Diverse Morphologies of Self‐Assemblies from Homoditopic 1,18‐Nucleotide‐Appended Bolaamphiphiles: Effects of Nucleobases and Complementary Oligonucleotides

The synthesis of 1,18‐nucleotide‐appended bolaamphiphiles (1 , 2 , 4 , and 6) is reported, in which a 3′‐phosphorylated guanidine, adenosine, thymidine, or cytidine is connected to each end of an octadecamethylene chain. Single‐component self‐assemblies and binary self‐assemblies with the complementary oligonucleotides dC ₂₀ , dT ₂₀ , dA ₂₀ , and dG ₂₀ are studied by atomic force microscopy, powder X‐ray diffraction analysis, temperature‐dependent UV absorption, circular dichroism, and attenuated total‐reflection Fourier‐transform infrared spectroscopy. The single‐component self‐assembly of 1 forms a two‐dimensional sheet, whereas the binary self‐assembly 1 / dC ₂₀ gives helical nanofibers. Non‐helical nanofibers are observed for the single‐component self‐assemblies of 2 and 4 , and helical nanofibers form from the binary self‐assembly 2 / dT ₂₀ . Interestingly, helical nanorod structures are obtained from the binary self‐assembly 4 / dA ₂₀ , and the aligned nanorods form a nematic phase. The single‐component and binary self‐assemblies from 6 give unilamellar vesicles owing to a lack of stacking interaction between the cytosine moieties.     

Visible‐Light‐Induced Self‐Organized Helical Superstructure in Orientationally Ordered Fluids

Light‐induced phenomena occurring in nature and in synthetic materials are fascinating and have been exploited for technological applications. Here visible‐light‐induced formation of a helical superstructure is reported, i.e., a cholesteric liquid crystal phase, in orientationally ordered fluids, i.e., nematic liquid crystals, enabled by a visible‐light‐driven chiral molecular switch. The cyclic‐azobenzene‐based chiral molecular switch exhibits reversible photoisomerization in response to visible light of different wavelengths due to the band separation of n–π* transitions of its trans‐ and cis‐isomers. Green light (530 nm) drives the trans‐to‐cis photoisomerization whereas the cis‐to‐trans isomerization process of the chiral molecular switch can be caused by blue light (440 nm). It is observed that the helical twisting power of this chiral molecular switch increases upon irradiation with green light, which enables reversible induction of helical superstructure in nematic liquid crystals containing a very small quantity of the molecular switch. The occurrence of the light‐induced helical superstructure enables the formation of diffraction gratings in cholesteric films.     

Stimuli‐Responsive,Shape‐Transforming Nanostructured Particles

Development of particles that change shape in response to external stimuli has been a long‐thought goal for producing bioinspired, smart materials. Herein, the temperature‐driven transformation of the shape and morphology of polymer particles composed of polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) block copolymers (BCPs) and temperature‐responsive poly(N‐isopropylacrylamide) (PNIPAM) surfactants is reported. PNIPAM acts as a temperature‐responsive surfactant with two important roles. First, PNIPAM stabilizes oil‐in‐water droplets as a P4VP‐selective surfactant, creating a nearly neutral interface between the PS and P4VP domains together with cetyltrimethylammonium bromide, a PS‐selective surfactant, to form anisotropic PS‐b‐P4VP particles (i.e., convex lenses and ellipsoids). More importantly, the temperature‐directed positioning of PNIPAM depending on its solubility determines the overall particle shape. Ellipsoidal particles are produced above the critical temperature, whereas convex lens‐shaped particles are obtained below the critical temperature. Interestingly, given that the temperature at which particle shape change occurs depends solely on the lower critical solution temperature (LCST) of the polymer surfactants, facile tuning of the transition temperature is realized by employing other PNIPAM derivatives with different LCSTs. Furthermore, reversible transformations between different shapes of PS‐b‐P4VP particles are successfully demonstrated using a solvent‐adsorption annealing with chloroform, suggesting great promise of these particles for sensing, smart coating, and drug delivery applications.     

