Functional Materials from Cellulose‐Derived Liquid‐Crystal Templates

Cellulose nanocrystals (CNCs), known for more than 50 years, have attracted attention because of their unique properties such as high specific strength and modulus, high surface area, and fascinating optical properties. Just recently, however, their potential in supramolecular templating was identified by making use of their self‐assembly behavior in aqueous dispersions in the presence of compatible precursors. The combination of the mesoporosity, photonic properties, and chiral nematic order of the materials, which are available as freestanding films, has led to a significant number of interesting and promising discoveries towards new functional materials. This Review summarizes the use of cellulose derivatives, especially CNCs, as novel templates and gives an overview of the recent developments toward new functional materials.     

Peptides as New Smart Bionanomaterials: Molecular‐Recognition and Self‐Assembly Capabilities

Biomolecules express exquisite properties that are required for molecular recognition and self‐assembly on the nanoscale. These smart capabilities have developed through evolution and such biomolecules operate based on smart functions in natural systems. Recently, these remarkable smart capabilities have been utilized in not only biologically related fields, but also in materials science and engineering. A peptide‐screening technology that uses phage‐display systems has been developed based on this natural smart evolution for the generation of new functional peptide bionanomaterials. We focused on peptides that specifically bound to synthetic polymers. These polymer‐binding peptides were screened by using a phage‐display peptide library to recognize nanostructures that were derived from polymeric structural features and were utilized for possible applications as new bionanomaterials. We also focused on self‐assembling peptides with β‐sheet structures that formed nanoscale, fibrous structures for applications in new bottom‐up nanomaterials. Moreover, nanofiber‐binding peptides were also screened to introduce the desired functionalities into nanofibers without the need for additional molecular design. Our approach to construct new bionanomaterials that employ peptides will open up excellent opportunities for the next generation of materials science and technology.     

Oriented Chiral DNA–Silica Film Guided by a Natural Mica Substrate

The formation of highly ordered chiral organic/inorganic films with high density and long‐range orientation is important in constructing chiral devices, such as broadband polarization devices, liquid‐crystal displays, or negative‐reflection materials. A feasible strategy is presented to fabricate three‐dimensional mesostructured chiral DNA–silica assemblies into large‐scale oriented arrangements. The highly ordered film was aligned by a mica crystal substrate with the bridging effect of suitable divalent metal ions, followed by the growth of the DNA–silica composite by bottom‐up assembly with a “quartet templating” method. This simple and effective route would perform well in the alignment and arrangement of highly charged biomolecules, such as polypeptides, proteins, viruses, and their inorganic assemblies, and furthermore could allow the fabrication of chiral optical materials with long‐range ordering.     

Preparation and Functions of Hybrid Membranes with Rings of Ag NPs Anchored at the Edges of Highly Ordered Honeycomb‐Patterned Pores

We report a new, simple strategy to apply honeycomb films for the patterning of colloidal particles. By combination of a “bottom‐up” breath figure method and the electrochemical properties of the honeycomb films of ferrocenyl‐based oligomers, highly ordered hybrid membranes coated with ring‐like patterning of 0D‐ and 1D‐Ag nanoparticles (NPs) have been fabricated. One interesting phenomenon is that the nucleation and adsorption of Ag dots occurred preferentially at the edges of the micropores. The hybrid membranes exhibited richly electrochemical activities towards reduction of iodate and enhanced effectively catalytic reduction of organic dyes. We believe that this method can be used to decorate and/or assemble functional metal NPs such as Au, Pd, and Cu on honeycomb‐patterned materials for the further applications of photonics, sensors, and catalysis.     

Oriented Gold Nanorod Arrays: Self‐Assembly and Optoelectronic Applications

Self‐assembly of anisotropic plasmonic nanomaterials into ordered superstructures has become popular in nanoscience because of their unique anisotropic optical and electronic properties. Gold nanorods (GNRs) are a well‐defined functional building block for fabrication of these superstructures. They possess important anisotropic plasmonic characteristics that result from strong local electric field and are responsive to visible and near‐IR light. There are recent examples of assembling the GNRs into ordered arrays or superstructures through processes such as solvent evaporation and interfacial assembly. In this Minireview, recent progress in the development of the self‐assembled GNR arrays is described, with focus on the formation of oriented GNR arrays on substrates. Key driving forces are discussed, and different strategies and self‐assembly processes of forming oriented GNR arrays are presented. The applications of the oriented GNR arrays in optoelectronic devices are also overviewed, especially surface enhanced Raman scattering (SERS).     

