Self-assembly Of Nanocrystals Research Articles

Oriented Linear Self-Assembly of Colloidal Nanocrystals through Regioselective Formation of Hydrogen-Bonded Supramolecular Bridges.

The linear assembly of nanocrystals (NCs) with orientational order presents a significant challenge in the field of colloidal assembly. This study presents an efficient strategy for assembling oleic acid (OAH)-capped, faceted rare earth NCs─such as nanorods, nanoplates, and nanodumbbells─into flexible chain-like superstructures. Remarkably, these NC chains exhibit a high degree of particle orientation even with an interparticle distance reaching up to 15 nm. Central to this oriented assembly method is the facet-selective adsorption of low-molecular-weight polyethylene glycol (PEG), such as PEG-400 (Mn = 400), onto specific facets of NCs. This regioselectivity is achieved by exploiting the lower binding affinity of OAH ligands on the (100) facets of rare earth NCs, enabling facet-specific ligand displacement and subsequent PEG attachment. By adjusting the solvent polarity, the linear assembly of NCs is induced by the solvophobic effect, which simultaneously promotes the formation of hydrogen-bonded PEG supramolecular bridges. These supramolecular bridges effectively connect NCs and exhibit sufficient robustness to maintain the structural integrity of the chains, despite the large interparticle spacing. Notably, even when coassembling different types of NCs, the resulting multicomponent chains still feature highly selective facet-to-facet connections. This work not only introduces a versatile method for fabricating well-aligned linear superstructures but also provides valuable insights into the fundamental principles governing the facet-selective assembly of NCs in solution.

Non-Volatile Memory Based on ZnO Thin-Film Transistor with Self-Assembled Au Nanocrystals.

Non-volatile memory based on thin-film transistor is crucial for system-on-panel and flexible electronic systems. Achieving high-performance and reliable thin-film transistor (TFT) memory still remains challenging. Here, for the first time, we present a ZnO TFT memory utilizing self-assembled Au nanocrystals with a low thermal budget, exhibiting excellent memory performance, including a program/erase window of 9.8 V, 29% charge loss extrapolated to 10 years, and remarkable endurance characteristics. Moreover, the memory exhibits favorable on-state characteristics with mobility, subthreshold swing, and current on-off ratio of 17.6 cm2V-1s-1, 0.71 V/dec, and 107, respectively. Our study shows that the fabricated TFT memory has great potential for practical applications.

Growth of Nanocrystal Superlattices from Liquid Crystals.

The growth of superlattices (SLs) made from self-assembled nanocrystals (NCs) is a powerful method for creating new materials and gaining insight into fundamental molecular dynamics. Previous explorations of NCSL syntheses have mostly compared them to crystallization. However, NCSL synthesis has not broadly shown cooling crystallization from saturated solutions as a reversible crystallization-dissolution process. We demonstrate the reversible growth of NCSLs by dispersing NCs in liquid crystal (LC) "smart solvents," and harnessing the transitions between the isotropic and nematic phases of the LCs. The growth mode and morphology can be tuned. This process is a model platform for studying crystallization and demonstrates great potential in manufacturing NCSLs as colloidal crystals through liquid-phase epitaxy or colloidal synthesis.

Iridescent transparent passive radiative cooling enabled by cellulose nanocrystal assemblies

Recently, passive daytime radiative cooling (PDRC) materials that reflect sunlight and transmit heat through atmospheric transparent windows to outer space without any energy consumption have attracted broad interest. However, most PDRC materials have the complicated structures, white or mirror-like appearance with poor transparency. Here, we reported a transparent iridescent PDRC coating material constructed by the evaporation-induced self-assembly (EISA) of cellulose nanocrystals (CNCs). The iridescent PDRC coating not only shows high light transparency (75 %) because the right-handed circularly polarized light can transmit the unique left-handed chiral nematic liquid crystal structure, but also shows high solar reflection efficiency (95.2 %) and infrared emission efficiency (96.5 %) that endows the coating with high radiative cooling efficiency (119 W/m2). More importantly, the PDRC coating can apply on polymethyl methacrylate (PMMA), polyethylene terephthalate (PET) film and textiles, and the substrate color has no negative impact for cooling. With the excellent radiative cooling efficiency, high transparency, facile preparation process and general applicability, the CNCs-based PDRC coating opens a new pathway toward the potential application of PDRC for environmental sustainability purpose.

Direct Synthesis of CuPd Icosahedra Supercrystals Studied by In Situ X-Ray Scattering.

