Structural Modifications to Polystyrene via Self‐Assembling Molecules

We have previously reported that small quantities of self‐assembling molecules known as dendron rodcoils (DRCs) can be used as supramolecular additives to modify the properties of polystyrene (PS). These molecules spontaneously assemble into supramolecular nanoribbons that can be incorporated into bulk PS in such a way that the orientation of the polymer is significantly enhanced when mechanically drawn above the glass‐transition temperature. In the current study, we more closely evaluate the structural role of the DRC nanoribbons in PS by investigating the mechanical properties and deformation microstructures of polymers modified by self‐assembly. In comparision to PS homopolymer, PS containing small amounts (≤ 1.0 wt.‐%) of self‐assembling DRC molecules exhibit greater Charpy impact strengths in double‐notch four‐point bending and significantly greater elongations to failure in uniaxial tension at 250 % prestrain. Although the DRC‐modified polymer shows significantly smaller elongations to failure at 1000 % prestrain, both low‐ and high‐prestrain specimens maintain tensile strengths that are comparable to those of the homopolymer. The improved toughness and ductility of DRC‐modified PS appears to be related to the increased stress whitening and craze density that was observed near fracture surfaces. However, the mechanism by which the self‐assembling DRC molecules toughen PS is different from that of conventional additives. These molecules assemble into supramolecular nanoribbons that enhance polymer orientation, which in turn modifies crazing patterns and improves impact strength and ductility.     

Wrapping Chiral Nanoribbons into Coiled and Condensed Microstructures in Supramolecular Hydrogels

Hierarchical self‐assembly of small molecules into supramolecular structures across various length scales is of prominent importance to deeply understand and mimic the biological systems. Here, chiral nanoribbons that assembled from chiral phenylalanine and achiral coumarin derivatives can curve and grow into higher ordered hollow microstructures, which exhibit enhanced acid and alkali resistance. This is predominantly facilitated by the subtle hydrogen bonding interactions and specific steric hindrance between the two molecules. With the addition of metal ions and consequently, the extra association via coordination, these nanoribbons can wrap in a more condensed fashion and eventually form solid microstructures. This study provides implications in understanding the hierarchically biological self‐assembly process and is helpful for the construction of advanced artificial biomedical materials.     

Solvent‐Controlled Assembly of Aromatic Glutamic Dendrimers for Efficient Luminescent Color Conversion

A binary supramolecular system where self‐sorting and coassembly behavior can be switched by changing the solvent polarity is hereby reported. Glutamic dendron is separately conjugated with pyrene and naphthalimide luminophores through an alkyl spacer. The resulting structurally similar building units can self‐assemble into one‐dimensional micro/nanostructures with hexagonal and lamellar packing, respectively. Varying solvents from polar aqueous solution to nonpolar decane is evidenced to profoundly inverse the superchirality and switch self‐sorted assembly to coassembly of the two building blocks. The moisture sensitivity of the naphthalimide moiety is considered the primary driving force for the self‐sorting phenomenon in aqueous solution, resulting in inevitable hydration to repel its stacking with hydrophobic pyrene moiety. On the other hand, the naphthalimide unit can integrate segmentally with the pyrene unit in decane, greatly facilitating the nanofiber growth and supramolecular gel formation along with improved energy transfer efficiency between luminophores. As a result, the coassembly‐based thin films show efficient luminescent color conversion upon the UV light irradiation. This research presents a useful route for the fabrication of controllable solution‐processed light emitting devices from self‐assembled multicomponent systems.     

Supramolecular Nanofibers of Curcumin for Highly Amplified Radiosensitization of Colorectal Cancers to Ionizing Radiation

