Decoding the Pathway-Dependent Self-Assembly of Polymer-Grafted Nanoparticles by Ligand Crystallization.

Functional metamaterials can be constructed by assembling nanoparticles (NPs) into well-ordered structures, which show fascinating properties at different length scales. Using polymer-grafted NPs (PGNPs) as a building block, flexible composite metamaterials can be obtained, of which the structure is significantly affected by the property of polymer ligands. Here, it is demonstrated that the crystallization of polymer ligands determines the assembly behavior of NPs and reveal a pathway-dependent self-assembly of PGNPs into different metastructures in solution. By changing the crystallization degree of polymer ligands, the arrangement structure of NPs can be tailored. When the polymer ligands highly crystallize, the PGNPs assemble into diamond-shaped platelets, in which the NPs arrange disorderedly. When the polymer ligands lowly crystallize, the PGNPs assemble into highly ordered 3D superlattices, in which the NPs pack into a body-centered-cubic structure. The structure transformation of PGNP assemblies can be achieved by thermal annealing to regulate the crystallization of polymer ligands. Interestingly, the diamond-shaped platelets remain "living" for seeded epitaxial growth of newly added crystalline species. This work demonstrates the effects of ligand crystallization on the crystallization of NP, providing new insights into the structure regulation of metamaterials.

Effect of Polymeric Ligand Grafting Region on Confined Assembly of Gold Nanorods in cylindrical nanopores.

The grafting region of polymeric ligands exhibit a significant influence on the assembly behavior of polymer tethered gold nanorods (AuNRs) in confined space. In this work, the effect of core size, molecular weight and grafting region of ligands on the assembly structure in cylindrical nanopores was investigated. It is found that polystyrene end-tethered AuNR (AuNR@End-PS) exhibits a dumbbell-like shape, while the AuNR with PS tethered on the entire surface (AuNR@Full-PS) shows a rod-like morphology that gradually transforms into a spherical shape as the molecular weight increases. AuNR@End-PS is affected by the special steric hindrance at both ends, and prefers to form special structures such as inclination arrangement, whereas AuNR@Full-PS prefers to be arranged shoulder-to-shoulder in a chain-like assembly. The confinement effect was studied as well by varying the diameter of pores. The results show that the nanoparticles prefer to arrange into a regular and ordered assembly structure in the strong confinement spaces. Under the synergy of confined spaces and ligands at both ends, the AuNRs@End-PS are more likely to form a tilted order-assembly structure. The results of this work could provide new ideas and guidance for the preparation of ordered assembly of AuNRs with novel structures.

Fabrication of Oriented Colloidal Crystals from Capillary Assembly of Polymer-Tethered Gold Nanoparticles.

Self-assembled colloidal crystals (CCs) or nanoparticle (NPs) superlattices have attracted significant attention due to their potential applications in many fields. However, due to the complex interactions that govern the self-assembly, it is difficult to predict and control the superstructure organization of CCs. Herein, a facile yet effective way is demonstrated to fabricate oriented CCs from capillary assembly of polymer-tethered gold NPs (AuNPs). Assembly mechanism of polymer-tethered AuNPs and their superlattice structures are systematically studied by in situ small-angle X-ray scattering (SAXS) technology. The results show that the oriented CCs of polymer-tethered AuNPs can be obtained upon solvent evaporation in a capillary tube and the oriented structure is mainly determined by the chain length of polymer ligands and size of AuNPs. Assembly of AuNPs tethered by short-chain ligand can result in oriented face-centered cubic (fcc) superlattice, whereas AuNPs tethered by long-chain ligand can assemble into an oriented body-centered tetragonal (bct) superlattice structure. Interestingly, in situ SAXS study shows that for the sample of bct superlattice structure, a transformation from fcc to bct superlattice upon solvent evaporation is observed, which strongly depends on chain length of ligands. This work provides a useful guide for polymer-tethered AuNPs to prepare orientation colloidal crystals.

Construction of Supramolecular Liquid-Crystalline Metallacycles for Holographic Storage of Colored Images.