Nanocrystal self-assembly into supercrystals provides a versatile platform for creating novel materials and devices with tailored properties. While common self-assembly strategies imply the use of purified nanoparticles after synthesis, conversion of chemical precursors directly into nanocrystals and then supercrystals in simple procedures has been rarely reported. Here, the nucleation and growth of CuPd icosahedra and their consecutive assembly into large closed-packed face-centered cubic (fcc) supercrystals are studied. To this end, the study simultaneously and in situ measures X-ray total scattering with pair distribution function analysis (TS-PDF) and small-angle X-ray scattering (SAXS). It is found that the supercrystals' formation is preceded by an intermediate dense phase of nanocrystals displaying short-range order (SRO). It is further shown that the organization of oleic acid/oleylamine surfactants into lamellar structures likely drives the emergence of the SRO phase and later of the supercrystals by reducing the volume accessible to particle diffusion. The supercrystals' formation as well as their disassembly are triggered by temperature. The study demonstrates that ordering of solvent molecules can be crucial in the direct synthesis of supercrystals. The study also provides a general approach to investigate novel preparation routes of supercrystals in situ and across several length scales via X-ray scattering.

In Situ X-ray Scattering Reveals Coarsening Rates of Superlattices Self-Assembled from Electrostatically Stabilized Metal Nanocrystals Depend Nonmonotonically on Driving Force.

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with promising functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases in situ and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small-angle X-ray scattering. By developing a quantitative model, we fit the time-dependent scattering patterns to obtain the phase diagram of the system and the kinetics of the colloidal and SL phases as a function of varying quench conditions. The extracted phase diagram is consistent with particles whose interactions are short in range relative to their diameter. We find the degree of SL order is primarily determined by fast (subsecond) initial nucleation and growth kinetics, while coarsening at later times depends nonmonotonically on the driving force for self-assembly. We validate these results by direct comparison with simulations and use them to suggest dynamic design principles to optimize the crystallinity within a finite time window. The combination of this measurement methodology, quantitative analysis, and simulation should be generalizable to elucidate and better control the microscopic self-assembly pathways of a wide range of bottom-up assembled systems and architectures.

Development of high-barrier composite films for sustainable reduction of non-biodegradable materials in food packaging application

Widely employed petroleum-based food packaging materials have inflicted irreparable harm on ecosystems, primarily stemming from their non-biodegradable attributes and recycling complexities. Inspired by natural nacre with a layered aragonite platelet/nanofiber/protein multi-structure, we prepared high-barrier composite films by self-assembly of cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), montmorillonite (MMT), polyvinyl alcohol (PVA) and alkyl ketene dimer (AKD). The composite films demonstrated outstanding barrier properties with oxygen vapor transmission of 0.193 g·mm·m−2·day−1 and water vapor transmission rates of 0.062 cm3·mm·m−2·day−1·0.1 MPa−1, which were significantly lower than those of most biomass-degradable packaging materials. Additionally, the impacts of mixing nanocellulose with various aspect ratios on the tensile strength and folding cycles of the films were examined. The exceptional resistance of the composite films to oil and water provides a novel and sustainable approach to reduce non-biodegradable plastic packaging.

Polyoxometalate Induced Assembly Into Surface Functionalized Multidimensional Heterostructures with Enhanced Catalytic Activity.

The self-assembly of inorganic nanocrystals offers an efficient way for the fabrication of functional materials. However, it is still challenging for the construction of multidimensional nanostructures with controllable shapes, compositions and functions. Here, a series of heterostructures in different dimensions by surface modification of polyoxometalate (POM) clusters is developed. Three kinds of POM clusters(phosphomolybdic acid (PMA), phosphotungstic acid (PTA) and silicotungstic acid (STA) and five kinds of metal oxides (TiO2 , VOx , La2 O3 , In2 O3 and Gd2 O3 ) can be used as building blocks, and a class of 1D, 2D and 3D heterostructures can be achieved by the control of surface ligand coverage. Compared with individual building blocks and other cluster-based superstructures, TiO2 -PMA superstructures exhibit enhanced catalytic activity toward thioether oxidations, which is attributed to the electron transfer between TiO2 and POM clusters.

Hepatic-Accumulated Obeticholic Acid and Atorvastatin Self-Assembled Nanocrystals Potentiate Ameliorative Effects in Treatment of Metabolic-Associated Fatty Liver Disease.