Flexible Chirality in Self‐Assembled N‐Annulated Perylenedicarboxamides

N‐annulated perylenedicarboxamides 1–3 form supramolecular polymers with a strong tendency to aggregate. The bundles of fibers formed generate a spontaneous anisotropy that conditions the chiroptical features of the described molecules in solution; a strong linear dichroism effect accompanies the circular dichroism (CD) outcome. There is no influence of the point chirality existing at the side chains of 1 and 2 , and these molecules present the same chiroptical features as achiral 3 . Mechanical rotary stirring increases the CD response and the sign of the dichroic signal changes with the stirring direction. Theoretical calculations indicate that the self‐assembly of 1–3 in helical columnar stacks generates atropisomers by the restricted rotation of the H‐bonded benzamide units. Molecular mechanics/molecular dynamics calculations predict a feasible intrastack stereomutation of the helical aggregates due to the rapid rupture/formation of the amide H‐bonds. This oscillating helicity, together with the fact that right‐ and left‐handed helices are predicted to be mostly isoenergetic, justifies the negligible contribution of the molecular chirality embedded in the paraffinic side chains of 1 and 2 . The reported CD behavior contributes to shed light on the physical processes promoting flexible macroscopic chirality that, in turn, can be utilized for the spectroscopic visualization of torsional flows generated in a vortex.     

Bioinspired Flexible Volatile Organic Compounds Sensor Based on Dynamic Surface Wrinkling with Dual‐Signal Response

Living systems can respond to external stimuli by dynamic interface changes. Moreover, natural wrinkle structures allow the surface to switch dynamically and reversibly from flat to rough in response to specific stimuli. Artificial wrinkle structures have been developed for applications such as optical devices, mechanical sensors, and microfluidic devices. However, chemical molecule‐triggered flexible sensors based on dynamic surface wrinkling have not been demonstrated. Inspired by human skin wrinkling, herein, a volatile organic compound (VOC)‐responsive flexible sensor with a switchable dual‐signal response (transparency and resistance) is achieved based on a multilayered Ag nanowire (AgNW)/SiO_x/polydimethylsiloxane (PDMS) film. Wrinkle structures can form dynamically in response to VOC vapors (such as ethanol, toluene, acetone, formaldehyde, and methanol) due to the instability of the multilayer induced by their different swelling capabilities. By controlling the modulus of PDMS and the thickness of the SiO_x layer, tunable sensitivities in resistance and transparency of the device are achieved. Additionally, the proximity mechanism of the solubility parameter is proposed, which explains the high selectivity of the device toward ethanol vapor compared with that of other VOCs well. This stimuli‐responsive sensor exhibits the dynamic visual feedback and the quantitative electrical signal, which provide a novel approach for developing smart flexible electronics.     

Amyloid Self‐Assembly of hIAPP8‐20 via the Accumulation of Helical Oligomers, α‐Helix to β‐Sheet Transition,and Formation of β‐Barrel Intermediates

The self‐assembly of human islet amyloid polypeptide (hIAPP) into β‐sheet‐rich nanofibrils is associated with the pathogeny of type 2 diabetes. Soluble hIAPP is intrinsically disordered with N‐terminal residues 8–17 as α‐helices. To understand the contribution of the N‐terminal helix to the aggregation of full‐length hIAPP, here the oligomerization dynamics of the hIAPP fragment 8–20 (hIAPP8‐20) are investigated with combined computational and experimental approaches. hIAPP8‐20 forms cross‐β nanofibrils in silico from isolated helical monomers via the helical oligomers and α‐helices to β‐sheets transition, as confirmed by transmission electron microscopy, atomic force microscopy, circular dichroism spectroscopy, Fourier transform infrared spectroscopy, and reversed‐phase high performance liquid chromatography. The computational results also suggest that the critical nucleus of aggregation corresponds to hexamers, consistent with a recent mass‐spectroscopy study of hIAPP8‐20 aggregation. hIAPP8‐20 oligomers smaller than hexamers are helical and unstable, while the α‐to‐β transition starts from the hexamers. Converted β‐sheet‐rich oligomers first form β‐barrel structures as intermediates before aggregating into cross‐β nanofibrils. This study uncovers a complete picture of hIAPP8‐20 peptide oligomerization, aggregation nucleation via conformational conversion, formation of β‐barrel intermediates, and assembly of cross‐β protofibrils, thereby shedding light on the aggregation of full‐length hIAPP, a hallmark of pancreatic beta‐cell degeneration.     