DNA Nanoribbon‐Templated Self‐Assembly of Ultrasmall Fluorescent Copper Nanoclusters with Enhanced Luminescence

Fluorescent copper nanoclusters (CuNCs) have been widely used in chemical sensors, biological imaging, and light‐emitting devices. However, individual fluorescent CuNCs have limitations in their capabilities arising from poor photostability and weak emission intensities. As one kind of aggregation‐induced emission luminogen (AIEgen), the formation of aggregates with high compactness and good order can efficiently improve the emission intensity, stability, and tunability of CuNCs. Here, DNA nanoribbons, containing multiple specific binding sites, serve as a template for in situ synthesis and assembly of ultrasmall CuNCs (0.6 nm). These CuNC self‐assemblies exhibit enhanced luminescence and excellent fluorescence stability because of tight and ordered arrangement through DNA nanoribbons templating. Furthermore, the stable and bright CuNC assemblies are demonstrated in the high‐sensitivity detection and intracellular fluorescence imaging of biothiols.     

Molecular assemblies of perylene bisimide dyes in water

Perylene bisimides are among the most valuable functional dyes and have numerous potential applications. As a result of their chemical robustness, photostability, and outstanding optical and electronic properties, these dyes have been applied as pigments, fluorescence sensors, and n‐semiconductors in organic electronics and photovoltaics. Moreover, the extended quadrupolar π system of this class of dyes has facilitated the construction of numerous supramolecular architectures with fascinating photophysical properties. However, the supramolecular approach to the formation of perylene bisimide aggregates has been restricted mostly to organic media. Pleasingly, considerable progress has been made in the last few years in developing water‐soluble perylene bisimides and their application in aqueous media. This Review provides an up‐to‐date overview on the self‐assembly of perylene bisimides through π–π interactions in aqueous media. Synthetic strategies for the preparation of water‐soluble perylene bisimides and the influence of water on the π–π stacking of perylene bisimides as well as the resulting applications are discussed.     

Growth of Hydrophilic CuS Nanowires via DNA‐Mediated Self‐Assembly Process and Their Use in Fabricating Smart Hybrid Films for Adjustable Chemical Release

Facile growth of CuS nanowires through self‐assembly and their application as building blocks for near‐infrared light‐responsive functional films have been demonstrated. It is found that DNA is a key factor in preparing the CuS material with defined nanostructure. An exclusive oriented self‐aggregate growth mechanism is proposed for the growth of the nanowires, which might have important implications for preparing advanced, sophisticated nanostructures based on DNA nanotechnology. By employing the hydrophilic CuS nanowire as an optical absorber and thermosensitive nanogel as guest reservoir inside alginate film, a new platform for the release of functional molecules has been set up. In vitro studies have shown that the hybrid film possesses excellent biocompatibility and the release rate of chemical molecules from the film could be controlled with high spatial and temporal precision. Our novel approach and the resulting outstanding combination of properties may advance both the fields of DNA nanotechnology and light‐responsive devices.     

Optical properties of mesoporous II-VI semiconductor compound films

Direct liquid crystal templating from non-ionic polyoxyethylene surfactants has been utilised to produce well-defined birefringent films of nanostructured cadmium telluride films which displayed good optical properties as evidenced by UV/VIS reflectance spectroscopy.     