Exploration of medicines for efficient and safe management of metabolic-associated fatty liver disease (MAFLD) remains a challenge. Obeticholic acid (OCA), a selective farnesoid X receptor agonist, has been reported to ameliorate injury and inflammation in various liver diseases. However, its clinical application is mainly limited by poor solubility, low bioavailability, and potential side effects. Herein a hepatic-targeted nanodrugs composed of OCA and cholesterol-lowering atorvastatin (AHT) with an ideal active pharmaceutical ingredient (API) content for orally combined treatment of MAFLD is created. Such carrier-free nanocrystals (OCAHTs) are self-assembled, not only improving the stability in gastroenteric environments but also achieving hepatic accumulation through the bile acid transporter-mediated enterohepatic recycling process. Orally administrated OCAHT outperforms the simple combination of OCA and AHT in ameliorating of liver damage and inflammation in both acetaminophen-challenged mice and high-fat diet-induced MAFLD mice with less systematic toxicity. Importantly, OCAHT exerts profoundly reverse effects on MAFLD-associated molecular pathways, including impairing lipid metabolism, reducing inflammation, and enhancing the antioxidation response. This work not only provides a facile bile acid transporter-based strategy for hepatic-targeting drug delivery but also presents an efficient and safe full-API nanocrystal with which to facilitate the practical translation of nanomedicines against MAFLD.

3D WRITING OF MULTICELLULAR TENDON-ON-CNC-CHIP MODELS

Relevant in vitro models emulating tendinopathies are highly needed to study these diseases and develop better treatments. We have recently proposed a new strategy that allows the automated 3D writing of microphysiological systems (MPS) embedded into its own biomimetic fibrillar support platform based on the self-assembling of cellulose nanocrystals (CNCs). Here, we explored this CNC platform for writing humanized in vitro tendon models using tendon decellularized extracellular matrix (dECM)-based bioinks to closely recapitulate the biophysical and biochemical cues of tendon cell niche and self-induce the tenogenic differentiation of stem cells. The proposed concept was further explored to study the crosstalk between the tendon core and vascular compartment.Porcine flexor tendons were decellularized to produce the dECM bioink hydrogel. hASCs were used as cell source and the bioink was directly printed within the CNC fluid gel. Tendon constructs were co-printed with compartmentalized microvascular structures to evaluate the cellular crosstalk with endothelial cells. The tendon-on-chip models showed high cell viability and proliferation during culture up to 21 days, and the synergy between dECM cues and printed patterns induced anisotropic cell organization similar to tendon tissues. Gene and protein analysis showed upregulation of the most important tendon related markers on tendon constructs, demonstrating that the biophysical and biochemical cues of dECM induced hASCs commitment toward tenogenic phenotype. In co-culture system, chemotaxis induced endothelial cells migration toward the tendon compartment, but without significant infiltration. Gene and protein expression results suggest that the cellular crosstalk established in this MPS with endothelial cells boosted hASCs tenogenesis, emulating tendon development stages.Overall, the proposed system might be promising for the automated fabrication of organotypic tendon-on-chip models that will be a valuable new tool to study tendon physiology, pathology, or the effect of drugs for the treatment of tendinopathy.Acknowledgments: EU H2020 for ERC-2017-CoG-772817; ERC-PoC-BioCHIPs-101069302; FCT/MCTES for 2022.05526.PTDC, 2020.03410.CEECIND, and PD/BD/129403/2017

Large-scale production of chiral nematic microspheres.

The membrane emulsification technique enables the self-assembly of cellulose nanocrystals (CNCs) confined within a spherical geometry for large-scale production. The resulting solid microspheres show long-range ordering with chiral nematic structures, and this fascinating hierarchical architecture can even be transferred to mesoporous carbon or silica microparticles by a sacrificial template method.

Oriented Self-assembly of Flexible MOFs Nanocrystals into Anisotropic Superstructures with Homogeneous Hydrogels Behaviors.

Building of metal-organic frameworks (MOFs) homogeneous hydrogels made by spontaneous crystallization remains a significant challenge. Inspired by anisotropically structured materials in nature, an oriented super-assembly strategy to construct micro-scale MOFs superstructure is reported, in which the strong intermolecular interactions between zirconium-oxygen (Zr─O) cluster and glutamic acid are utilized to drive the self-assembly of flexible nanoribbons into pumpkin-like microspheres. The confined effect between water-flexible building blocks and crosslinked hydrogen networks of superstructures achieved a mismatch transformation of MOFs powders into homogeneous hydrogels. Importantly, the elastic and rigid properties of hydrogels can be simply controlled by precise modulation of coordination and self-assembly for anisotropic superstructure. Experimental results and theoretical calculations demonstrates that MOFs anisotropic superstructure exhibits dynamic double networks with a superior water harvesting capacity (119.73gg-1) accompanied with heavy metal removal (1331.67mgg-1) and strong mechanical strength (Young's modulus of 0.3GPa). The study highlights the unique possibility of tailoring MOFs superstructure with homogeneous hydrogel behavior for application in diverse fields.