Design and construction of new functionalized supramolecular coordination complexes (SCCs) via coordination-driven self-assembly strategy is highly important in supramolecular chemistry and materials science. Herein, we present a family of well-defined metallacycles decorated with mesogenic forklike dendrons through the strategy of coordination-driven self-assembly. Due to the existence of mesogenic forklike dendrons, the obtained metallacycles displayed the smectic A liquid crystal phase at room temperature while their precursors exhibited the rectangular columnar liquid crystal phase. Interestingly, by taking advantage of the electrostatic interactions between the positively charged metallacycle and the negatively charged heparin, the doping of heparin induced a significant change of the liquid-crystalline behaviors of metallacycles. More importantly, the prepared liquid-crystalline metallacycles could be further applied for holographic storage of colored images. Notably, the rhomboidal metallacycle and hexagonal metallacycle gave rise to different holographic performances although they featured a similar liquid crystal phase behavior. Therefore, this research not only provides the first successful example of supramolecular liquid-crystalline metallacycles for holographic storage of colored images but also opens a new door for supramolecular liquid-crystalline metallacycles toward advanced optical applications.

Tunable Photonic Microspheres of Comb-Like Supramolecules.

Photonic crystals (PCs) are ideal candidates for reflective color pigments with high color purity and brightness due to tunable optical stop band. Herein, the generation of PC microspheres through 3D confined supramolecular assembly of block copolymers (polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP) and small molecules (3-n-pentadecylphenol, PDP) in emulsion droplets is demonstrated. The intrinsic structural colors of the PC microspheres are effectively regulated by tuning hydrogen-bonding interaction between P2VP blocks and PDP, where reflected color can be readily tuned across the whole visible spectrum range. Also, the effects of both PDP and homopolymer (hPS) on periodic structure and optical properties of the microspheres are investigated. Moreover, the spectral results of finite element method (FEM) simulation agree well with the variation of structural colors by tuning the periodicity in PC microspheres. The supramolecular microspheres with tunable intrinsic structural color can be potentially useful in the various practical applications including display, anti-counterfeit printing and painting.

Diffusion behavior of peptide amphiphiles containing different numbers of alkyl tails at a hydrophobic solid-liquid interface: single molecule tracking investigation.

Using the single molecule tracking technique, the diffusion behavior of peptide amphiphiles (PAs) with different numbers of alkyl tails at a hydrophobic solid-liquid interface has been investigated. The effect of the number of alkyl tails of PAs on molecular trajectories at the hydrophobic solid-liquid interface has been systematically studied. PA molecules display an intermittent motion consisting of immobilization and hopping processes, which has been well simulated by the continuous time random walk (CTRW) model. The results reveal that the hydrophobic interaction between the PAs and hydrophobic surface plays an important role in the diffusion behavior of PAs. Increasing the number of alkyl tails in PAs systematically reduces the mobility of PAs on the hydrophobic surface. Moreover, the diffusion behavior of PAs at the hydrophobic interface also shows pH dependence. A decrease in pH is beneficial to the motion of all PAs on the hydrophobic surface, which can be ascribed to the protonation of PAs in acidic solutions. Therefore, the hydrophobic interaction is crucial to the transport of peptide amphiphiles at hydrophobic interfaces which would be important for the design of peptides in biological applications.

Visible light-triggered gel-to-sol transition in halogen-bond-based supramolecules.

Photoresponsive supramolecular gels have aroused continuous attention because of their extensive applications; however, most studies utilize UV light, which inevitably brings about some health and environmental issues. The halogen bond is an important driving force for constructing supramolecules due to its high directionality, tunable strength, good hydrophobicity, and large size of the halogen atoms. Yet, it still remains a formidable challenge to utilize halogen bonds as a driving force to fabricate a visible light responsive gel. In this work, to fabricate such a gel, azopyridine-containing Azopy-Cn (n = 8, 10, 12) was selected as a halogen bond acceptor, while 1,2-bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene (BTFIPD) was chosen as both the halogen bond donor and visible light responsive moiety. The visible light response of BTFIPD resulted from the significant separation of n-π* energy levels between trans and cis isomers due to the introduction of an electron-withdrawing group (fluorine) to azobenzene at the ortho-position. Interestingly, the gel exhibited a good gel-to-sol transition behavior upon green light irradiation. At the same time, the morphologies varied from uniform narrow flakes to broad sheets with increasing illumination time. We provide an environmentally-friendly visible light-triggered method to regulate the phase transition of supramolecular materials in applications ranging from energy conversion to information storage.