Molecular Modelling of Bone Morphogenetic Protein‐2 (BMP‐2) by 3D‐Rapid Prototyping

Bone morphogenetic proteins (BMP) play a decisive role in bone development and osteogenesis. In the past they have been the subject of widespread research and clinical trials as stimulants of bone growth. Recently BMP‐2 has been chemically immobilized on implant surfaces leading to enhanced bone growth and accelerated integration in sheep. Although the 3D‐structure of BMP‐2 is known the surface topography has not been the subject of a detailed analysis. Therefore we have begun implementing the technique of 3D‐rapid prototyping as a novel method for gaining topographical information on the structure‐function relationship of proteins (Laub et al., 2001, FASEB J. 15, A543). 3D‐rapid prototyping allows the construction of accurate three‐dimensional models of proteins based on their x‐ray crystallographic data. In this way we constructed a 3D scale image of BMP‐2 of the size 140 mm × 70 mm × 50 mm corresponding to a ca. 20 × 10⁶ fold magnification (scale 1 nm = 2 cm). BMP‐2 is a twisted banana‐shaped molecule consisting of a convex and a concave face and has a horn‐like protuberance cross‐turned at 180° (long axis) at each end. In the center of the convex face there is a ca. 1 nm deep crater like pit ca. 1.8 nm in diameter. The concave face is characterized by a 6–7 nm long helical groove 0.8–1.6 nm wide and ca 0.8 nm deep, into which a left‐handed helix with a pitch of 8–9 nm and a helical radius of 0.35–0.45 nm can be fitted. The concave face of BMP‐2 therefore corresponds to an imprint (groove) of a left‐handed helix i. e. to an anti‐helix or anthelix. The possible endogenous ligands and functions of these structures are unknown. These results demonstrate that full scale 3D molecular models of proteins can lead to new perceptions in understanding the interactions between ligands and proteins by macroscopic viewing and in‐hand fitting of the molecules without the aid of a computer.     

Amide‐Catalyzed Phase‐Selective Crystallization Reduces Defect Density in Wide‐Bandgap Perovskites

Wide‐bandgap (WBG) formamidinium–cesium (FA‐Cs) lead iodide–bromide mixed perovskites are promising materials for front cells well‐matched with crystalline silicon to form tandem solar cells. They offer avenues to augment the performance of widely deployed commercial solar cells. However, phase instability, high open‐circuit voltage (V_oc) deficit, and large hysteresis limit this otherwise promising technology. Here, by controlling the crystallization of FA‐Cs WBG perovskite with the aid of a formamide cosolvent, light‐induced phase segregation and hysteresis in perovskite solar cells are suppressed. The highly polar solvent additive formamide induces direct formation of the black perovskite phase, bypassing the yellow phases, thereby reducing the density of defects in films. As a result, the optimized WBG perovskite solar cells (PSCs) (E_g ≈ 1.75 eV) exhibit a high V_oc of 1.23 V, reduced hysteresis, and a power conversion efficiency (PCE) of 17.8%. A PCE of 15.2% on 1.1 cm² solar cells, the highest among the reported efficiencies for large‐area PSCs having this bandgap is also demonstrated. These perovskites show excellent phase stability and thermal stability, as well as long‐term air stability. They maintain ≈95% of their initial PCE after 1300 h of storage in dry air without encapsulation.     

Reconfigurable Chiral Self‐Assembly of Peptides through Control of Terminal Charges

Self‐assembly of chiral nanostructures is of considerable interest, since the ability to control the chirality of these structures has direct ramifications in biology and materials science. A new approach to design chiral nanostructures from self‐assembly of N‐(9‐fluorenylmethoxycarbonyl)‐protected phenylalanine‐tryptophan‐lysine tripeptides is reported. The terminal charges can induce helical twisting of the assembled β‐sheets, enabling the formation of well‐defined chiral nanostructures. The degree and direction of twisting in the β‐sheets can be precisely tailored through in situ pH and temperature modulations. This enables the assembly of reconfigurable chiral nanomaterials with easily adjustable size and handedness. These results offer new insight into the mechanism of helical twist formation, which may enable the precise assembly of highly dynamical materials with potential applications in biomedicine, chiroptics, and chiral sensing.     

