Self-assembled Formation Research Articles

Two-Dimensional Self-Assembly of BODIPY Derivatives with Different Functional Groups at the Liquid-Solid Interface.

The 4,4-difluoro-boradiazaindacene (BODIPY) unit possesses a rigid aromatic backbone, which facilitates the formation of self-assemblies and aggregates. However, most current studies on the self-assemblies of BODIPY derivatives have relied on spectroscopic methods to indirectly gather information about the self-assembled structures. In this study, we presented three BODIPY derivatives (B-3OC12, B-3OC12-2I, and B-DOB-2OC12) that shared the same core but were decorated with different functional groups. The self-assembled structures were revealed using scanning tunneling microscopy (STM) in combination with density functional theory (DFT). The results showed that all the molecules self-assembled into lamellar structures. When modified with three dodecyloxy chains or with the introduction of additional halogen atoms, the B-3OC12 and B-3OC12-2I molecules tended to distribute in a staggered form to build a tetramer or dimer. In contrast, the B-DOB-2OC12 molecule, which contains a dioxaborole group, self-assembled in a head-to-tail manner. These results demonstrated that BODIPY derivatives self-assembled into different structures, depending on their distinct patterns of intermolecular interactions influenced by functional groups.

Coassembly of Charged Copolymer Amphiphiles Featuring pH-Regulated Antifouling Properties.

Understanding the formation of highly ordered structures through self-assembly is crucial for developing various biologically relevant systems. A significant expansion in the development of self-assembly chemistry features stable coassembly formation using a mixture of two oppositely charged polymers. This study provides insightful findings on the coassembly of hydrophobic coumarin-integrated cationic (P1-P3) and anionic (P1'-P3') copolymers toward the formation of vesicles in aqueous medium at pH 7.4, with a hydrodynamic diameter (Dh) of 160 ± 10 nm and electrically neutral zwitterionic surfaces, confirmed by dynamic light scattering. Upon varying the solution pH, an intriguing charge switchable behavior (+ve → 0 → -ve) and a drastic morphological transition to spherical aggregates of the vesicles were noticed. At pH 7.4, these coassembled vesicles possess a neutral surface charge, empowering them to resist nonspecific protein (pepsin and lysozyme) adsorption via electrostatic repulsion, as evidenced by size evolution and protein binding measurements. Additionally, the bilayer membrane allows for the encapsulation of hydrophilic and hydrophobic guest molecules and their sustained release in the presence of 10 mM esterase; thus, this study demonstrates potential applications of coassembly to serve as a drug delivery vehicle.

Probing the Interplay of Protein Self-Assembly and Covalent Bond Formation in Photo-Crosslinked Silk Fibroin Hydrogels.

Covalent crosslinking of silk fibroin via native tyrosine residues has been extensively explored; however, while these materials are very promising for biomedical, optical, soft robotics, and sensor applications, their structure and mechanical properties are unstable over time. This instability results in spontaneous silk self-assembly and stiffening over time, a process that is poorly understood. This study investigates the interplay between self-assembly and di-tyrosine bond formation in silk hydrogels photo-crosslinked using ruthenium (Ru) and sodium persulfate (SPS) with visible light. The effects of silk concentration, molecular weight, Ru/SPS concentration, and solvent conditions are examined. The Ru/SPS system enables rapid crosslinking, achieving gelation within seconds and incorporating over 90% of silk into the network, even at very low protein concentrations (≥0.75%wt/v). A model emerges where silk self-assembly both before and after crosslinking affects protein phase separation, mesoscale structure, and dynamic changes in the hydrogel network over time. Silk concentration has the greatest impact on hydrogel properties, with higher silk concentration hydrogels experiencing two orders of magnitude increase in stiffness within 1 week. This new understanding and ability to tune hydrogel properties and dynamic stiffening aids in developing advanced materials for 4D biofabrication, sensing, 3D cancer models, drug delivery, and soft robotics.

Hierarchical Structures of Amino Acid Derived Polyhydroxyurethanes: Promising Candidates as Drug Carriers and Cell Adhesive Scaffolds.