Engineering Crystallinity Gradients for Tailored CaO2 Nanostructures: Enabling Alkalinity-Reinforced Anticancer Activity with Minimized Ca2+/H2O2 Production.

CaO2 nanoparticles (CNPs) can produce toxic Ca2+ and H2O2 under acidic pH, which accounts for their intrinsic anticancer activity but at the same time raises safety concerns upon systemic exposure. Simultaneously realizing minimized Ca2+/H2O2 production and enhanced anticancer activity poses a dilemma. Herein, we introduce a "crystallinity gradient-based selective etching" (CGSE) strategy, which is realized by creating a crystallinity gradient in a CNP formed by self-assembled nanocrystals. The nanocrystals distributed in the outer layer have a higher crystallinity and thus are chemically more robust than those distributed in the inner layer, which can be selectively etched. CGSE not only leads to CNPs with tailored single- and double-shell hollow structures and metal-doped compositions but more surprisingly enables significantly enhanced anticancer activity as well as tumor growth inhibition under limited Ca2+/H2O2 production, which is attributed to an alkalinity-reinforced lysosome-dependent cell death pathway.

Nanoparticle Size Influences the Self-Assembly of Gold Nanorods Using Flexible Streptavidin-Biotin Linkages.

The self-assembly of colloidal nanocrystals remains of robust interest due to its potential in creating hierarchical nanomaterials that have advanced function. For gold nanocrystals, junctions between nanoparticles yield large enhancements in local electric fields under resonant illumination, which is suitable for surface-enhanced spectroscopies for molecular sensors. Gold nanorods can provide such plasmonic fields at near-infrared wavelengths of light for longitudinal excitation. Through the use of careful concentration and stoichiometric control, a method is reported herein for selective biotinylation of the ends of gold nanorods for simple, consistent, and high-yielding self-assembly upon addition of the biotin-binding protein streptavidin. This method was applied to four different sized nanorods of similar aspect ratio and analyzed through UV-vis spectroscopy for qualitative confirmation of self-assembly and transmission electron microscopy to determine the degree of self-assembly in end-linked nanorods. The yield of end-linked assemblies approaches 90% for the largest nanorods and approaches 0% for the smallest nanorods. The number of nanorods linked in one chain also increases with an increased nanoparticle size. The results support the notion that the lower ligand density at the ends of the larger nanorods yields preferential substitution reactions at those ends and hence preferential end-to-end assembly, while the smallest nanorods have a relatively uniform ligand density across their surfaces, leading to spatially random substitution reactions.

Chiral Pearlescent Cellulose Nanocrystals Films with Broad-Range Tunable Optical Properties for Anti-Counterfeiting Applications.

Pearlescent materials are of technological importance in a diverse array of industries from cosmetics to premium paints; however, chiral pearlescent materials remain unexplored. Here, chiral pearlescent films with on-demand iridescence and metallic appearance are simply organized by leveraging vertical pressure to direct the self-assembly of cellulose nanocrystals. The films are formed with a bilayer planar anchored left-handed chiral nematic architecture, in which the bottom layer is featured with a vertical gradient pitch, and the top layer is featured with a uniform pitch. Simultaneous reflection of the rainbow colors and an on-demand color of left-handed polarized light with angle-dependent wavelength and polarization state accounts for the unique optical phenomenon based on experimental observation and theoretical analysis. Such chiroptical property can be readily tuned with architectural design, enabling reproducible optical appearance with high fidelity. Bringing the pearlescence, iridescence, and specular reflection together endows cellulose nanocrystal films with rich and tunable chiroptical properties that can be used for anti-counterfeiting applications. The current work marks the beginning of chiral pearlescent materials from renewable resources, while the pressure-directed self-assembly provides a step toward scalable production.

In Situ Real-Time Observation of Formation and Self-Assembly of Perovskite Nanocrystals at High Temperature.

All-inorganic cesium lead halide perovskite nanocrystals (NCs) have received much attention due to their outstanding optical and electronic properties, but the underlying growth mechanism remains elusive due to their rapid formation process. Here, we report an in situ real-time study of the growth of Cs4PbBr6 NCs under practical synthesis conditions in a custom-made reactor. Through the synchrotron-based small-angle X-ray scattering technique, we find that the formation of Cs4PbBr6 NCs is accomplished in three steps: the fast nucleation process accompanied by self-focusing growth, the subsequent diffusion-limited Ostwald ripening, and the self-assembly of NCs into the face-centered cubic (fcc) superlattices at high temperature and the termination of growth. The simultaneously collected wide-angle X-ray scattering signals further corroborate the three-step growth model. The influence of superlattice formation is also elucidated, which improves the uniformity of the final NCs.

