Molecular Self-assembly Research Articles

Thermo-Chemical Cues-Mediated Strategy to Control Peptide Self-Assembly and Charge Transfer Complexation.

Peptide amphiphiles (PAs) are known for their remarkable ability to undergo molecular self-assembly, a process that is highly responsive to the local microenvironment. Herein, we design a pyrene tethered peptide amphiphile Py-VFFAKK, 1 that exhibits pathway-driven self-assembly from metastable nanoparticles to kinetically controlled nanofibers and thermodynamically stable twisted bundles upon modulations in pH, temperature, and chemical cues. The presence of the pyrene moiety ensures donation of the electron to an electron acceptor, namely, 7,7,8,8-tetracyanoquinodimethane (TCNQ), to form a supramolecular charge transfer complex in aqueous solution that was studied in detail with microscopic and spectroscopic techniques. Excitation of the donor species in its excimer state facilitates electron donation to the acceptor moiety, paving away a long-lived charge-separated state that persists for over a nanosecond, as ascertained through transient absorption spectroscopy. Finally, the self-assembled charge transfer complex is explored toward antimicrobial properties with Escherichia coli while maintaining biocompatibility toward L929 mice fibroblast cells.

Insight into molecular interactions and energetics of surfactant self-assembly in hydrated glucose-urea deep eutectic solvent

Self-assembled structures in highly biocompatible Natural Deep Eutectic Solvent (NADES) are gaining popularity as new drug delivery systems due to their inherent advantages. Although glucose-urea (GU) based NADES satisfies the criterion of an efficient DES in terms of low toxicity, stability at desirable pH range, low viscosity and biocompatible polarity its potential as a medium for molecular self-assembly is yet unexplored. In this work we present first systematic study of self-assembly of pharmaceutically important excipients like sodium deoxycholate (NaDC), cetylpyridinium chloride (CPC) and Brij 35 (B35) in three hydrated GUNADES using isothermal titration calorimetry. The findings are correlated to the microstructure of these solvents as delineated from molecular dynamics simulations. Micro-environment of the micelles in a typical hydrated GU NADES has been studied using time resolved fluorescence anisotropy measurements. Cyto-toxicity of the proposed NADES has been assessed using MTT assay. CMC values of the surfactants increased with increase in glucose-urea concentration in the NADES indicating increased solvophilicity in GUNADES. Fluorescence studies indicate higher polydispersity of sodium deoxycholate in water than GUNADES. Cyto-toxicity study of GU80 shows good biocompatibility.

Enhanced conductivity and stability of Prussian blue cathodes in sodium-ion batteries by surface vapor-phase molecular self-assembly

Enhanced conductivity and stability of Prussian blue cathodes in sodium-ion batteries by surface vapor-phase molecular self-assembly

Ovalbumin amyloid-like fibrils/resveratrol self-assembling hydrogel: Preparation, characterization and formation mechanism

Food protein amyloid-like fibrils can significantly increase solution viscosity and promote the formation of entangled gel network due to its high stiffness and extreme aspect ratios. In this study, the ability of hydrophobic resveratrol (RES) deposited on the surface of the ovalbumin (OVA) amyloid-like fibrils (OVAF) to form a new self-assembling hydrogel was explored. The results showed that the simple mixing of RES and OVAF at pH 6.5 can successfully drive the formation of hybrid hydrogels through molecular self-assembly. The interactions between OVAF and RES were confirmed by the results of transmission electron microscope and fluorescence spectra. Non-covalent interactions including hydrophobic interactions and hydrogen bonds played an important role in the formation of the OVAF/RES self-assembling hydrogels. Furthermore, the OVAF/RES hydrogel showed a dense structure, high water holding capacity and remarkable rheological properties. The viscosity and storage modulus of the hybrid hydrogels increased with the increase of the RES and OVAF concentrations. After gastrointestinal digestion, some fibrous structures in the OVAF/RES hydrogels remained, which allowed for continuous release of RES. In summary, the OVAF/RES hybrid hydrogels with tunable structures, encapsulation ability and self-assembly characteristics are expected to be candidates for the delivery of hydrophobic active polyphenols in the food industry.

Synthesis, Photophysical Properties and Self-Assembly of a Tetraphenylethylene-Naphthalene Diimide Donor-Acceptor Molecule.