Development of highly efficient radiosensitizers is urgently desirable for addressing the resistance of cancer cells to ionizing radiation, which is the main reason for the failure of radiotherapy. Here, it is reported for the first time that supramolecular nanomaterials can serve as an excellent nanoplatform for developing superior radiosensitizers. A new curcumin‐based supramolecular nanofiber (Cur‐SNF) by virtue of a self‐assembling short peptide is developed, which greatly boosts the radiosensitivity of colorectal cancers to ionizing radiation. The drug–peptide conjugate Curcumin‐FFE‐CS‐EE is synthesized and can self‐assemble into small‐molecule hydrogel containing Cur‐SNFs triggered by reductant. In vitro and in vivo radiosensitization studies reveal that as compared to free curcumin Cur‐SNFs show much better performance as a radiosensitizer to sensitize colorectal cancer cells to ionizing radiation thanks to the supramolecular nanostructure. Due to the exceptionally high radiosensitization efficacy, Cur‐SNFs in combination with radiation realize significant reduction in tumor volume in vivo. Besides, the molecular mechanism studies demonstrate that Cur‐SNFs promote the radiosensitivity of colorectal cancer cells through inhibiting radiation‐induced nuclear factor kappa B activation. Cur‐SNF achieves an ultralarge sensitizer enhancement ratio at 10% cell survival value of 2.01, the highest among currently reported curcumin‐based radiosensitizers.     

Supramolecular Photothermal Nanomaterials as an Emerging Paradigm toward Precision Cancer Therapy

The concept of the “supramolecular photothermal effects” refers to the collection property and photothermal conversion efficiency resulting from the supramolecular assembly of molecular photothermal sensitizers. This review considers organic supramolecular photothermal materials assembled at the nanoscale via various molecular self‐assembly strategies and associated with the organization of multiple noncovalent interactions. In these materials, the individual photosensitizer molecules are typically aggregated through self‐assembly in a certain form that exhibits enhanced biostability, increased photothermal conversion efficiency with photoluminescence quenching, and improved photothermal therapeutic effects in comparison with those of the monomeric photosensitizer molecules. These supramolecular photothermal effects are controlled or influenced by intermolecular noncovalent interactions, especially the hydrophobic effects, which are distinct from the mechanisms of conventional sensitizer molecules and polymers and inorganic photothermal agents. A focus lies on how self‐assembly strategies give rise to supramolecular photothermal effects, including polymer and protein fabrication, small molecule self‐assembly, and the construction of donor–acceptor binary systems. Emphases are placed on the rational design of supramolecular photothermal nanomaterials, drug delivery, and in vivo photothermal therapeutic effects. Finally, the key challenges and promising prospects of these supramolecular photothermal nanomaterials in terms of both technical advances and clinical translation are discussed.     

Macroscopically Aligned Ionic Self‐Assembled Perylene‐Surfactant Complexes within a Polymer Matrix

Ionic self‐assembled (ISA) surfactant complexes present a facile concept for self‐assembly of various functional materials. However, no general scheme has been shown to allow their overall alignment beyond local polydomain‐like order. Here we demonstrate that ionic complexes forming a columnar liquid‐crystalline phase in bulk can be aligned within polymer blends upon shearing, taken that the matrix polymers have sufficiently high molecular weight. We use an ISA complex of N,N′‐bis(ethylenetrimethylammonium)perylenediimide/bis(2‐ethylhexyl) phosphate (Pery‐BEHP) blended with different molecular weight polystyrenes (PS). Based on X‐ray scattering studies and transmission electron microscopy the pure Pery‐BEHP complex was found to form a two‐dimensional oblique columnar phase where the perylene units stack within the columns. Blending the complex with PS lead to high aspect ratio Pery‐BEHP aggregates with lateral dimension in the mesoscale, having internal columnar liquid‐crystalline order similar to the pure Pery‐BEHP complex. When the Pery‐BEHP/PS blend was subjected to a shear flow field, the alignment of perylenes can be achieved but requires sufficiently high molecular weight of the polystyrene matrix. The concept also suggests a simple route for macroscopically aligned nanocomposites with conjugated columnar liquid‐crystalline functional additives.     

Hierarchical Self‐Assembly of Peptide‐Coated Carbon Nanotubes

Numerous applications, from molecular electronics to super‐strong composites, have been suggested for carbon nanotubes. Despite this promise, difficulty in assembling raw carbon nanotubes into functional structures is a deterrent for applications. In contrast, biological materials have evolved to self‐assemble, and the lessons of their self‐assembly can be applied to synthetic materials such as carbon nanotubes. Here we show that single‐walled carbon nanotubes, coated with a designed amphiphilic peptide, can be assembled into ordered hierarchical structures. This novel methodology offers a new route for controlling the physical properties of nanotube systems at all length scales from the nano‐ to the macroscale. Moreover, this technique is not limited to assembling carbon nanotubes, and could be modified to serve as a general procedure for controllably assembling other nanostructures into functional materials.     

