Tunable Self-assembly Research Articles

Effective repulsive interaction between Janus polymer-grafted nanoparticles adhering to lipid vesicles.

The adhesion of nanoparticles to lipid vesicles causes curvature deformations to the membrane to an extent determined by the competition between the adhesive interaction and the membrane's elasticity. These deformations can extend over length scales larger than the size of a nanoparticle, leading to an effective membrane-curvature-mediated interaction between nanoparticles. Nanoparticles with uniform surfaces tend to aggregate into unidimensionally close-packed clusters at moderate adhesion strengths and endocytose at high adhesion strengths. Here, we show that the suppression of close-packed clustering and endocytosis can be achieved by the surface modification of the nanoparticles into Janus particles where a moiety of their surface is grafted with polymers under a good solvent condition. The osmotic pressure of the polymer brushes prevents membrane wrapping of the nanoparticles' moieties that are grafted with polymers, thus suppressing their endocytosis. Furthermore, a repulsion between polymer brushes belonging to two nearby nanoparticles destabilizes the dimerization of the nanoparticles over a wide range of values of the polymers' molecular weight and grafting density. This surface modification of nanoparticles should allow for reliable, non-close-packed, and tunable self-assemblies of nanoparticles.

Engineering ZIF-8@Ag Core-satellite Superstructures through Solvent-induced Tunable Self-assembly for Surface-Enhanced Raman Spectroscopy

Metal-organic frameworks (MOFs) based substrates have great potential for quantitative analysis of hazardous substances using surface-enhanced Raman spectroscopy (SERS) due to their significant signal enhancement, but face challenges like complex...

Kinetically blocked self-assembly of colloidal strings with tunable interactions in magnetic fields.

Tunable self-assembly driven by external electric or magnetic fields is of significant interest in modern soft matter physics. While extensively studied in two-dimensional systems, it remains insufficiently explored in three-dimensional systems. In this study, we investigated the formation of vertical strings from an initial monolayer system of particles deposited on a horizontal substrate under the influence of an external magnetic field using experiments, computer simulations, and theoretical frameworks. We demonstrated that the main mechanism of string self-assembly is merging, driven by the interplay between gravity and induced tunable interparticle interactions. During this process, the system has to overcome a saddle point on the energy landscape, whose height increases with the string height. At a certain point, further self-assembly becomes kinetically blocked in a metastable state, far from equilibrium. This contrasts sharply with the typical scenario for tunable self-assembly in two dimensions, where the resulting structures usually correspond to the equilibrium state. Therefore, this finding opens up opportunities for more detailed control of three-dimensional tunable self-assembly by designing and tuning various potential barriers along the kinetic pathways.

Tunable supramolecular self-assemblies based on cyclodextrin polymer as a loading platform for water-soluble drugs

Drug loading capacity is a crucial character of nano-scaled drug carriers to achieve high quality pharmaceutical preparations. However, efficient encapsulation of water-soluble small molecular drugs still faces large obstacles in many cases. Herein, we designed a novel supramolecular delivery system constructed by poly(β-cyclodextrin) containing benzoic acid groups (PCD-PA) and adamantyl terminated poly(ethylene glycol) (PEG-AD) to provide multiple intermolecular interactions for competent loading of water-soluble small-molecular drugs. PCD-PA had multiple host molecules, and PEG-AD could be inserted via host-guest interaction in different proportion to adjust the composition of supramolecular carrier. Meanwhile, π-π stacking and electrostatic interaction furnished by benzoic acid groups served as binding force for drug entrapment, which led to considerable loading capacity for several water-soluble drugs. Among the drugs with different chemical structures, mitoxantrone hydrochloride and doxorubicin hydrochloride bearing anthraquinone rings and several protonable amino groups acquired the highest loading content as about 14 % in PCD-PA3/PEG-AD supramolecular self-assemblies. Further computational simulations investigated the mechanism of drug loading based on the interactions between the carrier materials and the payloads. In addition, the weakly acidic environment obviously accelerated the release of certain drugs. All in all, this self-assembled supramolecular nano-system displayed great potentials as a delivery platform for diverse water-soluble drugs.