A Novel Design of Multi‐Mechanoresponsive and Mechanically Strong Hydrogels

A newly developed polyacrylamide‐co ‐methyl acrylate/spiropyran (SP) hydrogel crosslinked by SP mechanophore demonstrates multi‐stimuli‐responsive and mechanically strong properties. The hydrogels not only exhibit thermo‐, photo‐, and mechano‐induced color changes, but also achieve super‐strong mechanical properties (tensile stress of 1.45 MPa, tensile strain of ≈600%, and fracture energy of 7300 J m^?2). Due to a reversible structural transformation between spiropyran (a ring‐close) and merocyanine (a ring‐open) states, simple exposure of the hydrogels to white light can reverse color changes and restore mechanical properties. The new design approach for a new mechanoresponsive hydrogel is easily transformative to the development of other mechanophore‐based hydrogels for sensing, imaging, and display applications.     

Template‐Assisted Electroforming of Fully Semi‐Hard‐Magnetic Helical Microactuators

The authors report on the fabrication of semi‐hard‐magnetic microhelices using template‐assisted electroforming. The method consists of electrodepositing a material on a sacrificial mandrel on which a pattern has been previously written. To electroform the helical microswimmers, a helical template on a polymer‐coated metallic mandrel is created using a laser, which precisely ablates the polymer coating and exposes the mandrel surface. Subsequently, the semi‐hard‐magnetic material is electrodeposited in the trenches produced by the laser. In this investigation, the helical structures are obtained from an electrolyte, which enables the production of hard‐magnetic CoPt alloys. The authors also show that electroformed semi‐hard‐magnetic helical microswimmers can propel in viscous environments such as silicon oil in three dimensions and against gravity. Their manufacturing approach can be used for the fabrication of more complex architectures for a wide range of applications and can be potentially extended to any electroplatable material.

     

Vortex Core Transitions in Superfluid 3He in Uniaxially Anisotropic Aerogel

Vortex core transitions (VCTs) in the superfluid phases of liquid ³He in uniaxially stretched and compressed aerogels are theoretically investigated. Uniaxial deformation imposed on the aerogel alters superfluid pairing symmetries in aerogels and the axial and polar pairing states are favored. In this study, we examine whether the effects of the uniaxial anisotropy on the pairing symmetries are reflected in core states of a single vortex extending along the deformation axis. By numerically solving the Ginzburg-Landau equations, we find that in the compressed aerogel, the first order VCT appears at any pressure in the B-like phase, while in the stretched aerogel, the VCT in the B-like phase is lost. Further, the vortices in the A-like phase in the stretched aerogel, have a polar core state in place of the A-phase core of the nonsingular Mermin-Ho vortex.     

Stimuli‐Driven Control of the Helical Axis of Self‐Organized Soft Helical Superstructures

Supramolecular and macromolecular functional helical superstructures are ubiquitous in nature and display an impressive catalog of intriguing and elegant properties and performances. In materials science, self‐organized soft helical superstructures, i.e., cholesteric liquid crystals (CLCs), serve as model systems toward the understanding of morphology‐ and orientation‐dependent properties of supramolecular dynamic helical architectures and their potential for technological applications. Moreover, most of the fascinating device applications of CLCs are primarily determined by different orientations of the helical axis. Here, the control of the helical axis orientation of CLCs and its dynamic switching in two and three dimensions using different external stimuli are summarized. Electric‐field‐, magnetic‐field‐, and light‐irradiation‐driven orientation control and reorientation of the helical axis of CLCs are described and highlighted. Different techniques and strategies developed to achieve a uniform lying helix structure are explored. Helical axis control in recently developed heliconical cholesteric systems is examined. The control of the helical axis orientation in spherical geometries such as microdroplets and microshells fabricated from these enticing photonic fluids is also explored. Future challenges and opportunities in this exciting area involving anisotropic chiral liquids are then discussed.     