Waveguide-Integrated Colloidal Nanocrystal Supraparticle Lasers.

Supraparticle (SP) microlasers fabricated by the self-assembly of colloidal nanocrystals have great potential as coherent optical sources for integrated photonics. However, their deterministic placement for integration with other photonic elements remains an unsolved challenge. In this work, we demonstrate the manipulation and printing of individual SP microlasers, laying the foundation for their use in more complex photonic integrated circuits. We fabricate CdSxSe1-x/ZnS colloidal quantum dot (CQD) SPs with diameters from 4 to 20 μm and Q-factors of approximately 300 via an oil-in-water self-assembly process. Under a subnanosecond-pulse optical excitation at 532 nm, the laser threshold is reached at an average number of excitons per CQD of 2.6, with modes oscillating between 625 and 655 nm. Microtransfer printing is used to pick up individual CQD SPs from an initial substrate and move them to a different one without affecting their capability for lasing. As a proof of concept, a CQD SP is printed on the side of an SU-8 waveguide, and its modes are successfully coupled to the waveguide.

Tannic Acid-Induced Gelation of Aqueous Suspensions of Cellulose Nanocrystals.

Nanocellulose hydrogels are a crucial category of soft biomaterials with versatile applications in tissue engineering, artificial extracellular matrices, and drug-delivery systems. In the present work, a simple and novel method, involving the self-assembly of cellulose nanocrystals (CNCs) induced by tannic acid (TA), was developed to construct a stable hydrogel (SH-CNC/TA) with oriented porous network structures. The gelation process is driven by the H-bonding interaction between the hydroxyl groups of CNCs and the catechol groups of TA, as substantiated by the atoms in molecules topology analysis and FTIR spectra. Interestingly, the assembled hydrogels exhibited a tunable hierarchical porous structure and mechanical moduli by varying the mass ratio of CNCs to TA. Furthermore, these hydrogels also demonstrate rapid self-healing ability due to the dynamic nature of the H-bond. Additionally, the structural stability of the SH-CNC/TA hydrogel could be further enhanced and adjusted by introducing coordination bonding between metal cations and TA. This H-bonding driven self-assembly method may promote the development of smart cellulose hydrogels with unique microstructures and properties for biomedical and other applications.

Selective Self-assembly of Gold Nanocrystals Using Complementary Leucine Zipper Peptides

Abstract A heterodimeric leucine zipper (Lz)–based peptide hybrid was utilized as a molecular adhesive to bind two types of gold nanocrystals with different shapes. An acidic leucine zipper (LzE) and a basic leucine zipper (LzK) peptides with terminal cysteine are respectively adsorbed to the surface of spherical gold nanoparticles (LzE–Au NPs) and gold nanocubes (LzK–Au NCs). Transmission electron microscope (TEM) observation and visible (Vis) absorption spectroscopy revealed that LzE–Au NPs and LzK–Au NCs are selectively self-assembled in water. The dynamic self-assembly behavior is also confirmed by in-situ fluorescence resonance energy transfer between fluorescence dyes connected to LzE and LzK peptides and other control experiments.

Robust Cellulose Nanocrystal-Based Self-Assembled Composite Membranes Doped with Polyvinyl Alcohol and Graphene Oxide for Osmotic Energy Harvesting.

Osmotic energy from the salinity gradients represents a promising energy resource with stable and sustainable characteristics. Nanofluidic membranes can be considered as powerful alternatives to the traditional low-performance ion exchange membrane to achieve high-efficiency osmotic energy harvesting. However, the development of a highly efficient and easily scalable core membrane component from low-cost raw materials remains challenging. Here, a composite membrane based on the self-assembly of cellulose nanocrystals (CNCs) with polyvinyl alcohol (PVA) and graphene oxide (GO) nanoflakes as additives is developed to provide a solution. The introduction of soft PVA polymer significantly improves the mechanical strength and water stability of the composite membrane by forming a nacre-like structure. Benefiting from the abundant negative charges of CNC nanorods and GO nanoflakes and the generated network nanochannels, the composite membrane demonstrates a good cation-selective transport capacity, thus contributing to an optimal osmotic energy conversion of 6.5W m-2 under a 100-fold salinity gradient and an exemplary stability throughout 25 consecutive days of operation. This work provides an option for the development of nanofluidic membranes that can be easily produced on a large scale from well-resourced and sustainable biomass materials for high-efficiency osmotic energy conversion.