Water-Stable, Eight-electron Acceptor Drives Anion⋅⋅⋅Water Assisted Tunable Ionic Self-Assembly and Proton Conduction.

Organic π-scaffolds are being envisaged for new-age electron- and ion-responsive materials that can accumulate electrons as well as transport proton. However, such systems are extremely rare as electron-deficient scaffolds are unstable in aqueous solution. Here we detail the synthesis of a water-stable core-naphthalenediimide-nitrobenzyl-viologen based tetra-cation, which accumulates up to eight-electrons within an exceptionally narrow potential window of +0.05 V and -1.12 V. The supramolecular interactions and the ensuing ionic framework are tunable based on the three anions, e. g., Cl-, Br- and PF6 -, that are investigated in this work. The ionic framework is formed and supported by a range of H-bonds, in which, the nitro benzyl groups act as pillars connecting the 1D water-tapes and the halide anions. The water molecules are hydrogen-bonded with the halide anions and bestow a facile pathway for the proton conduction, with proton conductivity up to 3.19×10-3 S cm-1. In contrast, the ionic assembly formed by the lipophilic PF6 - anions do not host the water tapes and consequently the proton conductivity is found to be four orders of magnitude lower. This is a unique example, whereby proton conductivity is realized and is tunable within a highly electron-deficient, eight-electron acceptor, water-stable ionic supramolecular system.

Machine Learning-Assisted High-Throughput Identification and Quantification of Protein Biomarkers with Printed Heterochains.

Advanced in vitro diagnosis technologies are highly desirable in early detection, prognosis, and progression monitoring of diseases. Here, we engineer a multiplex protein biosensing strategy based on the tunable liquid confinement self-assembly of multi-material heterochains, which show improved sensitivity, throughput, and accuracy compared to standard ELISA kits. By controlling the material combination and the number of ligand nanoparticles (NPs), we observe robust near-field enhancement as well as both strong electromagnetic resonance in polymer-semiconductor heterochains. In particular, their optical signals show a linear response to the coordination number of the semiconductor NPs in a wide range. Accordingly, a visible nanophotonic biosensor is developed by functionalizing antibodies on central polymer chains that can identify target proteins attached to semiconductor NPs. This allows for the specific detection of multiple protein biomarkers from healthy people and pancreatic cancer patients in one step with an ultralow detection limit (1 pg/mL). Furthermore, rapid and high-throughput quantification of protein expression levels in diverse clinical samples such as buffer, urine, and serum is achieved by combining a neural network algorithm, with an average accuracy of 97.3%. This work demonstrates that the heterochain-based biosensor is an exemplary candidate for constructing next-generation diagnostic tools and suitable for many clinical settings.

Accelerated Engineering of ELP-Based Materials through Hybrid Biomimetic-De Novo Predictive Molecular Design.

Efforts to engineer high-performance protein-based materials inspired by nature have mostly focused on altering naturally occurring sequences to confer the desired functionalities, whereas de novo design lags significantly behind and calls for unconventional innovative approaches. Here, using partially disordered elastin-like polypeptides (ELPs) as initial building blocks this work shows that de novo engineering of protein materials can be accelerated through hybrid biomimetic design, which this work achieves by integrating computational modeling, deep neural network, and recombinant DNA technology. This generalizable approach involves incorporating a series of de novo-designed sequences with α-helical conformation and genetically encoding them into biologically inspired intrinsically disordered repeating motifs. The new ELP variants maintain structural conformation and showed tunable supramolecular self-assembly out of thermal equilibrium with phase behavior in vitro. This work illustrates the effective translation of the predicted molecular designs in structural and functional materials. The proposed methodology can be applied to a broad range of partially disordered biomacromolecules and potentially pave the way toward the discovery of novel structural proteins.