In this study, we examined the self-assembly of a series of biodegradable and biocompatible amino acid-based polyhydroxyurethanes (PHUs), investigating the structural influence of these polymers on their self-assembly and the resulting morphological features. The presence of hydrophilic and hydrophobic segments, along with carbonyl urethane, ester, and hydroxyl groups in the PHU backbone, facilitates intermolecular hydrogen bonding, enabling the formation of self-assemblies with hierarchical nanodimensional morphologies. We determined the critical aggregation concentration (CAC) and found that it largely depends on the PHU's structure. In-depth morphological studies demonstrated that the evolution of morphology proceeds in four steps: (1) the initial formation of micelles, which act as seeds at very low concentrations, (2) the elongation of these micelles into nanorod or nanopalette shapes below the CAC range, (3) the epitaxial growth of nanofibers at the CAC, and (4) the complete formation of fibrous mats above the CAC. Additionally, these hierarchical structures were utilized for the encapsulation and release of the drug doxorubicin (DOX). We observed that 75% of the encapsulated DOX was readily released in a mildly acidic environment, similar to the physiological conditions of cancer cells. Cellular uptake studies confirmed the effective uptake of the drug-loaded nanoassemblies into the cytoplasm of cells. Our studies also confirmed that these self-assembled structures can serve as effective cell adhesive scaffolds for tissue engineering applications.

Pyridine hydrazide glycoconjugate-based gelators: Facile synthesis and exploring their application in iodide sensing

Detection of iodide (I−) holds great importance because of its crucial role in various biological activities in the human body. However, its selective detection using small molecular systems has not been as well-explored as metal complex and metal-framework structures, which are expensive and difficult to synthesize. Here, we have reported the synthesis of a novel class of 4,6-O-protected sugar-pyridine hydrazide derivatives in an environmentally benign condition with moderate yield. The overall characterization was done using NMR, HRMS, single-crystal XRD, and DFT studies. Anomeric forms of the N-glucosylamines were assigned from NMR spectroscopy and single-crystal XRD studies. The selective sensing ability towards I− of the synthesized derivatives has been confirmed through colourimetry, UV–Vis and 1H NMR titration and gelation studies. The 4,6-O-butylidene derivatives 6(a–c) were utilized because of their better solubility for the selective detection of iodide ion in solution, whereas 4,6-O-benzylidene derivatives 7(a–c) were used for the same in gel state for their enhanced gelation ability. Furthermore, the morphology of the xerogels have been analyzed through SEM and the thermal ability has been determined by DSC spectra. The experimental studies suggest that the iodide anion takes part in self-assembly formation with the sugar-pyridine hydrazide derivatives through C–H···I− interaction, which, along with H-bonding, π–π stacking, van der Waal force of interaction enhances the gel formation.

Influence of hydrogen-bonded 3-mercaptopropionic acid bilayers on binary self-assembled monolayer formation

The influence of the monolayer order, defect density, and bilayer formation on the formation of binary self-assembled monolayers (SAMs) was investigated via the solution-phase displacement of 3-mercaptopropionic acid (MPA) by 1-decanethiol (DT). The ultrahigh vacuum scanning tunneling microscopy results confirm that well-ordered, pristine MPA SAMs are displaced at slower rates than MPA SAMs with less long-range order and greater defect density. Furthermore, MPA samples containing regions of an MPA bilayer displayed the slowest rates of displacement with DT. For pristine MPA samples and MPA samples with regions of an MPA bilayer, displacement with DT resulted in the formation of the low-density, lying down phase of DT. Our results suggest that the presence of an MPA bilayer, the result of hydrogen bonding between carboxylic acid groups in MPA, significantly lowers the rate of total displacement of MPA by DT compared to moderately defected MPA SAMs. These results highlight the importance of the structure, composition, and intermolecular forces, such as hydrogen bonding, when considering binary SAM formation via solution-phase displacement methods.

From disorder to order: A dynamic approach to mesophase formation in soft sphere model.

This study explores the dynamics of self-assembly and mesophase formation through molecular dynamics simulations of hexagonal and lamellar systems using a simplified coarse-grained model. We focus on characterizing the order-disorder transitions driven by temperature variations and emphasize the often overlooked disordered regime, which serves as a precursor to periodic mesoscale ordering. Our findings not only underscore the morphological richness of the disordered regime, comparable to that of its periodic counterparts, but also reveal the presence of clustering regimes within isotropic phases, thus corroborating prior experimental and theoretical observations. By employing the dynamic correlation coefficient, this work introduces a novel approach to understanding the fundamental mechanisms of mesophase formation, providing new insights into the complex dynamics of self-assembly.