Nanoengineering Hybrid Supramolecular Multilayered Biomaterials Using Polysaccharides and Self‐Assembling Peptide Amphiphiles

Developing complex supramolecular biomaterials through highly dynamic and reversible noncovalent interactions has attracted great attention from the scientific community aiming key biomedical and biotechnological applications, including tissue engineering, regenerative medicine, or drug delivery. In this study, the authors report the fabrication of hybrid supramolecular multilayered biomaterials, comprising high‐molecular‐weight biopolymers and oppositely charged low‐molecular‐weight peptide amphiphiles (PAs), through combination of self‐assembly and electrostatically driven layer‐by‐layer (LbL) assembly approach. Alginate, an anionic polysaccharide, is used to trigger the self‐assembling capability of positively charged PA and formation of 1D nanofiber networks. The LbL technology is further used to fabricate supramolecular multilayered biomaterials by repeating the alternate deposition of both molecules. The fabrication process is monitored by quartz crystal microbalance, revealing that both materials can be successfully combined to conceive stable supramolecular systems. The morphological properties of the systems are studied by advanced microscopy techniques, revealing the nanostructured dimensions and 1D nanofibrous network of the assembly formed by the two molecules. Enhanced C2C12 cell adhesion, proliferation, and differentiation are observed on nanostructures having PA as outermost layer. Such supramolecular biomaterials demonstrate to be innovative matrices for cell culture and hold great potential to be used in the near future as promising biomimetic supramolecular nanoplatforms for practical applications.     

Highly Efficient Multifunctional Supramolecular Gene Carrier System Self‐Assembled from Redox‐Sensitive and Zwitterionic Polymer Blocks

It has been a challenge to incorporate multiple features into a single gene carrier system to overcome numerous hurdles during the gene delivery. Herein, a supramolecular approach for building a multifunctional gene carrier system is demonstrated with the functions of disulfide bond based reduction‐responsive degradation and zwitterionic phosphorylcholine based extracellular stabilization and favorable cellular uptake. The gene carrier system is self‐assembled from two molecular building blocks: one host polymer, which is a redox‐sensitive β‐cyclodextrin based cationic star polymer, and one guest polymer, which is adamantyl end capped zwitterionic phosphorylcholine based polymer. The host and guest polymers self‐assemble to integrate multiple functions into one system, based on the host‐guest interaction between β‐cyclodextrin and adamantyl moieties. With the rational designs of both building blocks, the supramolecular gene carrier system possesses excellent protein stability, serum tolerance, cellular uptake and intracellular DNA release properties, and also low cytotoxicity. These features work simultaneously to achieve exceptionally high gene transfection efficiency, which is proven in MCF‐7 cell cultures using luciferase and green fluorescence protein reporter genes. Finally, the supramolecular gene carrier is applied to deliver the therapeutic p53 anti‐cancer gene in MCF‐7 cells, showing great potential for cancer gene therapy application.     

Organic–Inorganic Hierarchical Self‐Assembly into Robust Luminescent Supramolecular Hydrogel

Luminescent hydrogels are of great potential for many fields, particularly serving as biomaterials ranging from fluorescent sensors to bioimaging agents. Here, robust luminescent hydrogels are reported using lanthanide complexes as emitting sources via a hierarchical organic–inorganic self‐assembling strategy. A new organic ligand is synthesized, consisting of a terpyridine unit and two flexibly linked methylimidazole moieties to coordinate with europium(III) (Eu³⁺) tri‐thenoyltrifluoroacetone (Eu(TTA)₃), leading to a stable amphiphilic Eu³⁺‐containing monomer. Synergistic coordination of TTA and terpyridine units allows the monomer to self‐assemble into spherical micelles in water, thus maintaining the luminescence of Ln complexes in water. The micelles further coassemble with exfoliated Laponite nanosheets coated with sodium polyacrylate into networks based on the electrostatic interactions, resulting in the supramolecular hydrogel possessing strong luminescence, extraordinary mechanical property, as well as self‐healing ability. The results demonstrate that hierarchical organic–inorganic self‐assembly is a versatile and effective strategy to create luminescent hydrogels containing lanthanide complexes, giving rise to great potential applications as a soft material.     