Tunable self-assembly of lipid-based block polymeric micelles with temperature-sensitive poly(vinylcaprolactam) shell for effective anticancer drug delivery

Lipids, as naturally occurring biomolecules have emerged as promising carriers for delivering various therapeutic agents. However, only a few attempts have been made in terms of their applications as amphiphilic block copolymers for anticancer drug delivery. In this work, a biocompatible micellar drug delivery system with fatty acid-based polymer core and temperature-sensitive shell was developed. A series of amphiphilic block copolymers poly(vinyl stearate)/poly(vinyl laurate)-b-poly(N-vinylcaprolactam) (PVS/PVL-b-PNVCL) were synthesized via microwave-assisted reversible addition-fragmentation chain transfer polymerization in a controlled fashion. By varying the fatty acid type and hydrophilic/hydrophobic block lengths, the self-assembly behaviour of the block copolymer micelles proved to be highly tunable in terms of their morphology and particle size. Nile Red and hydrophobic anticancer drug doxorubicin (DOX) were effectively incorporated into the micelles, demonstrating high drug loading capacity, good serum stability, and temperature-dependent drug release characteristics of the polymeric micelles. In vitro studies using cell models revealed that blank PVS -b-PNVCL micelles are biocompatible with different cell lines, while DOX-loaded micelles were internalized into and accumulated in the cells, showing a high cytotoxic effect against HeLa cells. These findings suggest an opportunity for the development of safe and efficient lipid-based micellar system for smart drug delivery and cancer treatments.

Molecularly informed field theory for estimating critical micelle concentrations of intrinsically disordered protein surfactants.

The critical micelle concentration (CMC) is a crucial parameter in understanding the self-assembly behavior of surfactants. In this study, we combine simulation and experiment to demonstrate the predictive capability of molecularly informed field theories in estimating the CMC of biologically based protein surfactants. Our simulation approach combines the relative entropy coarse-graining of small-scale atomistic simulations with large-scale field-theoretic simulations, allowing us to efficiently compute the free energy of micelle formation necessary for the CMC calculation while preserving chemistry-specific information about the underlying surfactant building blocks. We apply this methodology to a unique intrinsically disordered protein platform capable of a wide variety of tailored sequences that enable tunable micelle self-assembly. The computational predictions of the CMC closely match experimental measurements, demonstrating the potential of molecularly informed field theories as a valuable tool to investigate self-assembly in bio-based macromolecules systematically.

Tunable Optical Properties and Self-Assemblies of a Water-Soluble Perimidinium Imide Dye

AbstractThe synthesis of unsymmetrically peri-annulated naphthalene dyes, perimidinium imides (PrIm), is reported. Compared with the symmetrical and popular analogous naphthalenediimide dyes, PrIm showed a red-shifted absorption maximum. The water-soluble dyes showed tunable self-assembly behaviors and optical properties. The dyes retain their photoluminescence properties in water.

Hourglass-Shaped Nanocages with Concaved Structures Based on Selective Self-Complementary Coordination Ligands and Tunable Hierarchical Self-Assembly.

Three-dimensional (3D) structures constructed via coordination-driven self-assemblies have recently garnered increasing attention due to the challenges in structural design and potential applications. In particular, developing new strategy for the convenient and precise self-assemblies of 3D supramolecular structures is of utmost interest. Introducing the concept of self-coordination ligands, herein the design and synthesis of two meta-modified terpyridyl ligands with selective self-complementary coordination moiety are reported and their capability to assemble into two hourglass-shaped nanocages SA and SB is demonstrated. Within these 3D structures, the meta-modified terpyridyl unit preferably coordinates with itself to serve as concave part. By changing the arm length of the ligands, hexamer (SA) and tetramer (SB) are obtained respectively. In-depth studies on the assembly mechanism of SA and SB indicate that the dimers could be formed first via self-complementary coordination and play crucial roles in controlling the final structures. Moreover, both SA and SB can go through hierarchical self-assemblies in solution as well as on solid-liquid interface, which are characterized by transmission electron microscope (TEM) and scanning tunneling microscopy (STM). It is further demonstrated that various higher-order assembly structures can be achieved by tuning the environmental conditions.

