Self-assembled Structures Research Articles

Understanding X-ray-induced isomerisation in photoswitchable surfactant assemblies.

Dynamic, responsive materials can be built using photosurfactants (PS) that self-assemble into ordered nanostructures, such as micelles or liquid crystals. These PS contain photoswitchable groups, such as azobenzene (Azo) or, more recently, arylazopyrazoles (AAPs), which change shape and polarity on photoisomerisation between the E and Z states, thus changing the self-assembled structure. Small-angle X-ray scattering (SAXS) is a powerful technique to probe the morphology of PS and can be used to measure the mechanisms of structural changes using in-situ light irradiation with rapid, time-resolved data collection. However, X-ray irradiation has been shown previously to induce Z-to-E isomerisation of Azo-PS, which can lead to inaccuracies in the measured photostationary state. Here, we investigate the effect of light and X-ray irradiation on micelles formed from two different PS, containing either an Azo or AAP photoswitch using SAXS with in-situ light irradiation. The effect of X-ray irradiation on the Z isomer is shown to depend on the photoswitch, solvent, concentration and morphology. We use this to create guidelines for future X-ray experiments using photoswitchable molecules, which can aid more accurate understanding of these materials for application in solar energy storage, catalysis or controlled drug delivery.

Polysaccharide Nanocrystals-Based Chiral Nematic Structures: From Self-Assembly Mechanisms, Regulation, to Applications.

Chiral architectures, one of the key structural features of natural systems ranging from the nanoscale to macroscale, are an infinite source of inspiration for functional materials. Researchers have been, and still are, strongly pursuing the goal of constructing such structures with renewable and sustainable building blocks via simple and efficient strategies. With the merits of high sustainability, renewability, and the ability to self-assemble into chiral nematic structures in aqueous suspensions that can be preserved in the solid state, polysaccharide nanocrystals (PNs) including cellulose nanocrystals (CNCs) and chitin nanocrystals (ChNCs) offer opportunities to reach the target. We herein provide a comprehensive review that focuses on the development of CNCs and ChNCs for the use in advanced functional materials. First, the introduction of CNCs and ChNCs, and cellulose- and chitin-formed chiral nematic organizations in the natural world, are given. Then, the self-assembly process of such PNs and the factors influencing this process are comprehensively discussed. After that, we showcased the emerging applications of the self-assembled chiral nematic structures of CNCs and ChNCs. Finally, this review concludes with perspectives on the challenges and opportunities in this field.

Silk fibroin-based wearable SERS biosensor for simultaneous sweat monitoring of creatinine and uric acid

Sweat biomarkers have the potential to offer valuable clinical insights into an individual's health and disease condition. Current sensors predominantly utilize enzymes and antibodies as biometric components to measure biomarkers present in sweat quantitatively. However, enzymes and antibodies are susceptible to interference by environmental factors, which may affect the performance of the sensor. Herein, we present a wearable microfluidic surface-enhanced Raman scattering (SERS) biosensor that enables the non-invasive and label-free detection of biomarkers in sweat. Concretely, we developed a bimetallic self-assembled anti-opal array structure with uniform hot spots, enhanced the Raman scattering effect, and integrated it into a silk fibroin-based sensing patch. Utilizing a silk fibroin substrate in the wearable SERS sensor imparts desirable properties such as softness, breathability, and biocompatibility, which enables the sensor to establish close contact with the skin without causing chemical or physical irritation. In addition, introducing microfluidic channels enables the controlled and high temporal resolution management of sweat, facilitating more efficient sweat collection. The proposed label-free SERS sensor can offer chemical ‘fingerprint’ information, enabling the identification of sweat analytes. As an illustration of the feasibility, we have effectively monitored the creatinine and uric acid levels in sweat. This study presents a versatile and highly sensitive approach for the simultaneous detection of biomarkers in human sweat, showcasing significant potential for application in point-of-care monitoring.