Breakthrough and future: nanoscale controls of compositions,morphologies, and mesochannel orientations toward advanced mesoporous materials

Currently, ordered mesoporous materials prepared through the self‐assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic‐based materials, for example, transition‐metal oxides, carbons, inorganic‐organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant‐based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation‐mediated direct templating (EDIT), spray‐dried techniques, and collaboration with hard‐templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic‐scale controls of mesochannels are important for innovative applications such as molecular‐scale devices and electrodes with enhanced diffusions of guest species. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 321–339; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900022     

Polymer physics inspired approaches for the study of the mechanical properties of amyloid fibrils

Amyloid structures constitute a class of highly ordered nanomaterials formed by insoluble protein aggregates. These aggregates are characterized by a cross‐β structural motif in which β‐sheets are oriented perpendicular to the fibril axis and bound together by a dense hydrogen bonding network. Although they have been associated with several neurodegenerative disorders, such as Alzheimer's and Parkinson's diseases, amyloid fibrils have also been found in many physiologically beneficial roles, for instance in adhesives and hormone storage. Inspired by this natural occurrence of functional amyloid, the hierarchal self‐assembly of these structures has recently been used to develop artificial biomaterials for applications in medicine and nanotechnology. In order to realize the full potential of amyloids as functional materials, it is important to understand their fundamental mechanical properties. This review explores a range of experimental strategies to determine the mechanical properties of amyloid fibrils and discusses the results in the context of polymer physics concepts. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 281–292     

Induction of periodic nanostructures in polythiophene films through block copolymer templating

A new class of periodically nanostructured polythiophene materials with high regularity and numerous morphologies is prepared through the cooperative self‐assembly of polythiophene derivatives with a templating block copolymer (BCP) and poly(1,4‐isoprene)‐block‐poly(methacrylic acid) (PMA). The selection of the hydrophilic and aprotic triethylene glycol (TEG) group as side chains on polythiophene and the use of hydrophilic and protic PMA are crucial to producing well‐ordered nanostructures in polythiophene films, as it enables selective coassembly within the hydrophilic domain through hydrogen bonding. The composite films are shown to have formed hexagonally packed cylinders with 28 nm periodicities based on small‐angle X‐ray scattering and transmission electron microscopy. The formation of hydrogen bonding is revealed by a shift in the carbonyl peak of PMA in the Fourier transform infrared spectra of the composite film relative to the neat film. This suggests that the TEG‐functionalized polythiophene selectively incorporates into PMA. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1105–1112     

Advances in Metal‐Free Heterocycle‐Based Columnar Liquid Crystals

Liquid crystals are ordered soft materials formed by self‐organized molecules and can potentially be used as new functional materials for electron‐, ion‐ or molecular‐transport; optical; and bio‐active materials. In particular, the columnar liquid crystals are promising candidates used in various optical and electronic devices. For this purpose, design and synthesis of unconventional materials are essential. In this review, we have summarized several approaches for the synthesis of columnar liquid crystals composed of various heterocyclic systems. We also outline their liquid crystalline and other relevant properties, and their suitability for applications in diverse fields.     

Breath Figure Arrays: Unconventional Fabrications,Functionalizations, and Applications

A breath figure (BF) is the water droplet array that forms when moisture comes in contact with a cold substrate. This water droplet array has been widely utilized in the past two decades as a versatile soft template for the fabrication of polymeric porous films. Accordingly, the ordered pores on the polymer films formed with such a method are named a breath figure array (BFA).The BF templating technique is undergoing rapid development. Several unconventional BF processes have been established to prepare porous films with unique morphologies or primary materials, and various newly developed functionalization techniques have significantly improved the performance of polymeric films with BFA, leading to novel applications, including templates, biosensors, and separation membranes. These recent achievements will be described in this Minireview.     

Advances of Metal‐Organic Frameworks in Energy and Environmental Applications

Nowadays, energy shortage and environmental pollution issues are increasingly severe and urgent to be solved. The effective storage and use of environmentally friendly fuels and removal of harmful gases from the environment are great challenges and of great importance both for the environment protection and for human health. Porous metal‐organic frameworks (MOFs) are highly ordered crystalline materials formed by the self‐assembly process of metal ions and organic ligands. Their good features such as ultrahigh porosity, large surface area, structural diversity and functionalities make them promising candidates for applications in energy and environmental fields. MOF thin films and MOF composites have also been investigated to further enhance the properties and introduce new functionalities. This review provides an overview of the synthesis methods of pristine MOFs, MOF thin films and MOF composites, and significant advances of MOFs in energy and environment applications such as energy storage (H₂, CH₄), CO₂ capture and separation, adsorption removal and sensing of harmful gases in the environment.     