Self-assembled formation of platinum single atoms and nanoclusters stabilized on MXene as an efficient catalyst for boosting electrocatalytic hydrogen evolution

Atomic isolated and dispersed single atom catalyst is ideal for high-performance industrial catalyst. However, the contribution from small amounts of nanoclusters coexisting with single atoms to the catalytic reaction activity is often neglected. In this work, a MXene-supported uniformly dispersed Pt single atoms and nanoclusters (Pt1+Ptn/MXene) were obtained by self-assembly through an impregnation method. The catalyst exhibits high electrochemical performance in the hydrogen evolution reaction with an overpotential of only 61.3 mV and a Tafel slope of 32.5 mV dec−1 at a current density of 10 mA cm−2 in an acidic environment. The XAFS analysis and further DFT calculation indicate that the synergistic effect between single atoms and nanoclusters can facilitate adsorption of H* and promote the HER reaction. This work provides an efficient method for integrating multiple active sites in noble metal catalysts.

Origin of Secondary Structure Transitions and Peptide Self-Assembly Propensity in Trifluoroethanol-Water Mixtures.

Membrane-peptide interactions are key to the formation of helical intermediates in the early stages of amyloidogenesis. Aqueous solutions of 2,2,2-trifluoroethanol (TFE) provide a membrane-mimetic environment capable of promoting and stabilizing local peptide interactions. Uperin 3.5 (U3.5), a 17-residue and amidated antimicrobial peptide, is unstructured in water but self-assembles into fibrils in the presence of salt. Secondary structure transitions linked to U3.5 self-assembly were investigated in TFE/water mixtures, in both the absence and presence of salt, to assess the role of membrane-peptide interactions on peptide self-assembly and amyloid formation. A 5-to-7-fold increase in fibril yield of U3.5 was observed at low TFE concentrations (10% TFE/water v/v) compared with physiological buffer but only in the presence of salt. No aggregation was observed in salt-free TFE/water mixtures. Circular dichroism spectra showed that partial helical structures, initially stabilized by TFE, transitioned to β-sheet-rich aggregates in a saline buffer. Molecular dynamics simulations confirmed that TFE and salt act synergistically to enhance peptide-peptide interactions, resulting in β-sheet-rich U3.5 oligomers at low TFE concentrations. Specifically, TFE stabilized amphipathic, helical intermediates, leading to increased peptide-peptide attraction through hydrophobic interactions. The presence of salt further enhanced the peptide-peptide interactions by screening positively charged residues. Thus, the study revealed the role of a membrane mimic in stabilizing helical intermediates on the pathway to amyloid formation in the antimicrobial U3.5 peptide.

Active interface bulging in Bacillus subtilis swarms promotes self-assembly and biofilm formation

Microbial communities such as biofilms are commonly found at interfaces. However, it is unclear how the physical environment of interfaces may contribute to the development and behavior of surface-associated microbial communities. Combining multimode imaging, single-cell tracking, and numerical simulations, here, we found that activity-induced interface bulging promotes colony biofilm formation in Bacillus subtilis swarms presumably via segregation and enrichment of sessile cells in the bulging area. Specifically, the diffusivity of passive particles is ~50% lower inside the bulging area than elsewhere, which enables a diffusion-trapping mechanism for self-assembly and may account for the enrichment of sessile cells. We also uncovered a quasilinear relation between cell speed and surface-packing density that underlies the process of active interface bulging. Guided by the speed-density relation, we demonstrated reversible formation of liquid bulges by manipulating the speed and local density of cells with light. Over the course of development, the active bulges turned into striped biofilm structures, which eventually give rise to a large-scale ridge pattern. Our findings reveal a unique physical mechanism of biofilm formation at air-solid interface, which is pertinent to engineering living materials and directed self-assembly in active fluids.

Biocompatible Preparation of Beta-Lactoglobulin/Chondroitin Sulfate Carrier Nanoparticles and Modification of Their Colloidal and Hydropathic Properties by Tween 80.