Modeling Polymer Dielectric/Pentacene Interfaces: On the Role of Electrostatic Energy Disorder on Charge Carrier Mobility

Force‐field and quantum‐chemical calculations are combined to model the packing of pentacene molecules at the atomic level on two polymer dielectric layers (poly(methyl methacrylate) (PMMA) versus polystyrene (PS)) widely used in field‐effect transistors and to assess the impact of electrostatic interactions at the interface on the charge mobility values in the pentacene layers. The results show unambiguously that the electrostatic interactions introduce a significant energetic disorder in the pentacene layer in contact with the polymer chains; a drop in the hole mobility by a factor of 5 is predicted with PS chains while a factor of 60 is obtained for PMMA due to the presence of polar carbonyl groups.     

Solid‐State Light Emission Controlled by Tuning the Hierarchical Superstructure of Self‐Assembled Luminogens

Solid‐state luminescence is an important strategy for color generation via molecular self‐assembly. Here, a new luminogen (AT₃EMIS) containing both a rigid chromophore and a flexible dendron is designed and synthesized for multicolor emission. The emission energy of the target material is precisely controlled by adjusting three different columnar arrays through thermal and mechanical stimulation. With well‐defined supramolecular organizations in different length scales, the luminescent properties of the light switch can be tuned.     

Hierarchical Self‐Assembly of a Dandelion‐Like Supramolecular Polymer into Nanotubes for use as Highly Efficient Aqueous Light‐Harvesting Systems

A dandelion‐like supramolecular polymer (DSP) with a “sphere‐star‐parachute” topological structure consisting of a spherical hyperbranched core and many parachute‐like arms is constructed by the non‐covalent host–guest coupling between a cyclodextrin‐endcapped hyperbranched multi‐arm copolymer (host) and many functionalized adamantanes with each having three alkyl chain arms (guests). The obtained DSPs can further self‐assemble into nanotubes in water in a hierarchical way from vesicles to nanotubes through sequential vesicle aggregation and fusion steps. The nanotubes have a bilayer structure consisting of multiple “hydrophobic‐hyperbranched‐hydrophilic” layers. Such a structure is very useful for constructing a chlorosome‐like artificial aqueous light‐harvesting system, as demonstrated here, via the incorporation of hydrophobic 4‐(2‐hydroxyethylamino)‐7‐nitro‐2,1,3‐benzoxadiazole as donors inside the hyperbranched cores of the nanotubes and the hydrophilic Rhodamine B as the acceptors immobilized on the nanotube surfaces. This as‐prepared nanotube light harvesting system demonstrates unexpectedly high energy transfer efficiency (above 90%) in water. This extends supramolecular polymers with more complex topological structure, special self‐assembly behavior, and new functionality.     

Reversible Quadruple Switching with Optical,Chiroptical, Helicity,and Macropattern in Self‐Assembled Spiropyran Gels

Enantiomeric glutamate gelators containing a spiropyran moiety are designed and found to self‐assemble into a nanohelix through gelation. Upon alternating UV and visible light irradiation, the spiropyran experiences a reversible change between a blue zwitterionic merocyanine state and a colorless closed ring state spiropyran in supramolecular gels. This photochromic switch causes a series of subsequent changes in the optical, chiroptical, morphological properties from supramolecular to macroscopic levels. While the solution of the gelator molecules does not show any circular dichroism (CD) signal in the region of 250–700 nm due to the fact that the chromophore is far from the chiral center, the gel shows chiroptical signals such as CD and circularly polarized luminescence (CPL) because of the chirality transfer by the self‐assembly. These signals are reversible upon alternating UV/vis irradiation. Therefore, a quadruple optical and chiroptical switch is developed successfully. During such process, the self‐assembled nanostructures from the enantiomeric supramolecular gels also undergo a reversible change between helices and fibers under the alternating UV and visible light trigger. Furthermore, a rewritable material fabricated from their xerogels on a glass is developed. Such rewritable material can be efficiently printed over 30 cycles without significant loss in contrast and resolution using UV and visible light.     