The development of new π-conjugated molecular structures with controlled self-assembly and distinct photophysical properties is crucial for advancing applications in optoelectronics and biomaterials. This study introduces the synthesis and detailed self-assembly analysis of tetraphenylethylene (TPE) functionalized naphthalene diimide (NDI), a novel donor-acceptor molecular structure referred to as TPE-NDI. The investigation specifically focuses on elucidating the self-assembly behavior of TPE-NDI in mixed solvents of varying polarities, namely chloroform: methylcyclohexane (CHCl3 : MCH) and chloroform: methanol (CHCl3 : MeOH). Employing a several analytical methodologies, including UV-Vis absorption and fluorescence emission spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and dynamic light scattering (DLS), these self-assembled systems have been comprehensively examined. The results reveal that TPE-NDI manifests as distinct particles in CHCl3 : MCH (fMCH =90 %), while transitioning to flower-like assemblies in CHCl3 : MeOH (fMeOH =90 %). This finding underscores the critical role of solvent polarity in dictating the morphological characteristics of TPE-NDI self-assembled aggregates. Furthermore, the study proposes a molecular packing mechanism, based on SEM data, offering significant insights into the design and development of functional supramolecular systems. Such advancements in understanding the molecular self-assembly new π-conjugated molecular structures are anticipated to pave the way for novel applications in material science and nanotechnology.

Biphasic control strategy of polymers and nanoparticles for viscous oil removal and molecular release: Synthesis, mechanism and applications

Responsive Pickering emulsions are an excellent platform to control the interfacial properties of oil–water systems. However, the removal of viscous crude oil from oily waste by external stimuli is still a challenge. Here, a dual-stimuli supramolecular assembly of the polymer and silica particles (PS) was designed to achieve desirable control of oil–water interfaces for viscous oil removal and controlled molecular release. The β-cyclodextrin-based polymer was fabricated through the atom transfer radical polymerization (ATRP) method for the host molecules responsive to UV light and amine-modified silica particles for the guest molecules responsive to pH. Utilizing their responsive properties, the PS system was demonstrated in this study to significantly enhance the oil washing efficiency (from 18.3% to 74.2%). Moreover, as the acidic condition was replaced by CO2 injection, it was further enhanced from 74.2% to 88.5%, which is beneficial to greener remediation and production. The responsive PS assembly was also applied for dye release with a slower or faster release of methyl red by tuning the stimuli (pH & UV light). The molecular mechanism was revealed via the molecular dynamics (MD) simulation, which articulates the interaction and motion of the PS system under various stimulations. More importantly, this novel assembly of the cyclodextrin-based polymer and amine-modified silica particles affords a simple and efficient route to enhance the removal of viscous oil waste and precisely control the molecular release. The findings of the molecular self-assembly in this work offer unique opportunities to integrate functional polymers and particles into the liquid–liquid interface, opening an avenue for applications in Pickering emulsions.

Tuning phase separation in DPPDTT/PMMA blend to achieve molecular self-assembly in the conducting polymer for organic field effect transistors.

The semiconductor/insulator blends for organic field-effect transistors are a potential solution to improve the charge transport in the active layer by inducing phase separation in the blends. However, the technique is less investigated for long-chain conducting polymers such as Poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPPDTT), and lateral phase separation is generally reported due to the instability during solvent evaporation, which results in degraded device performance. Herein, we report how to tailor the dominant mechanism of phase separation in such blends and the molecular assembly of the polymer. For DPPDTT/PMMA blends, we found that for higher DPPDTT concentrations (more than 75%) where the vertical phase separation mechanism is dominant, PMMA assisted in the self-assembly of DPPDTT to form nanowires and micro-transport channels on top of PMMA. The formation of nanowires yielded 13 times higher mobility as compared to pristine devices. For blend ratios with DPPDTT ≤ 50%, both the competing mechanisms, vertical and lateral phase separation, are taking place. It resulted in somewhat lower charge carrier mobilities. Hence, our results show that by systematic tuning of the blend ratio, PMMA can act as an excellent binding material in long-chain polymers such as DPPDTT and produce vertically stratified and aligned structures to ensure high mobility devices.

A Spike-like Self-Assembly of Polyaspartamide Integrated with Functionalized Nanoparticles.

The integration of nanoparticles (NPs) into molecular self-assemblies has been extensively studied with the aim of building well-defined, ordered structures which exhibit advanced properties and performances. This study demonstrates a novel strategy for the preparation of a spike-like self-assembly designed to enhance UV blocking. Poly(2-hydroxyethyl aspartamide) (PHEA) substituted with octadecyl chains and menthyl anthranilate (C18-M-PHEA) was successfully synthesized by varying the number of grafted groups to control their morphology and UV absorption. The in situ incorporation of polymerized rod-like TiO2 within the C18-M-PHEA self-aggregates generated spike-like self-assemblies (TiO2@C18-M-PHEA) with a chestnut burr structure in aqueous solution. The results showed that the spike-like self-assemblies integrated with TiO2 NPs exhibited a nine-fold increase in UV protection by simultaneous UV absorption and scattering compared with the pure TiO2 NPs formed via a bulk mixing process. This work provides a novel method for UV protection using self-assembling poly(amino acid)s derivatives integrated with functional nanoparticles to tune their morphology and organization.