Dopant-Free Squaraine-Based Polymeric Hole-Transporting Materials with Comprehensive Passivation Effects for Efficient All-Inorganic Perovskite Solar Cells.

Development of high-performance dopant-free hole-transporting materials (HTMs) with comprehensive passivation effects is highly desirable for all-inorganic perovskite solar cells (PVSCs). Squaraines (SQs) could be a candidate for dopant-free HTMs as they are natural passivators for perovskites. One major limitation of SQs is their relatively low hole mobility. Herein we demonstrate that polymerizing SQs into pseudo two dimensional (2D) p-π conjugated polymers could overcome this problem. By rationally using N,N-diarylanilinosquaraines as the comonomers, the resulting polysquaraine HTMs not only exhibit suitable energy levels and efficient passivation effects, but also achieve very high hole mobility close to 0.01 cm-2 V-1 s-1 . Thus as dopant-free HTMs for α-CsPbI2 Br-based all-inorganic PVSCs, the best PCE reached is 15.5 %, outperforming those of the doped-Spiro-OMeTAD (14.4 %) based control devices and among the best for all-inorganic PVSCs.

Scalable production of structurally colored composite films by shearing supramolecular composites of polymers and colloids.

Structurally colored composite films, composed of orderly arranged colloids in polymeric matrix, are emerging flexible optical materials, but their production is bottlenecked by time-consuming procedures and limited material choices. Here, we present a mild approach to producing large-scale structurally colored composite films by shearing supramolecular composites composed of polymers and colloids with supramolecular interactions. Leveraging dynamic connection and dissociation of supramolecular interactions, shearing force stretches the polymer chains and drags colloids to migrate directionally within the polymeric matrix with reduced viscous resistance. We show that meter-scale structurally colored composite films with iridescence color can be produced within several minutes at room temperature. Significantly, the tunability and diversity of supramolecular interactions allow this shearing approach extendable to various commonly-used polymers. This study overcomes the traditional material limitations of manufacturing structurally colored composite films by shearing method and opens an avenue for mildly producing ordered composites with commonly-available materials via supramolecular strategies.

Electrostatically Controlled ex Situ and in Situ Polymerization of Diacetylene-Containing Peptide Amphiphiles in Living Cells.

Precise control of diacetylene-containing peptide amphiphile (DPA) based supramolecular architectures is important for their in cellulo polymerization behaviors and biomedical applications. Herein, we reported two DPAs (cationic PA-NH2 and zwitterionic PA-OH) with a similar molecular structure, which exhibited completely opposite polymerization behaviors in aqueous solution and living cells. Specifically, PA-NH2 was unpolymerizable in aqueous solution but underwent in cellulo polymerization to respond to the intracellular microenvironment. On the contrary, zwitterionic PA-OH was polymerized in solution, rather than inside living cells. Based on the results of cell viability and total internal reflection fluorescent microscopy measurement, PA-OH exhibited higher affinity with cell membranes and lower cytotoxicity than those of PA-NH2. Therefore, it is suggested that the in cellulo polymerization of PA-NH2 should be responsive for greater cytotoxicity, rather than the membrane affinity. This study provides an in-depth understanding of the role of charge properties in the polymerization behavior of DPAs and seeks their potential biomedical applications.

Revealing the dynamic adsorption and diffusion of peptide amphiphile on supported lipid bilayer by single molecule experiment and simulation.

Dynamic adsorption and diffusion of peptide amphiphiles (PAs) with different numbers of alkyl tails on supported lipid bilayers (SLBs) were investigated by single molecule tracking experiment and molecule dynamic simulation. Experimental results show two distinct populations of PAs with different residence time. Residence time of adsorbed PAs increases with the increase of the alkyl tails, whereas diffusion coefficient monotonically decreases with rising the number of alkyl tails and also decreases with increasing the mobility of SLBs. All-atom molecule dynamic simulation results prove that the adsorption and diffusion of PAs on SLB surface are mainly determined by interactions between PAs and SLBs and also the intrinsic mobility of PAs in aqueous solution. The electrostatic interactions and the mobility of PAs are two dominated but contradictory coefficients for the adsorption and diffusion of PAs. By increasing the alkyl tails, the mobility of PAs decreases while the electrostatic property does not change significantly, resulting in the increase of residence time and decrease of diffusivity of PAs. Additionally, for the PAs with large number of alkyl tails (≥ 3 alkyl tails), steric hindrance of alkyl tails leads to the decrease of adsorption probability of PAs on SLB surface. These findings lay the groundwork for guiding the design of PAs with high cell affinity, potentially useful for efficient drug delivery.