Hierarchical Superstructures with Helical Sense in Self‐Assembled Achiral Banana‐Shaped Liquid Crystalline Molecules

The self‐assembly of 1,3‐phenylene bis[4‐(4‐n‐heptyloxybenzoyloxy)‐benzoates] (BC7) is studied to examine the formation of helical morphologies from achiral banana‐shaped liquid crystal molecules at different self‐assembling levels. Various hierarchical superstructures including flat‐elongated lamellar crystal, left‐ and right‐handed helical ribbons, and tubular texture are observed while the BC7 molecules self‐assemble in THF/H₂O solution. By contrast, only plate‐like morphology is observed in the self‐assembly of achiral linear shaped 1,4‐phenylene bis[4‐(4‐n‐heptyloxybenzoyloxy)‐benzoates] (LC7) molecules, indicating that the chirality of the self‐assembled texture is strongly dependent upon the molecular geometry of the achiral molecules. The formation of the helical superstructures, namely hierarchical chirality, is attributed to the conformational chirality from the achiral banana‐shaped liquid crystalline molecules, as evidenced by significant optical activity in time‐resolved circular dichroism experiments. Selective area electron diffraction is performed to examine the structural packing of the hierarchical superstructures. As observed, the molecular disposition of the lamellar crystal is identical to that of the helical superstructure. Also, the diffraction patterns of the helical superstructures appeared arc‐like patterns consisting of a series of reflections, suggesting that the helical morphology resulted from the curving of the lamellar crystals through a twisting and bending mechanism. Consequently, the model of molecular disposition in the self‐assembled helical superstructures from the achiral banana‐shaped molecules is proposed. The morphological evolution in this study may provide further understanding with respect to the chiral information transfer mechanism from specific molecular geometry to hierarchical chirality in the achiral banana‐shaped molecules.     

Self‐Assembled Sugar‐Substituted Perylene Diimide Nanostructures with Homochirality and High Gas Sensitivity

A new symmetrical sugar‐based perylenediimide derivative PTCDI‐BAG is synthesized and its aggregate morphologies and formation mechanisms are studied in detail in the mixed solvent system water/N,N‐dimethylformamide (H₂O/DMF) with changing volume ratios. PTCDI‐BAG molecules self‐assemble into planar ribbons in 20/80 and 40/60 H₂O/DMF (v/v), but their chiralities are opposite according to recorded circular dichroism (CD) spectra. With a further increase of the water content, only left‐handed helical nanowires are obtained in 60/40 and 80/20 H₂O/DMF (v/v) mixtures. By combining density functional theory (DFT) calculations with the experimental investigations, it is proposed that kinetic and thermodynamic factors play key roles in tuning PTCDI‐BAG structures and helicity. The formation of the ribbon is thermodynamically controlled in the 20/80 H₂O/DMF system, but kinetically controlled nucleation followed by thermodynamically controlled self‐assembly plays the governing roles for the formation of nanoribbons in 40/60 H₂O/DMF. Devices based on single nanoribbons for hydrazine sensing exhibit better performance than nanofiber bundles obtained in this study and achiral nanostructures reported in previous study. This study not only provides an elaborated route to tuning the structures and helicity of PTCDI molecules, but also provides new possibilities for the construction of high‐performance nanodevices.     

Impact of Polystyrene Oligomer Side Chains on Naphthalene Diimide–Bithiophene Polymers as n‐Type Semiconductors for Organic Field‐Effect Transistors

A series of naphthalene diimide‐based conjugated polymers are prepared with various molar percentage of low molecular weight polystyrene (PS) oligomer of narrow polydispersity as the side chain. The PS side chains are incorporated through preparation of a macromonomer by chain termination of living anionic polymerization. The effects of the PS side chains amount (0–20 mol%) versus overall sidechain on the electrical properties of the resulting polymers as n‐type polymer semiconductors in field‐effect transistors are investigated. We observe that all the studied polymers show similarly high electron mobility (≈0.2 cm² V^?1 s^?1). Importantly, the polymers with high PS side chain content (20 mol%) show a significantly improved device stability under ambient conditions, when compared to the polymers at lower PS content (0–10 mol%). By comparing this observation to the physical blending of the conjugated polymer with PS, we attribute the improved stability to the covalently attached PS side chains potentially serving as a molecular encapsulating layer around the conjugated polymer backbone, rendering it less susceptible to electron traps such as oxygen and water molecules.     