Lattice Symmetry-Guided Charge Transport and Recombination in Supramolecular Assemblies

Synthetic soft materials mimicking biological structures are promising for many applications in fields such as photovoltaics and photocatalysis. For these applications, a deep understanding of the charge- and energy-transfer mechanisms is required to build more efficient devices. In this work, we investigate self-assembled 2D supramolecular structures using angle-resolved photoluminescence (PL) imaging techniques and decompose the optical transition dipoles in the supramolecular structures. Combining these optical studies with Monte Carlo simulations, we reveal the important role played by lattice symmetry in charge dissociation, transport, and recombination, as well as the exciton spin states. These mechanistic findings have important implications for engineering soft materials towards efficient energy conversion and photocatalytic applications.

(Invited) Tailoring the Surface Chemistry and Assembling Structure of 2D Materials for Supercapacitors and Batteries

Energy storage devices are important components in portable electronics, electric vehicles, and the electrical distribution grid. Batteries and supercapacitors have achieved great success as the spearhead of electrochemical energy storage devices, but need to be further developed in order to meet the ever-increasing energy demands, especially attaining higher power and energy density, and longer cycling life. Rational design of electrode materials plays a critical role in developing energy storage systems with higher performance. Starting from the classical 2D material - graphene to the other new 2D materials for example MXene, I will introduce some of our recent works about how to design and tune the surface chemistry of 2D materials and how to tailor the structure of 2D materials. Specifically, the interlayer structure and the self-assembled unique structure will be discussed, and the use of various advanced characterization techniques (in situ/operando) to understand the materials and their energy storage mechanisms will be covered in my talk as well. Most importantly, I will also introduce how can we strategically use 2D materials in different applications from battery, supercapacitors to sensors.

Integrated Couplers of THz Radiation for Helical Slow-Wave Structures.

We have designed an integrated device that couples input and output coaxial horn antennas with a self-assembled helical slow-wave structure cradled in a v-groove on a silicon-on-insulator wafer. These devices will potentially enable the characterization of cold parameters and beam-wave interaction in slow-wave structures on a wafer level, i.e., without having to dice and package individual devices. In addition, such vertically integrated antennas and helical slow-wave structures may form the basis of compact and low-cost traveling-wave tube amplifiers operating at THz frequencies.

Procrystalline Self-Assembly of Desymmetrized Pentaphenylcyclopentadiene.

The interplay between the molecular shape and the intermolecular interaction plays a decisive role in self-assembled structures. Recently, inherent randomness of low ordered assemblies, resulting from lack of short- and long-range periodicities, has attracted significant attention due to the unique structural, electronic, and mechanical properties. Here, we present procrystalline self-assemblies of pentaphenyl cyclopentadienyl derivatives on Ag(111) and Au(111) with scanning tunneling microscopy, operating at 4.3 K under ultrahigh vacuum conditions. Two examples, using 5-fold symmetric molecules substituted with methyl or fluorine groups, show that weak interactions, such as π-π stacking, CH-π interactions, and CH···F hydrogen bonding, play a pivotal role in formation of the procrystalline assembly. Our results may give insights into the intricate relationship between the molecular shape and the intermolecular interaction in the formation of non-crystalline assemblies.

Influence of topography on nano-mechanical properties of cylindrical magnetron sputtered TiN films

Numerous studies on Nano-mechanical behavior of the thin films explained primarily in terms of their film morphology and particle size rather than film topography. Therefore, the current study investigates the effect of film topography on the nano-mechanical characteristics of the film. Ti/TiN multilayer thin films were deposited at varying deposition pressures by using an indigenously developed Cylindrical Magnetron Sputtering (CMS) unit. Surface crystallographic information is characterized by synchrotron-based Grazing Incidence XRD analysis. Film growth follows self-assembled nano hill architecture as revealed by AFM and in situ Scanning Probe Microscopy images. The tribo-mechanical properties of the film is dependent on the height and spacing of its self-assembled structure, which experiences either crushing or buckling under the indenter load, thereby affecting film characteristics. Film deposited at moderate pressure exhibits superior wear behavior, attributed to the interplay between Plasticity Index (PI) and Depth Recovery Ratio (DRR). The study primarily focused on film growth phenomena by using cylindrical targets and their influence on nanomechanical properties of the film.