The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [R‐ and S‐1‐(4‐Chlorophenyl)ethylammonium]2PbI4

2D organic–inorganic lead iodide perovskites have recently received tremendous attention as promising light absorbers for solar cells, due to their excellent optoelectronic properties, structural tunability, and environmental stability. However, although great efforts have been made, no 2D lead iodide perovskites have been discovered as ferroelectrics, in which the ferroelectricity may improve the photovoltaic performance. Here, by incorporating homochiral cations, 2D lead iodide perovskite ferroelectrics [R‐1‐(4‐chlorophenyl)ethylammonium]₂PbI₄ and [S‐1‐(4‐chlorophenyl)ethylammonium]₂PbI₄ are successfully obtained. The vibrational circular dichroism spectra and crystal structural analysis reveal their homochirality. They both crystalize in a polar space group P1 at room temperature, and undergo a 422F1 type ferroelectric phase transition with transition temperature as high as 483 and 473.2 K, respectively, showing a multiaxial ferroelectric nature. They also possess semiconductor characteristics with a direct bandgap of 2.34 eV. Nevertheless, their racemic analogue adopts a centrosymmetric space group P2₁/c at room temperature, exhibiting no high‐temperature phase transition. The homochirality in 2D lead iodide perovskites facilitates crystallization in polar space groups. This finding indicates an effective way to design high‐performance 2D lead iodide perovskite ferroelectrics with great application prospects.     

Superior Functionality by Design: Selective Ozone Sensing Realized by Rationally Constructed High‐Index ZnO Surfaces

A new technique is reported for the transformation of smooth nonpolar ZnO nanowire surfaces to zigzagged high‐index polar surfaces using polycrystalline ZnO thin films deposited by atomic layer deposition (ALD). The c‐axis‐oriented ZnO nanowires with smooth nonpolar surfaces are fabricated using vapor deposition method and subsequently coated by ALD with a ZnO particulate thin film. The synthesized ZnO–ZnO core–shell nanostructures are annealed at 800 °C to transform the smooth ZnO nanowires to zigzagged nanowires with high‐index polar surfaces. Ozone sensing response is compared for all three types of fabricated nanowire morphologies, namely nanowires with smooth surfaces, ZnO–ZnO core–shell nanowires, and zigzagged ZnO nanowires to determine the role of crystallographic surface planes on gas response. While the smooth and core–shell nanowires are largely non‐responsive to varying O₃ concentrations in the experiments, zigzagged nanowires show a significantly higher sensitivity (ppb level) owing to inherent defect‐rich high‐index polar surfaces.     

Reconfigurable Microscale Frameworks from Concatenated Helices with Controlled Chirality

The utility of helical structures in driving motion of microorganisms and plants has inspired efforts to develop synthetic stimuli‐responsive helical architectures for self‐motile and shape‐morphing systems. While several approaches to responsive helices based on hydrogels and liquid crystalline polymers have been reported, they have so far been limited to macroscopic (cm scale) dimensions, and have not been applied to concatenated helices with more than two segments. Here, a robust method for microfabrication of helices inspired by Bauhinia seedpods, based on trilayer samples consisting of rigid plastic stripes sandwiching a swellable temperature‐responsive hydrogel, is reported and the formation of responsive shape‐controlled frameworks from concatenated multiple helices (multihelices) with controlled chirality is demonstrated. The block angle at each helical junction is controlled by the change in stripe direction, while the torsion angle defined by each segment of three helices is prescribed by the net twist of the middle segment, providing simple geometric design rules for the fabrication of complex 3D structures. This work opens new directions in programming 3D shapes by providing new insight into helical segments as building blocks, with potential applicability to the fabrication of scaffolds for cell culture, reconfigurable microfluidic channels, and microswimmers.     