Self-Assembly of Polymer End-Tethered Gold Nanorods into Two-Dimensional Arrays with Tunable Tilt Structures.

We demonstrated a facile yet effective strategy for self-assembly of polymer end-tethered gold nanorods (GNRs) into tunable two-dimensional (2D) arrays with the assistance of supramolecules of hydrogen bonded poly(4-vinyl pyridine) (P4VP) and 3-n-pentadecylphenol (PDP). Well-ordered 2D arrays with micrometer size were obtained by rupturing the assembled supramolecular matrix with a selective solvent. The formation of long-range ordered 2D arrays during a drying process was observed via small-angle X-ray scattering. Interestingly, the packing structure of the ordered arrays strongly depends on the molecular weight (Mw) of the polymer ligands and the size of the GNRs. By increasing Mw of the polymer ligands, tilted arrays can be obtained. The average angle between GNRs and the surface normal direction of the layered 2D arrays changes from 0 to 37° with the increase in Mw of the polymer ligands. A mechanism for assembly behavior of dumbbell shapes with a soft shell structure has been proposed. The resulting GNR arrays with different orientations showed anisotropic surface-enhanced Raman scattering (SERS) performance. We showed that the vertically ordered GNR arrays exhibited ∼3 times higher SERS signals than the tilt ordered arrays. The results prove that the polymer end-tethered GNRs can be used as a building block for preparing the tilted 2D arrays with tunable physicochemical properties, which could have a wide range of potential applications in photonics, electronics, plasmonics, etc.

Lipidated gemini peptide amphiphiles with enhanced loading capacity and cell membrane affinity for drug delivery.

Lipidated peptide amphiphiles exhibit high affinity for plasma cell membranes, good cell internalization and improved stability against degradation, which make them attractive as a drug delivery system. However, low drug loading capacity limits their application for drug delivery. Herein, we developed a gemini peptide amphiphile with enhanced membrane activity and endosomal escape, containing dodecanoic acid hydrophobic tails at the N-terminus, rhodamine on the pendant chain and an active targeting peptide sequence (GRGDS). The presence of rhodamine not only provides high drug loading capability due to the π-π stacking interaction between camptothecin (CPT) and rhodamine, but also promotes peptide amphiphiles to form compact spherical micelles, as well as allows for fluorescence imaging. Single-molecule total internal reflection fluorescence microscopy investigation reveals gemini peptide amphiphile has higher affinity for plasma cell membranes than single-tail peptide amphiphile. Meanwhile, better cell internalization of gemini peptide amphiphile was confirmed by flow cytometry and confocal laser scanning microscopy. Moreover, CPT-loaded gemini peptide amphiphile induced enhanced cytotoxicity in cancer cells when compared to free CPT, indicating that lipidated peptide amphiphile with π-conjugates on the pendant chain and two hydrophobic tails can serve as a highly efficient drug delivery vehicle.

Dopant-Free Crossconjugated Hole-Transporting Polymers for Highly Efficient Perovskite Solar Cells.

Currently, there are only very few dopant-free polymer hole-transporting materials (HTMs) that can enable perovskite solar cells (PVSCs) to demonstrate a high power conversion efficiency (PCE) of greater than 20%. To address this need, a simple and efficient way is developed to synthesize novel crossconjugated polymers as high performance dopant-free HTMs to endow PVSCs with a high PCE of 21.3%, which is among the highest values reported for single-junction inverted PVSCs. More importantly, rational understanding of the reasons why two isomeric polymer HTMs (PPE1 and PPE2) with almost identical photophysical properties, hole-transporting ability, and surface wettability deliver so distinctly different device performance under similar device fabrication conditions is manifested. PPE2 is found to improve the quality of perovskite films cast on top with larger grain sizes and more oriented crystallization. These results help unveil the new HTM design rules to influence the perovskite growth/crystallization for improving the performance of inverted PVSCs.