Graft onto approaches for nanocellulose-based advanced functional materials.

The resurgence of cellulose as nano-dimensional 'nanocellulose' has unlocked a sustainable bioeconomy for the development of advanced functional biomaterials. Bestowed with multifunctional attributes, such as renewability and abundance of its source, biodegradability, biocompatibility, superior mechanical, optical, and rheological properties, tunable self-assembly and surface chemistry, nanocellulose presents exclusive opportunities for a wide range of novel applications. However, to alleviate its intrinsic hydrophilicity-related constraints surface functionalization is inevitably needed to foster various targeted applications. The abundant surface hydroxyl groups on nanocellulose offer opportunities for grafting small molecules or macromolecular entities using either a 'graft onto' or 'graft from' approach, resulting in materials with distinctive functionalities. Most of the reviews published to date extensively discussed 'graft from' modification approaches, however 'graft onto' approaches are not well discussed. Hence, this review aims to provide a comprehensive summary of 'graft onto' approaches. Furthermore, insight into some of the recently emerging applications of this grafted nanocellulose including advanced nanocomposite formulation, stimuli-responsive materials, bioimaging, sensing, biomedicine, packaging, and wastewater treatment has also been reviewed.

Naphthalimide-based conjugated macrocycles possessing tunable self-assembly and supramolecular binding behaviours.

The special geometric configurations and optoelectronic properties of p-conjugated macrocycles have always been the focus of materials science. The incorporation of building moieties with different features into macrocycles can not only change their geometric configurations, but also realize the regulation of intramolecular charge transfer, which is expected to bring unusual performance in supramolecular chemistry and optoelectronic devices. Herein, four novel p-conjugated macrocycles based on typical electron acceptor units naphthalimide (NMI) with aryl or alkyl substitutions were reported. The different substitutions on NMI had greatly affected the self-assembly behaviours of these macrocycles. Alkyl substituted NP2b and NP3b showed obvious self-aggregation in solution, while similiar phenomenon was not found in aryl substituted macrocycles NP2a and NP3a, which can be attributed to the steric hindrance caused by rigid aryl groups that could affect the aggregation of macrocycles in solution. In addition, all the macrocycles exhibited supramolecular encapsulation with C70, in which the larger macrocycles NP3a and NP3b with twisted geometries showed stronger binding affinity towards C70 than the corresponding small-size macrocycles NP2a and NP2b with near-planar geometries. Our studies have greatly extended the family of macrocycles based on NMI, pointing out the direction for further supramolecular studies and applications on p-conjugated macrocycles.

Transferring Micellar Changes to Bulk Properties via Tunable Self-Assembly and Hierarchical Ordering.

Hierarchical self-assembly is an effective means of preparing useful materials. However, control over assembly across length scales is a difficult challenge, often confounded by the perceived need to redesign the molecular building blocks when new material properties are needed. Here, we show that we can treat a simple dipeptide building block as a polyelectrolyte and use polymer physics approaches to explain the self-assembly over a wide concentration range. This allows us to determine how entangled the system is and therefore how it might be best processed, enabling us to prepare interesting analogues to threads and webs, as well as films that lose order on heating and "noodles" which change dimensions on heating, showing that we can transfer micellar-level changes to bulk properties all from a single building block.