Synthesis and nonlinear optical properties of side chain liquid crystalline polymers containing azobenzene push–pull chromophores

Azobenzene monomeric precursors bearing piperazine as donor moiety with different withdrawing groups and derived side chain polymethacrylates have been prepared and characterized. Monomers having terminal cyano or nitro groups, and the corresponding polymers, exhibited smectic A phases. Linear and nonlinear optical properties of every monomer and thin films of the cyano polymer ( pol‐PZ‐CN ) have been also studied. UV‐vis spectroscopy revealed out‐of‐plane orientation in the as prepared films, as confirmed by waveguide refractive index measurements. Moreover, absorption spectra indicated the presence of azo aggregates in these films. The initial molecular arrangement has been modified by applying thermal annealing within the mesophase range and UV‐blue irradiation. Although thermal annealing resulted in a significant amplification of the out‐of‐plane optical anisotropy due to thermotropic self‐organization of side chain azo moieties, irradiation with 440 nm light induced some disruption of aggregates. The nonlinear optical response of Corona poled films has been studied by second harmonic generation measurements, and the influence of the molecular arrangement on the nonlinear d_ij coefficients has been analyzed. The more efficient poling corresponded to preirradiated films. In any case, a noticeable degree of polar order (70% of the initial d₃₃ value) remained for several months after the poling in films kept at RT. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 232–242, 2010     

Advanced materials based on polymer cocrystalline forms

Polymeric “cocrystalline forms,” that is, structures were a polymeric host and a low‐molecular‐mass guest are cocrystallized, were early recognized, and in many cases also well characterized by X‐ray diffraction studies. However, only in the last two decades cocrystalline forms have received attention in material science, due to the ability (of few of them) to maintain an ordered polymer host structure even after guest removal, thus leading to the formation of “nanoporous‐crystalline forms,” for which many applications in the fields of molecular separation and sensors have been proposed. Moreover, in the last decade, an accurate control of the orientation of the polymer cocrystalline phases has been achieved, thus leading to a control of the orientation of the guest molecules, not only in the crystalline phase but also in macroscopic films. In addition, on the basis of this orientation control, in the last few years, cocrystalline films where active molecules are present as guests of polymer cocrystalline phases have been proposed for optical, magnetic and electric applications. In the last few years, it has been also discovered that polymer cocrystallization, when induced by nonracemic guest molecules, can produce stable chiral optical films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Macroporous Oxide Platforms Templated by Non‐Close‐Packed Spherical Copolymer Aggregates

Exclusive organic templating of macroporous oxide films is reported by using non‐close and lose packing of spherical copolymer aggregates, in combination with facile control of condensation degree/density of inorganic oxide frameworks. Unique macroporous oxide films, mainly titania showing highly porous, crystalline, and versatile properties, can be fabricated with continuous design from unusual 3‐D net‐shape to tunable spherical macrostructures, which expands the preparation of other inorganic oxide films (silica, alumina, and zirconia) and possibly adapts the use of other assembled organic polymers. The macroporous structures are helpful for effective accommodation of bulky biomoleculeshigh and diffusivity of organic molecules (useful for photocatalysts). Unusual structural variation, expansion of spherical voids, is also observed, being useful for fine tuning of optical property.     

π–π Interactions Between Aromatic Groups in Amphiphilic Molecules: Directing Hierarchical Growth of Porous Zeolites

The development of hierarchical macro‐ or mesoporous zeolites is essential in zeolite synthesis because the size of the micropores limits mass transport and their use as industrial catalysts for bulky molecules. Although major breakthroughs have been achieved, fabricating crystallographically ordered mesoporous zeolites using a templating strategy is still an unsolved challenge. This minireview highlights our recent efforts on the self‐assembly of amphiphilic molecules to obtain ordered hierarchical MFI zeolites by introducing aromatic groups into the hydrophobic tail of the amphiphilic molecules. Owing to the geometric matching between the self‐assembled aromatic tails and the MFI framework, a) single‐crystalline mesostructured zeolite nanosheets (SCZNs), b) SCZNs with a 90° rotational intergrowth structure, c) a hierarchical MFI zeolite with a two‐dimensional square P4mm mesostructure, and d) a single‐crystalline mesoporous ZSM‐5 with three‐dimensional pores and sheetlike mesopores layered along the a‐axis were successfully synthesized.