Tuning stability, rheology, and fire-extinguishing performance of advanced firefighting foam material by inorganic nanoparticle flame retardants

HypothesisNanoparticle-stabilized foams are extremely stable, and flame retardant inorganic nanoparticles should be able to add sealing capacity of firefighting foams on flammable liquid fuels, and hence enhance fire extinguishment performance on liquid fuel fire. In practice, how do flame retardant nanoparticles resist the destructive effect of oil molecules on foam and tune foam properties? ExperimentsWe have prepared a nanoparticle-enhanced foam comprising of hydrocarbon surfactant, short-chain fluorocarbon surfactant, and nanoparticles. The interactions among nanoparticles and surfactant molecules were characterized by using dynamic surface tension and conductivity. Stability, rheology, and oil resistivity on liquid fuel of the nanoparticle-enhanced foam were evaluated systematically. Fire suppression effectiveness of the foams was verified based on a standard experiment. FindingsFoam stability and oil resistivity were enhanced due to self-assembled network structures formed by jammed aggregates composed by nanoparticles and surfactants in Plateau borders and bubble films, providing structural recoverability and enhanced viscoelasticity within foam. Foams containing nano-SiO2, nano-CaCO3, nano-Al(OH)3, and nano-Mg(OH)2 show difference in fire extinguishment due to different ability to enhance foam properties. Foam containing nano-Al(OH)3 shows the strongest adaptation and could shorten fire extinguishing time by 2 times and prolong burn-back time by 2.3 times compared with commercial product.

Precise tuning of porphyrin self-assembly and photo-activated antimicrobial activity via metal ion coordination

Bacterial drug resistance has emerged as a significant threat to global human health, prompting the need for alternative antimicrobial strategies. Photodynamic therapy (PDT) has garnered widespread attention as a promising antimicrobial approach that circumvents the issue of bacterial resistance. Porphyrin is a class of photosensitizers with promising potential. In this study, we utilized the strategy of precise tuning of self-assembly of porphyrin through the coordination of metal ions to achieve the efficient and selective photo-activated antimicrobial. Typically, the selected porphyrin (TPPS4) serves as the foundation for an investigation into the role of metal ions (Mn+) as regulatory agents. The coordination of various metal ions (Bi3+, Ca2+, Zn2+, and Mn2+), with TPPS4 results in differentiated molecular stacking, which in turn affects the morphology of the self-assembled structures and their capacity to generate reactive oxygen species (ROS), ultimately leading to varied antimicrobial activities. The study found that the antibacterial capability of the system is positively correlated with its ability to generate reactive oxygen species (TPPS4-Bi ≈ TPPS4-Ca > TPPS4 >TPPS4-Zn >TPPS4-Mn). This work paves the way for the development of novel photodynamic antimicrobial agents that are both highly potent and minimally toxic, offering a significant advancement in the field of antimicrobial therapy.

DNA-Based Conductors: From Materials Design to Ultra-Scaled Electronics.

Photolithography has been the foundational fabrication paradigm in current high-performance electronics. However, due to the limitation in fabrication resolution, scaling beyond a 20-nm critical dimension for metal conductors presents a significant challenge for photolithography. Structural DNA nanotechnology emerges as a promising alternative to photolithography, allowing for the site-specific assembly of nano-materials at single-molecule resolution. Substantial progresses have been achieved in the ultra-scaled DNA-based conductors, exhibiting novel transport characteristics and small critical dimensions. This review highlights the structure-transport property relationship for various DNA-based conductors and their potential applications in quantum/semiconductor electronics, going beyond the conventional scope focusing mainly on the shape diversity of DNA-templated metals. Different material synthesis methods and their morphological impacts on the conductivities are discussed in detail, with particular emphasis on the conducting mechanisms, such as insulating, metallic conducting, quantum tunneling, and superconducting. Furthermore, the ionic gating effect of self-assembled DNA structures in electrolyte solutions is examined. This review also suggests potential solutions to address current challenges in DNA-based conductors, encouraging multi-disciplinary collaborations for the future development of this exciting area.

