particularly for the poorly understood kinetic and dynamic processes at the atomic scale. Recent advances in colloidal self-assembly have enabled the programmable creation of novel materials with tailored properties. We here provide an overview and comparison of both passive and active colloidal self-assembly, with a discussion on the energy landscape and interactions governing both types. In the realm of passive colloidal assembly, many impressive and important structures have been realized, including colloidal molecules, one-dimensional chains, two-dimensional lattices, and three-dimensional crystals. In contrast, active colloidal self-assembly, driven by optical, electric, chemical, or other fields, involves more intricate dynamic processes, offering more flexibility and potential new applications. A comparative analysis underscores the critical distinctions between passive and active colloidal assemblies, highlighting the unique collective behaviors emerging in active systems. These behaviors encompass collective motion, motility-induced phase segregation, and exotic properties arising from out-of-equilibrium thermodynamics. Through this comparison, we aim to identify the future opportunities in active assembly research, which may suggest new application domains.

The Effect of Monomer Size on Fusion and Coupling in Colloidal Quantum Dot Molecules.

The fusion step in the formation of colloidal quantum dot molecules, constructed from two core/shell quantum dots, dictates the coupling strength and hence their properties and enriched functionalities compared to monomers. Herein, studying the monomer size effect on fusion and coupling, we observe a linear relation of the fusion temperature with the inverse nanocrystal radius. This trend, similar to that in nanocrystal melting, emphasizes the role of the surface energy. The suggested fusion mechanism involves intraparticle ripening where atoms diffuse to the reactive connecting neck region. Moreover, the effect of monomer size and neck filling on the degree of electronic coupling is studied by combined atomistic-pseudopotential calculations and optical measurements, uncovering strong coupling effects in small QD dimers, leading to significant optical changes. Understanding and controlling the fusion and hence coupling effect allows tailoring the optical properties of these nanoscale structures, with potential applications in photonic and quantum technologies.

Photo‐Induced Self‐assembly of Copolymer‐Capped Nanoparticles into Colloidal Molecules

AbstractColloidal molecules (CMs) are precisely defined assemblies of nanoparticles (NPs) that mimic the structure of real molecules, but externally programming the precise self‐assembly of CMs is still challenging. In this work, we show that the photo‐induced self‐assembly of complementary copolymer‐capped binary NPs can be precisely controlled to form clustered ABx or linear (AB)y CMs at high yield (x is the coordination number of NP‐Bs, and y is the repeating unit number of AB clusters). Under UV light irradiation, photolabile p‐methoxyphenacyl groups of copolymers on NP‐A*s are converted to carboxyl groups (NP‐A), which react with tertiary amines of copolymers on NP‐B to trigger the directional NP bonding. The x value of ABx can be precisely controlled between 1 and 3 by varying the irradiation duration and hence the amount of carboxyl groups generated on NP‐As. Moreover, when NP‐A* and NP‐B are irradiated after mixing, the assembly process generates AB clusters or linear (AB)y structures with alternating sequence of the binary NPs. This assembly approach offers a simple yet non‐invasive way to externally regulate the formation of various CMs on demand without the need of redesigning the surface chemistry of NPs for use in drug delivery, diagnostics, optoelectronics, and plasmonic devices.

Photo-Induced Self-assembly of Copolymer-Capped Nanoparticles into Colloidal Molecules.

Colloidal molecules (CMs) are precisely defined assemblies of nanoparticles (NPs) that mimic the structure of real molecules, but externally programming the precise self-assembly of CMs is still challenging. In this work, we show that the photo-induced self-assembly of complementary copolymer-capped binary NPs can be precisely controlled to form clustered ABx or linear (AB)y CMs at high yield (x is the coordination number of NP-Bs, and y is the repeating unit number of AB clusters). Under UV light irradiation, photolabile p-methoxyphenacyl groups of copolymers on NP-A*s are converted to carboxyl groups (NP-A), which react with tertiary amines of copolymers on NP-B to trigger the directional NP bonding. The x value of ABx can be precisely controlled between 1 and 3 by varying the irradiation duration and hence the amount of carboxyl groups generated on NP-As. Moreover, when NP-A* and NP-B are irradiated after mixing, the assembly process generates AB clusters or linear (AB)y structures with alternating sequence of the binary NPs. This assembly approach offers a simple yet non-invasive way to externally regulate the formation of various CMs on demand without the need of redesigning the surface chemistry of NPs for use in drug delivery, diagnostics, optoelectronics, and plasmonic devices.

Theoretical Investigation on the Metamaterials Based on the Magnetic Template-Assisted Self-Assembly of Magnetic-Plasmonic Nanoparticles for Adjustable Photonic Responses.

The assembly of artificial nano- or microstructured materials with tunable functionalities and structures, mimicking nature's complexity, holds great potential for numerous novel applications. Despite remarkable progress in synthesizing colloidal molecules with diverse functionalities, most current methods, such as the capillarity-assisted particle assembly method, the ionic assembly method based on ionic interactions, or the field-directed assembly strategy based on dipole-dipole interactions, are confined to focusing on achieving symmetrical molecules. But there have been few examples of fabricating asymmetrical colloidal molecules that could exhibit unprecedented optical properties. Here, we introduce a microfluidic and magnetic template-assisted self-assembly protocol that relies mainly on the magnetic dipole-dipole interactions between magnetized magnetic-plasmonic nanoparticles and the mechanical constraints resulting from the specially designed traps. This novel strategy not only requires no specific chemistry but also enables magnetophoretic control of magnetic-plasmonic nanoparticles during the assembly process. Moreover, the assembled asymmetrical colloidal molecules also exhibit interesting hybridized plasmon modes and produce exotic optical properties due to the strong coupling of the individual nanoparticle. The ability to fabricate asymmetrical colloidal molecules based on the bottom-up method opens up a new direction for the fabrication of novel microscale structures for biosensing, patterning, and delivery applications.