Polymer‐Modified ZnO Nanoparticles as Electron Transport Layer for Polymer‐Based Solar Cells

The optimization of interfacial layer plays a critical role in the ultimate use of polymer‐based solar cells (PSCs). By introducing an insulating polymer, polystyrene (PS), into the ZnO nanoparticles (NPs) with large particle size, an electron transport layer (ETL) with a thickness of more than 130 nm is produced. The doping of PS not only improves the film quality of ZnO NPs to generate a denser, smoother, and more uniform ETL, but also increases the contact properties between the hydrophilic ZnO and hydrophobic active layer. In comparison to control devices, the power conversion efficiencies (PCEs), short circuit current densities, and fill factors of PSCs with the PS‐modified ETL for a typical fullerene system PTB7‐Th:PC₇₁BM and, also, a nonfullerene system PBDB‐T:ITIC are increased, with PCEs from 8.49% to 9.54% and 10.03% to 11.05%, respectively. The reproducibility, mechanical endurance, and ambient stability of the PSCs with the PS‐modified ZnO NP ETL are significantly improved. The combination of the insulating polymer and ZnO NPs provides a simple, low‐cost way to realize the commercialization of high performance, flexible PSCs.     

Cover Picture: A Route to Self‐Organized Honeycomb Microstructured Polystyrene Films and Their Chemical Characterization by ToF‐SIMS Imaging (Adv. Funct. Mater. 7/2007)

The cover shows a composition of different characterization images of an auto‐organized polystyrene film obtained through breath‐figure imprinting, as reported by Sami Yunus and co‐workers on p. 1079. Water‐droplet condensation, represented as a synthetic perspective image (top), is responsible for ordered microstructuring during film formation. The following perspectives are taken from SEM and from three negative ToF‐SIMS images that allow deduction of the surface chemical composition. The background is an SEM picture of a polydimethylsiloxane molding of the self‐organized film. A new type of polymer compound that allows the formation of highly ordered microstructured films by casting from a volatile solvent in the presence of humidity, and its characterization by ToF‐SIMS (time‐of‐flight secondary‐ion mass spectrometry) are presented. A honeycomb structure is obtained by activation of 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl (TEMPO)‐terminated polystyrene (PS) with p‐toluenesulfonic acid (PTSA). The mechanism of this activation reaction, leading to a more polar PS termination, is deduced from simple experiments and supported by ToF‐SIMS characterization. Positive and negative ToF‐SIMS imaging allows different chemical regions correlating to the film morphology to be distinguished. This new, straightforward activation process, together with ToF‐SIMS chemical imaging, provides a better understanding of the phenomena underlying the formation of these films by directly linking the role of polar terminations to the microscale self‐organization. This new method, transposable to other organic acids, suggests interesting new perspectives in the field of self‐organized chemical and topographical patterning.     

Fibrillar Constructs from Multilevel Hierarchical Self‐Assembly of Discotic and Calamitic Supramolecular Motifs

We here report on polymeric solid‐state self‐assembly leading to organization over six length scales, ranging from the molecular scale up to the macroscopic length scale. We combine several concepts, i.e., rod‐like helical and disc‐like liquid crystallinity, block copolymer self‐assembly, DNA‐like interactions to form an ionic polypeptide–nucleotide complex and packing frustration to construct mesoscale fibrils. Ionic complexation of anionic deoxyguanosine monophosphate (dGMP) and triblock coil–rod–coil copolypeptides is used with cationic end blocks and a helical rod‐like midblock. The guanines undergo Hoogsteen pairing to form supramolecular discs, they π‐stack into columns that self‐assemble into hexagonal arrays that are controlled by the end blocks. Packing frustration between the helical rods from the block copolymer midblock and the discotic motif limits the lateral growth of the assembly thus affording mesoscale fibrils, which in turn, form an open fibrillar network. The concepts suggest new rational methodologies to construct structures on multiple length scales in order to tune polymer properties.