The electrostatic complexation of the protein beta-lactoglobulin (β-LG) with the anionic polysaccharide chondroitin sulfate (CS) and the subsequent stabilization by thermal treatment were studied to achieve the well-defined nanoparticles (NPs). The formation of the well-defined NPs was obtained at pH 4 with a hydrodynamic radius from 60 to 80 nm. NP aggregation was observed at pH 1.5 because of the loss of the anionic charge of chondroitin sulfate on the surface of the NPs. After thermal treatment, the NPs exhibited stability against a pH increase to pH 7 while a stronger aggregation at pH 1.5 was observed. Core-shell structures were found at pH 7 after thermal treatment, indicating a possible mechanism of partial disintegration. The addition of Tween 80 (T80) before thermal treatment led to the formation of T80 self-assemblies inside the NPs. This caused an increase in the hydrophobicity of the inner and outer surfaces of the NPs as it was observed by fluorescence spectroscopy. The ζ-potential of the complexes and NPs was about -20 mV while the presence of T80 did not affect it. FTIR spectra verified changes of the secondary structure of β-LG in its complexes with CS and T80. The thermally treated NPs exhibited high surface and overall hydrophobicity and stability in high salinity and biocompatible solutions. The thermally treated NPs showed colloidal and physicochemical stability for 1 month, which were enhanced by the addition of T80. Due to the nature of the precursors and their colloidal properties, the NPs are highly promising for applications as biocompatible drug delivery nanocarriers while T80 acts as an agent to modify their properties.

Tuning Preferential Molecular Adsorption and Self-Assembled Molecular Network Formation at the Liquid–Solid Interface: The Impact of Annealing and Confinement

Tuning Preferential Molecular Adsorption and Self-Assembled Molecular Network Formation at the Liquid–Solid Interface: The Impact of Annealing and Confinement

Thin Film Formation of HSA in the Presence of CTAB-Capped Gold Nanorods through Phase Separation.

Phase behavior in protein-nanoparticle systems in light of protein corona formation has been investigated. We report the formation of HSA thin films following the addition of a solid protein to a solution of CTAB-capped gold nanorods (AuNRs) via phase separation. The phase separation behavior was observed through UV-vis spectroscopy, turbidity assays, and DLS studies. UV-vis spectra for the protein-AuNR solution indicated a possible self-assembly formation by CTAB-HSA complexes and AuNR-HSA conjugates. The turbidity was found to increase linearly up to 30-50% v/v for each component. The growth phase slope is proportional to the concentration of the components, AuNRs, and HSA, with no lag phase. Dynamic light scattering (DLS) shows the formation of larger aggregates with time, implying a segregated phase of AuNR-HSA and a CTAB-HSA-AuNR network. ζ-potential values confirm surface modification, implying protein corona formation on nanorods. The thin films were also characterized using SEM, AFM, SAXS, XPS, FTIR, and TGA studies. SEM images show a smooth surface with a reduced number of pores, indicating the compactness of the deposited structure. AFM shows two different structural pattern formations with the deposition, indicating possible self-assembly of the protein-conjugated nanoparticles. FTIR studies indicate a change in the hydrogen bonding network and confirm the CTAB-HSA-AuNR complex network formation. The XPS studies indicate Au-S bond formation, along with Au-S-S-Au interactions. SAXS studies indicate the formation of aggregates (oligomers), as well as the presence of dominant attractive intermolecular interactions in the thin films.

Corrosion inhibition of stainless steel through the formation of hydrophobic nanoporous oxide layer

