Oligopeptide‐Assisted Self‐Assembly of Oligothiophenes: Co‐Assembly and Chirality Transfer

The biomolecule‐assisted self‐assembly of semiconductive molecules has been developed recently for the formation of potential bio‐based functional materials. Oligopeptide‐assisted self‐assembly of oligothiophene through weak intermolecular interactions was investigated; specifically the self‐assembly and chirality‐transfer behavior of achiral oligothiophenes in the presence of an oligopeptide with a strong tendency to form β‐sheets. Two kinds of oligothiophenes without (QT) or with (QTDA) carboxylic groups were selected to explore the effect of the end functional group on self‐assembly and chirality transfer. In both cases, organogels were formed. However, the assembly behavior of QT was quite different from that of QTDA. It was found that QT formed an organogel with the oligopeptide and co‐assembled into chiral nanostructures. Conversely, although QTDA also formed a gel with the oligopeptide, it has a strong tendency to self‐assemble independently. However, during the formation of the xerogel, the chirality of the oligopeptide can also be transferred to the QTDA assemblies. Different assembly models were proposed to explain the assembly behavior.     

Two‐Component Fibers/Gels and Vesicles Formed from Hetero‐Double‐Helices of Pseudoenantiomeric Ethynylhelicene Oligomers with Branched Side Chains

A methodology for the formation of fibers/gels and vesicles by molecular assembly and for controlling their properties is presented. Two‐component systems of pentamer (P)‐ 5 and tetramer (M)‐ 4 pseudoenantiomeric ethynylhelicenes with decyloxycarbonyl (D) and 4‐methyl‐2‐(2‐methylpropyl)‐1‐pentyloxycarbonyl (bD) side‐chains have been examined. Distinct aggregates were formed by changing the solvent for the three combinations of (P)‐bD‐ 5 /(M)‐bD‐ 4 , (P)‐D‐ 5 /(M)‐bD‐ 4 , and (P)‐D‐ 5 /(M)‐D‐ 4 . In toluene, (P)‐bD‐ 5 /(M)‐bD‐ 4 , (P)‐D‐ 5 /(M)‐bD‐ 4 , and (P)‐D‐ 5 /(M)‐D‐ 4 all formed gels and fibrous assemblies were observed by AFM. The minimum gel‐forming concentration (MGC) decreased in the order (P)‐bD‐ 5 /(M)‐bD‐ 4 >(P)‐D‐ 5 /(M)‐bD‐ 4 >(P)‐D‐ 5 /(M)‐D‐ 4 . In diethyl ether, vesicular formation was observed by dynamic light scattering (DLS), AFM, and TEM, and the size of the vesicles decreased in the order (P)‐bD‐ 5 /(M)‐bD‐ 4 >(P)‐D ‐ 5 /(M)‐bD‐ 4 >(P)‐D ‐ 5 /(M)‐D ‐ 4 . Both fiber/gel and vesicle formation were accompanied by enhanced CDs and redshifted UV/Vis absorption bands with a change in color to deep yellow. These are novel two‐component oligomeric systems that form assemblies of fibers/gels or vesicles depending on the solvent, and the structures and properties of the assemblies can be fine‐tuned by changing the combination of oligomers. In m‐difluorobenzene, a homogeneous solution was obtained with (P)‐D‐ 5 /(M)‐bD‐ 4 , which again exhibits enhanced CDs and redshifted UV/Vis absorptions. Vapor pressure osmometry analysis showed the formation of a bimolecular heteroaggregate. The study has indicated that pseudoenantiomeric oligomers form hetero‐double‐helices that hierarchically assemble to form fibers/gels and vesicles.     

Self‐Assembly Studies of a Chiral Bisurea‐Based Superhydrogelator

A chiral bisurea‐based superhydrogelator that is capable of forming supramolecular hydrogels at concentrations as low as 0.2 mM is reported. This soft material has been characterized by thermal studies, rheology, X‐ray diffraction analysis, transmission electron microscopy (TEM), and by various spectroscopic techniques (electronic and vibrational circular dichroism and by FTIR and Raman spectroscopy). The expression of chirality on the molecular and supramolecular levels has been studied and a clear amplification of its chirality into the achiral analogue has been observed. Furthermore, thermal analysis showed that the hydrogelation of compound 1 has a high response to temperature, which corresponds to an enthalpy‐driven self‐assembly process. These particular thermal characteristics make these materials easy to handle for soft‐application technologies.     