Enhancing Molecular n‐Type Doping of Donor–Acceptor Copolymers by Tailoring Side Chains

In this contribution, for the first time, the molecular n‐doping of a donor–acceptor (D–A) copolymer achieving 200‐fold enhancement of electrical conductivity by rationally tailoring the side chains without changing its D–A backbone is successfully improved. Instead of the traditional alkyl side chains for poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl](NDI)‐alt‐5,5′‐(2,2′‐bithiophene)} (N2200), polar triethylene glycol type side chains is utilized and a high electrical conductivity of 0.17 S cm^?1 after doping with (4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine is achieved, which is the highest reported value for n‐type D–A copolymers. Coarse‐grained molecular dynamics simulations indicate that the polar side chains can significantly reduce the clustering of dopant molecules and favor the dispersion of the dopant in the host matrix as compared to the traditional alkyl side chains. Accordingly, intimate contact between the host and dopant molecules in the NDI‐based copolymer with polar side chains facilitates molecular doping with increased doping efficiency and electrical conductivity. For the first time, a heterogeneous thermoelectric transport model for such a material is proposed, that is the percolation of charge carriers from conducting ordered regions through poorly conductive disordered regions, which provides pointers for further increase in the themoelectric properties of n‐type D–A copolymers.     

Light‐Driven Reversible Transformation between Self‐Organized Simple Cubic Lattice and Helical Superstructure Enabled by a Molecular Switch Functionalized Nanocage

Self‐organized stimuli‐responsive smart materials with adjustable attributes are highly desirable for a plethora of device applications. Simple cubic lattice is quite uncommon in soft condensed matter due to its lower packing factor. Achieving a stable simple cubic soft lattice and endowing such a lattice with dynamic reconstruction capability solely by a facile light irradiation are of paramount significance for both fundamental studies and engineering explorations. Herein, an elegant stable self‐organized simple cubic soft lattice, i.e., blue phase II, in a chiral liquid crystal (LC) system is disclosed, which is stable down to room temperature and exhibits both reversible lattice deformation and transformation to a helical superstructure, i.e., cholesteric LC, by light stimulation. Such an amazing trait is attained by doping a judiciously designed achiral photoresponsive molecular switch functionalized polyhedral oligomeric silsesquioxane nanocage into a chiral LC host. An unprecedented reversible collapse and reconstruction of such a high symmetric simple cubic blue phase II driven by light has been achieved. Furthermore, a well‐defined conglomerate micropattern composed of simple cubic soft lattice and helical superstructure, which is challenging to fabricate in organic and inorganic crystalline materials, is produced using photomasking technology. Moreover, the promising photonic application based on such a micropattern is demonstrated.     

Chiral Nanostructures from Helical Copolymer–Metal Complexes: Tunable Cation–π Interactions and Sergeants and Soldiers Effect

Poly(phenylacetylene) (PPA) copolymers containing (R)‐ or (S)‐MPA as minor chiral pendant can be forced to selectively adopt the right‐ o left‐handed helix, in the presence of small amounts of Na⁺ or Ag⁺ (“Sergeants and Soldiers Effect”) by addition of a donor cosolvent. The helical sense depends exclusively on the chiral monomer/donor cosolvent ratio, and this allows a perfect on/off tuning of the helicity of the copolymer. When the amount of the donor cosolvent is low, the metal ion complex is stabilized by a cation–π interaction, which is selectively cleaved when the amount of cosolvent is higher. Macroscopically chiral nanospheres and nanotubes composed by helical copolymers with P or M helical sense are also described. Our results demonstrate that it is possible to obtain the two enantiomeric helical structures (P and M helicities) and the corresponding nanospheres and nanotubes from a single helical copolymer, by controlled activation/deactivation of the Sergeant and Soldiers Effect with a donor cosolvent.     

A Dual‐Stimuli‐Responsive Sodium‐Bromine Battery with Ultrahigh Energy Density

Stimuli‐responsive energy storage devices have emerged for the fast‐growing popularity of intelligent electronics. However, all previously reported stimuli‐responsive energy storage devices have rather low energy densities (<250 Wh kg^–1) and single stimuli‐response, which seriously limit their application scopes in intelligent electronics. Herein, a dual‐stimuli‐responsive sodium‐bromine (Na//Br₂) battery featuring ultrahigh energy density, electrochromic effect, and fast thermal response is demonstrated. Remarkably, the fabricated Na//Br₂ battery exhibits a large operating voltage of 3.3 V and an energy density up to 760 Wh kg^?1, which outperforms those for the state‐of‐the‐art stimuli‐responsive electrochemical energy storage devices. This work offers a promising approach for designing multi‐stimuli‐responsive and high‐energy rechargeable batteries without sacrificing the electrochemical performance.