Solid-Phase Molecular Self-Assembly Enabled Glue-Free Antifatigue Laminate Programmable Materials.

Repeated programmability has emerged as a desired property in smart device engineering, but the programmability will fatigue upon repeated applications due to the unmatched mechanical property between the layer materials and the polymeric glue that is required to integrate the two individual oriented layers. It is reported here that glue-free antifatigue programmable laminate materials can be made with films resulted from solid-phase molecular self-assembly (SPMSA). The SPMSA films are created by squeezing the precipitates of oppositely charged polyelectrolytes and DTAB with a noodle machine, where the hydrophobic DTAB molecules self-assembled into wormlike micelles and oriented along the squeezing direction. The surface molecules in this film are endowed with sufficient mobility in the presence of hydration water, so that two such films are able to be pressed into a laminate material owing to the hydrophobic and electrostatic interactions between the molecules on the two adjacent surfaces. As the water evaporated gradually, the left laminate materials are glue-free with the same composition. When many of such films are integrated with specific designs, complicated shape programming is able to be achieved, and the programmability is reversible without fatigue. The current strategy is envisioned as a potent intriguing pathway leading to advanced programable materials.

Assembly of multilayer phthalocyanine vanadium oxide molecules on Ag<sub>2</sub>Sb alloy monolayer

Fabricating ordered molecular films and further tuning their assembly behavior is important for constructing organic devices with diverse performances. By using high-resolution scanning tunneling microscopy, in this work, we demonstrate that well-organized vanadyl phthalocyanine (VOPc) films can be formed <i>via</i> ‘bottom-up’ molecular self-assembly on a binary alloy Ag<sub>2</sub>Sb/Ag(111). The Ag<sub>2</sub>Sb monolayer is prepared by evaporating Sb atoms on clean Ag(111) and followed by annealing. The VOPc molecules are deposited on the Ag<sub>2</sub>Sb layer <i>via</i> thermal evaporation. The molecular configuration, structural and orbital characteristics of VOPc are clearly clarified at a submolecular level. It is found that initially the ordered VOPc membrane only exhibits the O-up adsorption configuration. Its square-shaped unit cell consists of five VOPc molecules where two adsorption orientations coexist with the horizontal axis of VOPc which is rotated by about 11° or 21° relative to the side of the unit cell. Due to the molecular dipole-dipole interaction, further-deposited molecules result in the assembly of the second-layer VOPc films with the O-down configuration and the square-shaped unit cell that contains only one VOPc molecule. Subsequently, due to the dipole-dipole interaction between layered molecules, following VOPc molecular layers adopt alternating O-up and O-down configurations as well as the square-shaped unit cell, similar to the case of the second layer. In addition, we find that the molecular orbitals overlap in each assembled molecular layer due to the π-π interaction which could facilitate the charge transport along the π stacking direction of VOPc. This research provides possibility to regulate the adsorption configuration and assembly behavior of functional organic molecules on metal surfaces by forming surface alloys.

On-surface synthesis - Ullmann coupling reactions on N-heterocyclic carbene functionalized gold nanoparticles.

Organic on-surface syntheses promise to be a useful method for direct integration of organic molecules onto 2-dimensional (2D) flat surfaces. In the past years, there has been an increasing understanding of the mechanistic details of reactions on surfaces, however, mostly under ultra-high vacuum on very defined surfaces. Herein, we expand the scope to gold nanoparticles (AuNps) in solution via an Ullmann reaction of aryl halides connected via N-heterocyclic carbenes (NHCs) to AuNps. Through design and syntheses of various organic precursors, we address the influence of the contact angle, reactivity of the halogen and the proximity of the entire coupling partner on on-surface reactivities, thus, establishing general parameters governing organic on-surface syntheses on AuNps in solution, in comparison with the reactivity on defined surfaces under ultra-high vacuum. The retention of such halogenated Nps even at higher reaction temperatures holds great promise in the fields of materials engineering, nanotechnology and molecular self-assembly, while expanding the toolbox of organic chemistry synthesis in accessing various covalent architectures.