Double Metal Ions Competitively Control the Guest‐Sensing Process: A Facile Approach to Stimuli‐Responsive Supramolecular Gels

A facile approach to the design of stimuli‐responsive supramolecular gels (SRSGs) termed double‐metal‐ion competitive coordination control is reported. By this means, the fluorescence signals and guest‐selective responsiveness of the SRSGs are controlled by the competitive coordination of two different metal ions with the gelators and the target guest. To demonstrate this approach, a gelator G2 based on multiple self‐assembly driving forces was synthesized. G2 could form Ca²⁺‐coordinated metallogel CaG with strong aggregation‐induced emission (AIE). Doping of CaG with Cu²⁺ results in AIE quenching of CaG and formation of Ca²⁺‐ and Cu²⁺‐based metallogel CaCuG. CaCuG could fluorescently detect CN^? with specific selectivity through the competitive coordination of CN^? with the Cu²⁺ and the coordination of Ca²⁺ with G2 again. This approach may open up routes to novel stimuli‐responsive supramolecular materials.     

Supramolecular Dendrimers: Convenient Synthesis by Programmed Self‐Assembly and Tunable Thermoresponsivity

We report here the noncovalent synthesis of thermosensitive dendrimers. Short oligoguanosine strands were linked to the focal point of a dendron by using “click chemistry”, and quadruplex formation was used to drive the self‐assembly process in the presence of metal ions. The dynamic nature of these noncovalent assemblies can be exploited to create combinatorial libraries of dendrimers as demonstrated by the co‐assembly of two components. These supramolecular dendrimers showed thermoresponsive behavior that can be tuned by varying the templating cations or the number of guanines in the oligonucleotide strand.     

Multi‐Stimuli‐Responsive Polymer Materials: Particles,Films, and Bulk Gels

Stimuli‐responsive polymers have received tremendous attention from scientists and engineers for several decades due to the wide applications of these smart materials in biotechnology and nanotechnology. Driven by the complex functions of living systems, multi‐stimuli‐responsive polymer materials have been designed and developed in recent years. Compared with conventional single‐ or dual‐stimuli‐based polymer materials, multi‐stimuli‐responsive polymer materials would be more intriguing since more functions and finer modulations can be achieved through more parameters. This critical review highlights the recent advances in this area and focuses on three types of multi‐stimuli‐responsive polymer materials, namely, multi‐stimuli‐responsive particles (micelles, micro/nanogels, vesicles, and hybrid particles), multi‐stimuli‐responsive films (polymer brushes, layer‐by‐layer polymer films, and porous membranes), and multi‐stimuli‐responsive bulk gels (hydrogels, organogels, and metallogels) from recent publications. Various stimuli, such as light, temperature, pH, reduction/oxidation, enzymes, ions, glucose, ultrasound, magnetic fields, mechanical stress, solvent, voltage, and electrochemistry, have been combined to switch the functions of polymers. The polymer design, preparation, and function of multi‐stimuli‐responsive particles, films, and bulk gels are comprehensively discussed here.     

Self‐Assembled Gels for Biomedical Applications

Natural and synthetic gel‐like materials have featured heavily in the development of biomaterials for wound healing and other tissue‐engineering purposes. More recently, molecular gels have been designed and tailored for the same purpose. When mixed with, or conjugated to therapeutic drugs or bioactive molecules, these materials hold great promise for treating/curing life‐threatening and degenerative diseases, such as cancer, osteoarthritis, and neural injuries. This focus review explores the latest advances in this field and concentrates on self‐assembled gels formed under aqueous conditions (i.e., self‐assembled hydrogels), and critically compares their performance within different biomedical applications, including three‐dimensional cell‐culture studies, drug delivery, and tissue engineering. Although stability and toxicity issues still need to be addressed in more detail, it is clear from the work reviewed here that self‐assembled gels have a bright future as novel biomaterials.     

Self‐Assembly and Structural Evolvement of Polyoxometalate‐Anchored Dendron Complexes

A cationic dendritic molecule that has alkyl chains has been synthesized and employed to encapsulate anionic polyoxometalates through electrostatic interactions. The prepared surfactant‐encapsulated polyoxometalate (SEP) complexes were used as building blocks to fabricate self‐assemblies in solution and the solid state. Monodispersion, lamellar, and columnar assemblies of SEP complexes have been characterized in detail. With increasing the number of peripheral cationic dendrons on inorganic clusters, the SEPs undergo changes from globular assemblies to monodispersions in solution and from lamellar assemblies to hexagonal columnar structures in the solid state, depending on the amounts of cationic dendrons in the complexes. The structural evolvement was simulated through consideration of the size and shape of the cationic dendron and polyanionic clusters, and the experimental results are in good agreement with the interpretation of the simulations. The present research demonstrates a new kind of dendritic complex and provides a route for controlling their assembling states by simply alternating the number of cationic dendrons in the complexes.     