Highly Performing Sodium Metal Batteries Reinforced by a Self-Regulated Dual-Layered Solid Electrolyte Interphase via a Metal-Organic Framework.

Sodium-metal batteries, heralded for high energy density and cost-effectiveness, are compromised by an unstable solid electrolyte interphase (SEI) and dendrite formation, which hinder practical applications. Herein, a zirconium-based metal-organic framework nanostructure coating (ZMOF-NSC) was constructed in a low-loss, flexible manner. Comprehensive studies show that ZMOF-NSC, with its periodically ordered nanochannels and organized pore structures, enhances ion transport and decreases the Na+ migration energy barrier, thus ensuring uniform ion flux and achieving uniform spherical deposition. Additionally, ZMOF-NSC facilitates partial desolvation, catalyzing the formation of an inorganic-rich, dual-layered SEI that effectively protects the anode and suppresses dendrite formation. Consequently, the ZMOF-NSC@Na symmetric battery exhibits an impressive lifespan of over 2500 h, demonstrating extended operational longevity. The Na3V2(PO4)3∥ZMOF-NSC@Na batteries demonstrate exceptional cycling stability with 81% capacity retention after 2000 cycles at 10 C, maintaining stability over 3000 cycles at 20 C. Moreover, the NVP∥ZMOF-NSC@Na battery achieves an energy density of 370 Wh kg-1 and a power density of 10,484 W kg-1, indicating superior durability and performance. This significant finding highlights the significant potential of structured MOFs to induce a dual-layered SEI, advancing the commercialization of durable, dendrite-free sodium metal batteries. The precise design of self-assembled pore structures and surface active sites in MOFs demonstrates significant potential in advancing the commercialization of durable, dendrite-free electrodes of metal-based rechargeable batteries.

Tunable Dual Self-Healing Composite Coatings with Self-Assembled Structures Regulated by Janus Nanoparticles.

The durability of concrete structures can be enhanced in a convenient and permanent manner through the surface protection of cementitious materials with composite polymer coatings. However, polymer coatings are susceptible to various mechanical and physical deterioration in complex and variable environments. In this paper, the theory of polymer microstructure regulation was employed to improve the sustainability of the protective performance of composite coatings. The self-assembled core-shell structure regulated by amphiphilic Janus nanoparticles is employed to modify the tunable polystyrene acrylate-polysiloxane self-healing coatings. The results demonstrate that the adhesion strength of the prepared self-assembled coating reached 3.7 MPa, which is sufficient to resist the damage to the microstructure of cementitious materials caused by physical erosion, seepage, and ionic corrosion. The self-healing coating, regulated by Janus particles, exhibited a residual creep of only 57.03% and a maximum loss angle tangent of 0.381. Furthermore, the material exhibited a superior shape memory function due to the presence of strong hydrogen bonding. The regulated self-healing coating repaired the polymer structural damage under mechanical and thermal deformation by bridging and filling effects. The coating demonstrated a tensile strength recovery of up to 71.23% in a wetted state, accompanied by a rapid restoration of its electrochemical properties and corrosion resistance. Furthermore, the self-healing emulsion penetrates the substrate defects and forms numerous polymer crystalline particles that effectively fill the microcracks.