This study investigates anti-corrosion properties of anodized and hydrophobically modified anodized SUS 304 stainless steel (SS 304). Utilizing electrochemical anodization and subsequent annealing, a well-ordered hexagonally closed-packed nanoporous oxide layer on the SS 304 surface, designated as AAS, was successfully developed. Then, a self-assembled monolayer of silane molecules, namely, octadecyltrimethoxysilane (ODTS) and 1 H,1 H,2 H,2 H-perfluorooctyltriethoxysilane (PFTS), was formed on the nanoporous oxide layer of annealed-anodized SS 304. The FTIR study confirmed the formation of the self-assembly of silane molecules on nanoporous oxide surface. The self-assembled monolayers exhibited hydrophobic surface where hydrophobicity increases with increase of silane molecule concentration and gives a water contact angles measure of 127.60° and ∼ 128.83° for 0.50 wt% ODTS and 0.50 wt% PFTS, respectively. The potentiodynamic polarization study revealed a corrosion rate of 1.485 × 10−3 mm year−1 for AAS, 0.614 × 10−3 mm year−1 for 0.50 wt% ODTS-AAS, and 0.348 × 10−3 mm year−1 for 0.50 wt% PFTS-AAS. This represents a significant reduction in corrosion rate compared to bare stainless steel (4.385 × 10−3 mm year−1) when exposed to a simulated sea water environment. The AAS, 0.50 wt% ODTS-AAS and 0.50 wt% PFTS-AAS exhibited corrosion inhibition efficiency of 66.13 %, 85.97 % and 92.06 %, respectively. Electrochemical impedance analysis revealed that PFTS exhibits roughly double the effective charge transfer resistance of ODTS and 7.4 times higher than that of annealed anodized stainless steel, confirming superior corrosion inhibition capability. Overall, this research illuminates the mechanism behind self-assembled monolayer formation, resulting in the development of hydrophobic surfaces and the inhibition of corrosion on nanoporous oxide layers on stainless steel surfaces.

Reversing the Trend: Deciphering Self-Assembly of Unconventional Amphiphiles Having Both Alkyl-Chain and PEG.

In the field of molecular self-assembly, the core of an assembly is always made up of hydrophobic moiety like a long alkyl chain, whereas the outer part has always been a hydrophilic moiety such as poly(ethylene glycol) (PEG), or charged species. Hence, reversing the trend to manifest self-assembled structures with a PEG core and a surface consisting of alkyl chains in aqueous system is incredibly challenging. Herein, we architected a unique class of cationic bolaamphiphiles containing low molecular weight PEG and alkyl chains of different lengths. The bolaamphiphiles spontaneously form vesicles without external stimuli. These vesicles are unprecedented because PEG makes up the vesicle core, while the alkyl chains appear on the vesicles' exterior. Hence, this particular design reverses the usual trend of self-assembly formation. The vesicle size increases with the increase in alkyl chain-length. To our great surprise, we obtained large micelles for longest alkyl-chain amphiphile, which in turn act as a gemini amphiphile. The shift from a particular bolaamphiphile to gemini amphiphile with the variation of alkyl chain is also unexplored. Therefore, this specific class of self-assembled structure would compound a new paradigm in molecular self-assembly and supramolecular chemistry.

Crystallization-Inspired Design and Modeling of Self-Assembly Lattice-Formation Swarm Robotics.

Self-assembly formation is a key research topic for realizing practical applications in swarm robotics. Due to its inherent complexity, designing high-performance self-assembly formation strategies and proposing corresponding macroscopic models remain formidable challenges and present an open research frontier. Taking inspiration from crystallization, this paper introduces a distributed self-assembly formation strategy by defining free, moving, growing, and solid states for robots. Robots in these states can spontaneously organize into user-specified two-dimensional shape formations with lattice structures through local interactions and communications. To address the challenges posed by complex spatial structures in modeling a macroscopic model, this work introduces the structural features estimation method. Subsequently, a corresponding non-spatial macroscopic model is developed to predict and analyze the self-assembly behavior, employing the proposed estimation method and a stock and flow diagram. Real-robot experiments and simulations validate the flexibility, scalability, and high efficiency of the proposed self-assembly formation strategy. Moreover, extensive experimental and simulation results demonstrate the model's accuracy in predicting the self-assembly process under different conditions. Model-based analysis indicates that the proposed self-assembly formation strategy can fully utilize the performance of individual robots and exhibits strong self-stability.

Implementation of the Su-Schrieffer-Heeger Model in the Self-Assembly Si-In Atomic Chains on the Si(553)-Au Surface.