Spin‐Crossover Physical Gels: A Quick Thermoreversible Response Assisted by Dynamic Self‐Organization

Iron(II) triazolate coordination polymers with lipophilic sulfonate counterions with alkyl chains of different lengths have been synthesized. In hydrocarbon solvents, these polymers formed a physical gel and showed a thermoreversible spin transition upon the sol–gel phase transition. The formation of a hydrogen‐bonding network between the triazolate moieties and sulfonate ions, bridged by water molecules, was found to play an important role in the spin‐crossover event. The spin‐transition temperature was tuned over a wide range by adding a small amount of 1‐octanol, a scavenger for hydrogen‐bonding interactions. This additive was essential for the iron(II) species to adopt a low‐spin state. Compared with nongelling references in aromatic solvents, the spin‐crossover physical gels are characterized by their quick thermal response, which is due to a rapid restoration of the hydrogen‐bonding network, possibly because of a dynamic structural ordering through an enhanced lipophilic interaction of the self‐assembling components in hydrocarbon solvents.     

N‐Boc‐Protected 1,2‐Diphenylethylenediamine‐Based Dendritic Organogels with Multiple‐Stimulus‐Responsive Properties

A new class of poly(benzyl ether) dendrimers, decorated in their cores with N‐Boc‐protected 1,2‐diphenylethylenediamine groups, were synthesized and fully characterized. It was found that the gelation capability of these dendrimers was highly dependent on dendrimer generation, and the second‐generation dendrimer (R,R)‐G₂DPENBoc proved to be a highly efficient organogelator. A number of experiments (SEM, TEM, FTIR spectroscopy, ¹H NMR spectroscopy, rheological measurements, UV/Vis absorption spectroscopy, CD, and XRD) revealed that these dendritic molecules self‐assembled into elastically interpenetrating one‐dimensional nanostructures in organogels. The hydrogen bonding, π–π, and solvophobic interactions were found to be the main driving forces for formation of the gels. Most interestingly, these dendritic organogels exhibited smart multiple‐stimulus‐responsive behavior upon exposure to environmental stimuli such as temperature, anions, and mechanical stress.     

Gels at Extremely Low Weight Fractions Formed by Irreversible Self‐Assembly of Proteins

Food‐grade biomaterials, like β‐lactoglobulin, bovine serum albumin, and ovalbumin, can assemble into fibrils. Using the irreversible fibril formation for β‐lactoglobulin, gels can be formed even at protein concentrations of 0.07%. These fibrillar mesostructures form new structuring materials for food and pharmaceutical applications.

TEM micrograph of β‐lg at pH 2, after heating at 80 °C for 10 h and then the pH was adjusted to pH 8.     

Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

Dendronized Triangular Oligo(phenylene ethynylene) Amphiphiles: Nanofibrillar Self‐Assembly and Dye Encapsulation

Triangular‐shaped oligo(phenylene ethynylene) amphiphiles 1 a and 1 b decorated in their periphery with two‐ and four‐branched hydrophilic triethyleneglycol dendron wedges, have been synthesized and their self‐assembling properties in solution and onto surfaces investigated. The steric demand produced by the dendritic substituents induces a face‐to‐face rotated π stacking of the aromatic moieties. Studies on the concentration and temperature dependence confirm this mechanism and provide binding constants of 1.2×10⁵ and 1.7×10⁵ M ^?1 in acetonitrile for 1 a and 1 b , respectively. Dynamic and static light scattering measurements complement the study of the self‐assembly in solution and demonstrate the formation of rod‐like supramolecular structures in aqueous solution. The nanofibers formed in solution can be efficiently transferred onto surfaces. Thus, TEM images reveal the presence of strands of various thickness, with the most common being several micrometers long and with diameters of around 70 nm. Some of these nanofibers present folded edges that are indicative of their ribbon‐like nature. Interestingly, compound 1 b can also form thick filaments with a rope‐like appearance, which points to a chiral arrangement of the fibers. AFM images under highly diluted conditions also reveal long fibers with height profiles that fit well with the molecular dimensions calculated for both amphiphiles. Finally, we have demonstrated the intercalation of the hydrophobic dye Disperse Orange 3 within the filaments and its subsequent release upon increasing the temperature.     

Biocatalytic Self‐Assembly of Supramolecular Charge‐Transfer Nanostructures Based on n‐Type Semiconductor‐Appended Peptides

The reversible in situ formation of a self‐assembly building block (naphthalenediimide (NDI)–dipeptide conjugate) by enzymatic condensation of NDI‐functionalized tyrosine ( NDI‐Y ) and phenylalanine‐amide ( F‐NH₂ ) to form NDI‐YF‐NH₂ is described. This coupled biocatalytic condensation/assembly approach is thermodynamically driven and gives rise to nanostructures with optimized supramolecular interactions as evidenced by substantial aggregation induced emission upon assembly. Furthermore, in the presence of di‐hydroxy/alkoxy naphthalene donors, efficient charge‐transfer complexes are produced. The dynamic formation of NDI‐YF‐NH₂ and electronic and H‐bonding interactions are analyzed and characterized by different methods. Microscopy (TEM and AFM) and rheology are used to characterize the formed nanostructures. Dynamic nanostructures, whose formation and function are driven by free‐energy minimization, are inherently self‐healing and provide opportunities for the development of aqueous adaptive nanotechnology.