2D hexagonal assembly of a dipolar rotor with a close interval of 0.8 nm using a triptycene-based supramolecular scaffold.

Controlling the rotation of carbon-carbon bonds, which is ubiquitous in organic molecules, to create functionality has been a subject of interest for a long time. In this context, it would be interesting to explore whether cooperative and collective rotation could occur if dipolar molecular rotors were aligned close together while leaving adequate space for rotation. However, it is difficult to realize such structures as bulk molecular assemblies, since molecules generally tend to assemble into the closest packing structure to maximize intermolecular forces. To tackle this question, we examined an approach using a supramolecular scaffold composed of a tripodal triptycene, which has been demonstrated to strongly promote the assembly of various molecular and polymer units into regular "2D hexagonal packing + 1D layer" structures. We found that a molecule (1) consisting of a dipolar 1,2-difluorobenzene rotor sandwiched by two 10-ethynyl-1,8,13-tridodecyloxy triptycenes, successfully self-assembles into the desired structure, where the dipolar rotor units align two-dimensionally at a close interval of approximately 0.8 nm while having a degree of freedom for rotational motion. Here we describe the self-assembly behavior of 1 in comparison with the general trend in molecular self-assembly, as well as the motility of the two-dimensionally aligned molecular rotors investigated using solid-state 19F-MAS NMR spectroscopy.

Localized self-assembly of macroscopically structured supramolecular hydrogels through reaction-diffusion.

Localized molecular self-assembly has been developed as an effective approach for the fabrication of spatially resolved supramolecular hydrogels, showing great potential for many high-tech applications. However, the fabrication of macroscopically structured supramolecular hydrogels through molecular self-assembly remains a challenge. Herein, we report on localized self-assembly of low molecular weight hydrogelators through a simple reaction-diffusion approach, giving rise to various macroscopically patterned supramolecular hydrogels. This is achieved on the basis of an acid-catalyzed hydrazone supramolecular hydrogelator system. The acid was pre-loaded in a polydimethylsiloxane (PDMS) substrate, generating a proton gradient in the vicinity of the PDMS surface after immersing the PDMS in the aqueous solution of the hydrogelator precursors. The acid dramatically accelerates the in situ formation and self-assembly of the hydrazone hydrogelators, leading to localized formation of supramolecular hydrogels. The growth rate of the supramolecular hydrogels can be easily tuned through controlling the concentrations of the hydrogelator precursors and HCl. Importantly, differently shaped supramolecular hydrogel objects can be obtained by simply changing the shapes of PDMS. This work suggests that reaction-diffusion-mediated localized hydrogelation can serve as an approach towards macroscopically structuralized supramolecular hydrogels, which may find potential applications ranging from tissue engineering to biosensors.

Self-assembly morphology transition mechanism of similar amphiphilic molecules.

Molecular self-assembly is a powerful synthesis method for nanomaterials. Promoting the development of self-assembly is not only conducive to the efficient preparation of nanomaterials but also promotes progress in other research fields. Therefore, it is necessary to enhance the advancement of molecular self-assembly, and the key is to deepen the understanding of the correlation between molecular characteristics and self-assembly morphologies. However, some similar amphipihlic molecules self-assemble into assemblies with significant morphology difference, which is challenging to clear the mechanism for experimenters. In this work, we explore the microscopic mechanism of six similar molecules by MD simulations, and the influences of molecular conformation, atomic groups, and polycyclic aromatic hydrocarbons on morphologies are discussed in detail. Our findings enrich the design principles of amphiphilic molecules for self-assembly, which promotes the modular design of molecular self-assembly.

Extraordinary cycling performance of high-voltage spinel LiNi0.5Mn1.5O4 materials enabled by interfacial engineering via molecular self-assembly

Interfacial engineering via self-assembly of decanoic acid (DA) molecules enables extraordinary cycling performance of high-voltage spinel LiNi0.5Mn1.5O4 (LNMO) materials.

A convenient protonated strategy for constructing nanodrugs from hydrophobic drug-inhibitor conjugates to reverse tumor multidrug resistance.