Indium-decorated Si atomic chains on a stepped Si(553)-Au substrate are proposed as an extended Su-Schrieffer-Heeger (SSH) model, revealing topological end states. An appropriate amount of In atoms on the Si(553)-Au surface induce the self-assembly formation of trimer SSH chains, where the chain unit cell comprises one In atom and two Si atoms, confirmed by scanning tunneling microscopy images and density functional calculations. The electronic structure of the system, examined through scanning tunneling spectroscopy, manifests three electron bands within the Si-In chain, accompanied by additional midgap topological states exclusively appearing at the chain's end atoms. To elucidate the emergence of these topological states, a tight-binding model for a finite-length-extended SSH chain is proposed. Analysis of the energy spectra, density of states functions, and eigenfunctions demonstrates the topological nature of these self-assembled atomic chains.

Self-assembly formation of Co quantum dot loaded N-doped porous carbon cathode for quinoline degradation in the electro-Fenton system

Quinoline is high toxicity and difficult biodegradation in oil washing wastewater. Therefore, efficient removal of quinoline contaminant from water bodies poses a major challenge. Hence, Co quantum dot loaded N-doped porous carbon (CoNC) nanosheets grown in situ on carbon cloth were fabricated as cathode for the degradation of quinoline in electro-Fenton system. Under optimal conditions (c(Fe2+) = 0.5 mM, U = -0.3 V, pH = 3), quinoline was completely degraded within 15 min with superior apparent rate constant of 0.385 min−1, which was 19.6 times higher than that of the ZIF-L precursor, due to the abundance of Co QDs active sites and hydrophilicity and electrical conductivity of N-doped porous carbon. In addition, three reaction pathways for quinoline were deduced by combining Density Functional Theory (DFT) calculation and Liquid Chromatography-Mass Spectrometry (LC-MS). More importantly, in situ FTIR and free energy calculations were analyzed to reveal that pathway Ⅰ as spontaneous reaction was the main reaction pathway. Finally, the toxicity of the intermediates was assessed with ECOSAR software and E. coli experiments, and the overall toxicity decreased during the degradation reactions. This work provides novel perspectives on environmental protection by designing in-situ grown cathodes through self-assembly method, thereby effectively purifying pollutants from wastewater.

Deterministic Single-Row-Droplet Catalyst Formation for Uniform Growth Integration of High-Density Silicon Nanowires.

Planar silicon nanowires (SiNWs), grown by using low temperature catalytic approaches, are excellent 1D channel materials for developing high-performance logics and sensors. However, a deterministic position and size control of the metallic catalyst droplets, that lead to the growth of SiNWs, remains still a significant challenge for reliable device integration. In this work, we present a convenient but powerful edge-trimming catalyst formation strategy, which can help to produce a rather uniform single-row of indium (In) catalyst droplets of Dcat = 67 ± 5 nm in diameter, with an exact one-droplet-on-one-step arrangement. This approach marks a significant achievement in self-assembled catalyst formation and offers a foundation to attain a reliable and scalable growth of density SiNW channels, via an in-plane solid-liquid-solid (IPSLS) mechanism, with a uniform diameter down to Dnw = 35 ± 4 nm, and do not rely on high-precision lithography techniques. Prototype SiNW-based field effect transistors (FETs) are also fabricated, with a high Ion/Ioff current ratio and small subthreshold swing of >107 and 262 mV·dec-1, respectively, indicating a reliable new routine to integrate a wide range of SiNW-based logic, sensor, and display applications.

Ionic-storage capacitance enhanced by a self-assembled CoO-Nafion nanocoating on single-walled carbon nanotubes

We introduce a novel approach for enhancing ion-storage capabilities through the self-assembled formation of ternary nanowires, consisting of a CoO-and-Nafion nanocomposite encasing metallic single-walled carbon nanotubes (SWNTs). These nanowires highlight the indispensable role of the conductor-semimetallic SWNT-CoO heterojunction in expediting the redox reaction kinetics of the CoO while the Nafion component facilitates the transport of hydroxide ions. Consequently, supercapacitors comprising the ternary nanowires deliver the specific capacitance of calculated 18.84 mF cm−2, five times higher than those obtained at the counterpart devices that lack Nafion and/or CoO. This self-assembly method precisely organizes functional components within the nanowires, aligning with electrochemical principles to optimize charge transfer and minimize concentration gradients for improved electrochemical polarization. Our function-enhanced ternary nanowires, together with their straightforward synthetic process, promise an alternative opportunity for formulating high-performance ion-storage electrodes and thus pave the way for their application in next-generation supercapacitor technologies.