Deformation mode and energy absorption of self-assembly CFRP composites cellular structure by 3D printing

Compared with traditional cellular structures, self-assembly structures exhibit significantly higher assembly flexibility, allowing for more scientific and rational protection design in the realm of structural protection. Moreover, self-assembly structure had the potential to mitigate the rapid decrease of load bearing capacity often observed in integral molding due to plastic hinge failure between adjacent cells. Therefore, self-assembly CFRP composites cellular structure was proposed, Quasi-static compression test and finite element simulation were carried out to analyze the deformation modes and energy absorption characteristics. Hexagon (H) structure formed a shear failure band, and re-entrant (R) structure was fully densified with large deflection. The deformation of inclined struts of HR and RH structures were well compatible. The total absorption energy of R structure was max, and H structure was min. The specific energy absorption and mean compression force of two-layer structures were higher, but the increasing number of layers could reduce the peak compression force, RH and R structures showed excellent energy absorption ability.

Ready, Set, Grow: From Micelles to Giant Vesicles via Biocatalytic Activation.

Controlling physicochemical processes that drive changes in supramolecular aggregates is an important objective toward creating artificial soft micro- and nanomachines. Previous research explored the morphology control of membrane-based materials subjected to externally imposed chemical stimuli. Here, we modulate the microscale morphology of pH-responsive assemblies by using biocatalysis to internally generate changes in global pH. Catalytic reactions offer flexibility in the mechanism and rate at which stimuli are introduced to responsive assemblies, ultimately enabling precision and control over size and morphology. We observed, by dynamic light scattering and fluorescence microscopy, substantial microscale differences between assemblies subjected to manually titrated pH changes compared to biocatalytically activated pH changes, including the growth of giant vesicles from micelles. Coarse-grained molecular dynamics simulations of these metastable self-assembled structures provided insight into the thermodynamics and kinetics of the preferred structures. These results demonstrate the feasibility of using biocatalytic reactions to modulate the size and morphology of supramolecular assemblies, from micelles to giant vesicles.

Graphene nanoribbon hydrogel scaffold for highly conductive and robust polyimide nanocomposite

Although highly loaded graphitic nanocarbon materials effectively enhance the electrical, mechanical, and thermal properties of polymeric materials, their practical implementation has been hindered by severe aggregation issues. Here, we propose a method to achieve homogeneous nanocarbon-polyimide (PI) composites by integrating graphene oxide nanoribbons (GONRs) with polyamic acid ammonium (PAA) salt, a precursor of PI. Self-assembled scaffold structure of GONRs hydrogel enables the uniform integration and immobilization of PAA within the GONR scaffold, mitigating aggregation concerns. The resulting GONR/PAA hydrogel, formed through physical interactions, can be coated onto substrates via a shear stress-induced bar coating method due to its viscoelastic rheological properties. Subsequent heat treatment at 400 °C triggers the imidization reaction of PAA and the reduction of GONR, facilitating the formation of uniformly integrated GNR/PI nanocomposite coatings. Under optimized conditions, incorporating a high-loading GONR content in PAA (95 wt% of GONR and 5 wt% of PAA) yielded GNR/PI composites with excellent mechanical properties, exhibiting a hardness of 0.75 GPa and an elastic modulus of 8.3 GPa. Additionally, this GNR/PI composite displayed a good electrical conductivity of 3890 S/m, attributed to the electrical pathways formed by GNRs within the PI matrix.

The combined effect of pH and NaCl on the susceptibility of Listeria monocytogenes to rhamnolipids

The use of natural and sustainable additives, that are less aggressive to the environment, is a trend in the food industry. Rhamnolipids (RL) biosurfactants have shown potential for controlling food pathogens however, due to the presence of free carboxyl groups, the pH and ionic strength may influence the properties of such surfactants. In this study, we describe the antimicrobial activity of RL under different pH values and NaCl concentrations, towards both planktonic and biofilms of Listeria monocytogenes. RL were effective at pH 5.0 and the addition of 5 % NaCl improved the bactericidal efficacy for planktonic and sessile cells. The effect of NaCl was more pronounced at pH above 6 showing a significant increase in RL antimicrobial activity. At pH 7.0 planktonic population was eradicated by RL only when salt was present whereas biofilm viability was decreased by 5 log with MBIC varying from > 2500.0 mg/L (RL) to 39.0 mg/L (RL + 5 % NaCl). Larger vesicular and lamellar RL self-assembly structures were predominant when NaCl was present, suggesting their association with the antimicrobial activity observed. The pH and ionic strength of the medium are important parameters to be considered for the development of RL-based strategies to control L. monocytogenes.