Combination therapy has proven effective in counteracting tumor multidrug resistance (MDR). However, the pharmacokinetic differences among various drugs and inherent water insolubility for most small molecule agents greatly hinder their synergistic effects, which makes the delivery of drugs for combination therapy in vivo a key problem. Herein, we propose a protonated strategy to transform a water-insoluble small molecule drug-inhibitor conjugate into an amphiphilic one, which then self-assembles into nanoparticles for co-delivery in vivo to overcome tumor MDR. Specifically, paclitaxel (PTX) is first coupled with a third-generation P-glycoprotein (P-gp) inhibitor zosuquidar (Zos) through a glutathione (GSH)-responsive disulfide bond to produce a hydrophobic drug-inhibitor conjugate (PTX-ss-Zos). Subsequently treated with hydrochloric acid ethanol solution (HCl/EtOH), PTX-ss-Zos is transformed into the amphiphilic protonated precursor and then forms nanoparticles (PTX-ss-Zos@HCl NPs) in water by molecular self-assembly. PTX-ss-Zos@HCl NPs can be administered intravenously and accumulated specifically at tumor sites. Once internalized by cancer cells, PTX-ss-Zos@HCl NPs can be degraded under the overexpressed GSH to release PTX and Zos simultaneously, which synergistically reverse tumor MDR and inhibit tumor growth. This offers a promising strategy to develop small molecule self-assembled nanoagents to reverse tumor MDR in combination therapy.

Attractive acceptor-acceptor interactions in self-complementary quadruple hydrogen bonds for molecular self-assembly.

Molecular self-assembly provides the means for creating large supramolecular structures, extending beyond the capability of standard chemical synthesis. To harness the power of self-assembly, it is necessary to understand its driving forces. A potent method is to exploit self-complementary hydrogen bonding, where a molecule interacts with its own copy by suitable positions of hydrogen-bond donor (D) and acceptor (A) groups. With four hydrogen bonds, there are two possible self complementary patterns: the DDAA/AADD and the DADA/ADAD motifs. Of these, the DDAA pattern is usually more stable. The traditional explanation assumes that the secondary interactions between equal groups, that is, between donors (D⋯D) or acceptors (A⋯A), are repulsive. DDAA arrays would then have two, and DADA arrays six repulsive interactions. Here, using high-end quantum chemical analysis, we show that contrary to the traditional explanation, the secondary A⋯A interactions are, in fact, attractive. We revise the model of secondary interactions accordingly.

A stable and visualized fatty acid-based phase transition material constructed by solid-phase molecular self-assembly for thermal management.

Fatty acids are excellent thermal management materials for thermal storage, release and preventing thermal runaway. However, the leakage of fatty acids leads to instability and prevents their application in thermal management. Herein, a stable and visualized fatty acid-based phase transition material P-S/PA was constructed through solid-state molecular self-assembly strategy from polydiallyldimethylammonium chloride (PDDA), sodium dodecyl benzene sulfonate (SDBS) and palmitic acid (PA). The electrostatic interaction between PDDA and SDBS and hydrophobic interaction between PA and SDBS can prevent PA leakage during phase transition, achieving stability. After 1000 cycles, the changes in the phase transition enthalpy (ΔH M, ΔH C) were less than 1%. The structural similarity also made P-S/PA phase transition visible, and the transmittance changed significantly from 0% to 68% during phase transition. In addition, P-S/PA can be remolded by hot-pressing without performance changes, showing temperature adjustability on varying the fatty acid carbon chain length. Thus, the stable and visualized P-S/PA fatty acid-based phase transition material constructed by solid-phase molecular self-assembly has promising application in thermal management.

The effect of hydrogen bonding on the π depletion and the π-π stacking interaction.

Non-covalent interactions such as hydrogen bonding and π-π stacking are essential types of interactions governing molecular self-assembly. The π-π stacking ability of aromatic rings depends on the electron density of the π orbitals, which is affected by the electron-withdrawing or electron-donating properties of the substituents. We have here studied the effect of hydrogen bonding on the strength of the π-π stacking interactions by calculating the binding energies at the explicitly correlated Møller-Plesset (MP2-F12) perturbation theory level using polarized triple-ζ quality basis sets. The stacking interactions in the presence of hydrogen bonding are found to be stronger than in the absence of the hydrogen bonding suggesting that hydrogen bonds lead to π depletion, which affects the aromatic character of the aromatic rings and increases the strength of the π-π stacking interaction. We have also studied how hydrogen bonding affects the stacking interaction by calculating local orbital locator integrated pi over plane (LOLIPOP) indices. Comparing LOLIPOP indices with the stacking-interaction energies calculated at the MP2-F12 level shows that there is no clear correlation between the stacking-interaction energies and LOLIPOP indices.

Single-Bond Linked and Vinylene-Bridged Azulenyl Bis(squaraine) Dyes: Design, Synthesis and Molecular Self-Assembly Behaviors†

Two azulenyl bis(squaraine) dyes were designed and synthesized, whose main structural difference lied on the connection model between two monomeric units. Their self-assembly behaviors were investigated in the mixed solvents...