Janus-Type Dendrimers Based on Highly Branched Fluorinated Chains with Tunable Self-Assembly and 19F Nuclear Magnetic Resonance Properties

Tuning the self-assembly of dendritic amphiphiles represents a major challenge for the design of advanced nanomaterials for biomimetic applications. The morphology of the final aggregates, in fact, critically depends on the primary structure of the dendritic building blocks as well as the environmental conditions. Here we report a new family of fluorinated Janus-type dendrimers (FJDs), based on a short-chain and branched fluorinated synthon with 27 magnetically equivalent fluorine atoms, linked to bis-MPA polyester dendrons of different generations. Increasing size, flexibility, and number of peripheral hydroxyl groups, we observed a peculiar self-assembly behavior in bulk and in aqueous media as a consequence of the subtle balance between their fluorinated and hydrophilic portions. The lowest generation FJDs formed spherical nanoparticles in water, e.g., micelles, showing a single 19F NMR peak with good signal-to-noise ratio and over time stability, making them promising as 19F-MRI traceable probes. The highest generation FJD, instead, presented an interesting morphological transition from multilamellar dendrimersomes to tubules as a consequence of a subtle balance of intra- and intermolecular forces that compete at the interface. Interestingly, a reduction of the local mobility of CF3 groups passing from dendrimersomes to tubules switches off the 19F NMR signal. The transition mechanism has been rationalized by coarse-grain simulations as well as demonstrated by using cosolvents of different nature (e.g., fluorinated) that promote conformational changes, ultimately reflected in the self-assembly behavior. Short and branched fluorinated chains have here been demonstrated as new moieties for the design of FJDs with tunable self-assembly behavior for potential applications as biocompatible 19F MRI probes in the construction of theranostic platforms.

Tailor made synthesis of water-soluble polythiophene-graft-poly(caprolactone-block-dimethylaminoethyl methacrylate) copolymer and their pH tunable self-assembly and optoelectronic properties

Here, we report a novel water-soluble polythiophene graft block copolymer i.e.; polythiophene-graft-poly(caprolactone-block-dimethylaminoethyl methacrylate)(PTh-g-PCL-b-PDMAEMA, P1) using combined polymerization techniques e.g. oxidative polymerization, ring-opening polymerization (ROP), atom-transfer radical polymerization (ATRP), and click chemistry; where π-conjugated polythiophene (PTh) is situated as the main chain and polycaprolactone-block-poly(dimethylamino ethyl methacrylate) remains anchored from the PTh backbone. The final polymer was characterized by 1H NMR and FT-IR spectroscopy. Self-assembly behavior of the P1 polymer is investigated by high resolution-transmission electron microscopy and dynamic light scattering. Interestingly, both UV–vis and fluorescence emission peaks are shifted gently towards higher wavelength region for decreasing pH from 10 to 3, plausibly due to extension of PTh backbone caused by the repulsion of protonated –NMe2 group of grafted PDMAEMA segment. The results show variation of nanostructures from micelle to vesicle to multi-vesicular assembly with the variation of pH from 3 to 7 to 10. The dc-conductivity values at pH 3, 7, 10 are 0.40 ± 0.09, 0.11 ± 0.04, and 0.12 ± 0.04 μS/cm, respectively and the highest value at pH 3 is for the uncoiled polythiophene chain arising from the ionic repulsion of protonated -N(CH3)2 group of grafted PDMAEMA block. The I-V characteristic data shows semiconducting nature with signature of organic mixed electronic and ionic conductivity (OMEIC) at pH3.

A unique amphiphilic triblock copolymer, nontoxic to human blood and potential supramolecular drug delivery system for dexamethasone

The drug delivery system (DDS) often causes toxicity, triggering undesired cellular injuries. Thus, developing supramolecules used as DDS with tunable self-assembly and nontoxic behavior is highly desired. To address this, we aimed to develop a tunable amphiphilic ABA-type triblock copolymer that is nontoxic to human blood cells but also capable of self-assembling, binding and releasing the clinically used drug dexamethasone. We synthesized an ABA-type amphiphilic triblock copolymer (P2L) by incorporating tetra(aniline) TANI as a hydrophobic and redox active segment along with monomethoxy end-capped polyethylene glycol (mPEG2k; Mw = 2000 g mol−1) as biocompatible, flexible and hydrophilic part. Cell cytotoxicity was measured in whole human blood in vitro and lung cancer cells. Polymer-drug interactions were investigated by UV–Vis spectroscopy and computational analysis. Our synthesized copolymer P2L exhibited tuned self-assembly behavior with and without external stimuli and showed no toxicity in human blood samples. Computational analysis showed that P2L can encapsulate the clinically used drug dexamethasone and that drug uptake or release can also be triggered under oxidation or low pH conditions. In conclusion, copolymer P2L is nontoxic to human blood cells with the potential to carry and release anticancer/anti-inflammatory drug dexamethasone. These findings may open up further investigations into implantable drug delivery systems/devices with precise drug administration and controlled release at specific locations.