Novel boehmite and η-alumina nanostructures synthesized using a green ultrasonic-assisted hydrothermal method by clove extract for water treatment

In the paper, a novel three-dimensional self-assembly flower-like structure consisting of one-dimensional needle-like η-alumina as well as spherical boehmite and η-alumina nanoparticles synthesized through the green ultrasonic-assisted hydrothermal method (GUAH) is introduced. Also, the effects of clove extract and calcination of nanoparticles (NPs) at 550 °C on the properties of the NPs are studied. The results declare that the extract concentration and calcination affect the crystallinity of the NPs, and amorphous NPs are formed at a higher concentration of clove extract. Notably, the extract concentration predominantly impacts the optical properties of the NPs, yielding a wide range of bandgap energies from 2.3 to 4.7 eV. Moreover, the specific surface area of 173 to 330 m2/g, and 195 to 327 m2/g are obtained for boehmite and η-alumina NPs, respectively. Evaluating the efficiencies of the NPs in treating water containing copper ions (194 ppm) under varying pH conditions demonstrates high removal rates at short contact times (10 min) achieved by specific η-alumina NPs as a good candidate for water treatment from Cu2+ ions.

Mechanical properties of agarose hydrogels tuned by amphiphilic structures

Agarose is a biocompatible polysaccharide that is capable to form physically cross-linked hydrogels in aqueous dispersion. These materials offer a wide range of applications and are commonly used in the food industry or electrophoresis. Moreover, due to their favourable characteristics (biocompatibility, high water absorption, porosity), agarose hydrogels have recently also found applications also in drug delivery systems, wound dressing, and extracellular matrix (ECM) modelling. This paper presents a comprehensive rheological characterization of agarose hydrogels with various self-assembled amphiphilic structures (CTAB, TTAB, SDS, Tween 20) acting as simple membrane structure models. These findings demostrated that the presence of surfactants of diverse charge above their critical micellar concentration (CMC) can enhance hydrogel mechanical properties. Moreover, pronounced enhancement was observed for cationic surfactant, and even concentrations below CMC resulted in a higher stiffness of the hydrogel. Therefore, both the electrostatic effect and the amphiphilic structure effect can have a significant impact on the rheological properties on agarose hydrogels. These findings are of a significant interest in the field of polymer and surfactants interactions, since agarose is widely considered essentially uncharged. However, it is assumed, that traces of negatively charged groups on the agarose backbone can have a significant impact when interacting with oppositely charged surfactants. Moreover, these findings could be beneficial for better understanding of interaction of polysaccharides (e.g. agarose) and self-assembled amphiphilic structures and can also be considered as a crude model of ECM in which membrane structures are embedded.

Subtle chemical modification around the flavin core to create diverse morphological assembly and sensing application

Herein, an intricate interplay of the non-covalent interactions induced via subtle chemical modification around the flavin core was envisaged to generate a diverse array of morphological features. Three different flavin analogues with the covalently linked carboxylic group, a glycine or proline entity were chosen along with a simple flavin entity and were investigated for their photophysical and morphological behavior. A systematic structural variation around flavin core has resulted in the formation of irregular shaped, fibrous, tapered fibers, sphere shaped and punctured disk shaped self-assembled structures. Interestingly, the carboxylic-flavin analogue was found to differentiate between monovalent alkali versus divalent alkaline earth metal ions. Overall, the present study highlights the importance of subtle structural engineering in regulating the diverse modes for self-assembled structures, which might be playing a role in designing chemical structures for practical applications.