Reversible photo-responsive gel-sol transitions of robust organogels based on an azobenzene-containing main-chain liquid crystalline polymer.

Stimuli-responsive supramolecular gels have been widely investigated, but the construction of a liquid crystalline gel with a high mechanical property and reversible photo-response still remains a challenge. This is due to the difficulty of designing gelators with liquid crystal properties and gelation abilities in organic solvents simultaneously. In this study, an azobenzene-containing main-chain polyester (Azo-mLCP) with a pendant amide group was synthesized. The organogel of Azo-mLCP via a hydrogen bond in dioxane possessed reversible thermal- and photo-responsive behaviours. The organogel exhibited a good self-supporting ability when the concentration of the gelator was more than 7.5 wt%. The rapid trans-to-cis isomerization of Azo-mLCP in solution was studied via UV-Vis absorption spectra. In addition, the gel-to-sol transition of the organogel could be triggered efficiently by an incomplete trans-to-cis conversion strategy. This study opens a way for the main-chain liquid crystalline polymers to serve in potential applications in photo-responsive robust actuators, electro-optical devices, and so on.

Highly Luminescent Liquid Crystals in Aggregation Based on Platinum(II) Complexes.

Luminescent liquid crystals (LLCs) attract considerable attention because of their broad applications in displays, chemosensors, and anti-counterfeiting. However, it remains challenging to achieve a high luminescence efficiency in LCs because of the common aggregation-caused quenching effect. Herein, we demonstrate a facile approach to designing LLCs with a high quantum yield up to 88% by deliberately tuning the aggregation behavior of platinum(II) complexes with alkoxy chains (CnH2n+1O-). LLCs in hexagonal columnar and rectangular columnar phases are achieved when n = 12 and 16, respectively, as revealed by one-dimensional wide-angle X-ray diffraction and small-angle X-ray scattering. These LLCs are able to not only exhibit strong emission at elevated temperatures but also show attractive reversible vapochromism upon alternative CH2Cl2 and EtOH fuming, which imparts added functions and promises technological utility.

Moebius strips of chiral block copolymers.

The Moebius topology (twisted, single-sided strip) is intriguing because of its structural elegance and distinct properties. Here we report the generation of block copolymer Moebius strips via a fast self-assembly of chiral block copolymer polystyrene-block-poly(D-lactide acid) (PS-b-PDLA) in tetrahydrofuran/water mixed solvents. The Moebius strip is formed by morphological evolution from large compound micelle (LCM) to spindle-like micelle (SLM) and then to toroid with a 180° twist along the ring. Mechanism insight reveals that a subtle balance of crystallization of PDLA and microphase separation between PS and PDLA chains dominates the formation of Moebius strips. An intriguing helix-helix transition occurs during the chiral transfer from microphase to assemblies, which is driven by relaxation of the internal stress within SLM related to orientated stretching of PS chains. Mesoporous chiral channels can be generated within Moebius strips after removal of PDLA, which are interesting in chiral recognition, separation and asymmetric catalysis.

Metallosupramolecular Photonic Elastomers with Self-Healing Capability and Angle-Independent Color.

Photonic elastomers that can change colors like a chameleon have shown great promise in various applications. However, it still remains a challenge to produce artificial photonic elastomers with desired optical and mechanical properties. Here, the generation of metallosupramolecular polymer-based photonic elastomers with tunable mechanical strength, angle-independent structural color, and self-healing capability is reported. The photonic elastomers are prepared by incorporating isotropically arranged monodispersed SiO2 nanoparticles within a supramolecular elastomeric matrix based on metal coordination interaction between amino-terminated poly(dimethylsiloxane) and cerium trichloride. The photonic elastomers exhibit angle-independent structural colors, while Young's modulus and elongation at break of the as-formed photonic elastomers reach 0.24 MPa and 150%, respectively. The superior elasticity of photonic elastomers enables their chameleon-skin-like mechanochromic capability. Moreover, the photonic elastomers are capable of healing scratches or cuts to ensure sustainable optical and mechanical properties, which is crucial to their applications in wearable devices, optical coating, and visualized force sensing.