Prospective on doping engineering of conductive polymers for enhanced interfacial properties

Conductive polymers that combine the advantages of traditional polymers and organic conductors have recently received more and more attention in applications such as sensors, smart electronics, display, and energy conversion/storage. Interface properties including conductivity, mechanical properties, and mass transport/immobilization are key factors affecting the performance of these devices. Doping engineering provides an effective method to enhance interface properties of conducting polymers and bring new functions for practical applications. In this Perspective, we review some application examples of doping-tunable interfacial properties of conducting polymers with advanced features, i.e., enhancing conductivity by doping; tunable self-assembly of conductive polymers; structure-derived elasticity and its application in flexible pressure sensors; and enhanced interfacial transport and its applications in biosensors and lithium ion battery. Furthermore, this Perspective also discusses the challenges of this field and some possible solutions.

Tunable self-assemblies of whey protein isolate fibrils for pickering emulsions structure regulation

Protein fibrils are potential emulsifiers with a highly pH-dependent structure. Therefore, the influence of pH on the self-assemblies of whey protein isolate (WPI) fibrils was investigated through turbidity, transmission electron microscopy, and small-angle X-ray scattering tests. Next, the effects of fibril structure on the interfacial profiles and physical properties of stabilized Pickering emulsions were studied. With an increase in pH from 2.0 to 5.0, the cross-sectional radius of WPI fibrils increased from 1.87 ± 0.12 nm to 7.75 ± 0.33 nm, while with a further increase in pH to 7.0, the fibrils decreased to single strand. For all pH conditions, the WPI fibrils effectively absorbed at the oil-water interface. At pH 5.0, the contact angle of fibrils was the maximum (50.6°), and the diffusion rate was the fastest. The d4,3 values of the WPI fibril-stabilized Pickering emulsions were around 70–80 μm with no significant differences. Moreover, the Pickering emulsions stabilized by fibrils assembled at pH 5.0 showed a predominantly elastic gel-like behavior and high stability. This work clarifies the relationship between the structure of assembled WPI fibrils and their emulsifying properties, and it provides a theoretical basis for developing emulsion-based delivery systems.

Glycopeptide-Conjugated Aggregation-Induced Emission Luminogen: A pH-Responsive Fluorescence Probe with Tunable Self-Assembly Morphologies for Cell Imaging.

pH values play an important role in various cell biological processes. Abnormal pH values in living systems are frequently associated with the development of diseases such as cancers, infection, and other diseases. Real-time monitoring of the changes of pH values in vivo will give us the significant indication for these diseases' progression. Within those pH-sensitive imaging probes, aggregation-induced emission (AIE) molecules exhibit great potential in aqueous imaging environment due to their high fluorescence quantum yield and stability. However, the modulation of the AIE probe with pH sensitivity and light-up property face challenges. Here, we introduced a new glycopeptide-modified AIE probe (TGO) based on the optimized solid-phase peptide synthesis approach. The response to pH of the peptide: DDDD progression changed hydrophobicity and hydrophilicity, resulting in the change of the amphipathicity balance. When modulating the pH from 5.5 to 8.0, the adverse protonation of the peptide induced assembled nanostructure transformation from nanolamellae to nanomicelles. Meanwhile, the pH-induced charge change in peptides can greatly influence the microenvironment of the AIEgen, resulting in the increase of fluorescence intensity.