Integrating DNA Photonic Wires into Light‐Harvesting Supramolecular Polymers

An approach combining DNA nanoscaffolds with supramolecular polymers for the efficient and directional propagation of light‐harvesting cascades has been developed. A series of photonic wires with different arrangements of fluorophores in DNA‐organized nanostructures were linked to light‐harvesting supramolecular phenanthrene polymers (SPs) in a self‐assembled fashion. Among them, a light‐harvesting complex (LHC) composed of SPs and a photonic wire of phenanthrene, Cy3, Cy5, and Cy5.5 chromophores reveals a remarkable energy transfer efficiency of 59 %. Stepwise transfer of the excitation energy collected by the light‐harvesting SPs via the intermediate Cy3 and Cy5 chromophores to the final Cy5.5 acceptor proceeds through a Förster resonance energy transfer mechanism. In addition, the light‐harvesting properties are documented by antenna effects ranging from 1.4 up to 23 for different LHCs.     

Site‐Directed,On‐Surface Assembly of DNA Nanostructures

Two‐dimensional DNA lattices have been assembled from DNA double‐crossover (DX) motifs on DNA‐encoded surfaces in a site‐specific manner. The lattices contained two types of single‐stranded protruding arms pointing into opposite directions of the plane. One type of these protruding arms served to anchor the DNA lattice on the solid support through specific hybridization with surface‐bound, complementary capture oligomers. The other type of arms allowed for further attachment of DNA‐tethered probe molecules on the opposite side of the lattices exposed to the solution. Site‐specific lattice assembly and attachment of fluorophore‐labeled oligonucleotides and DNA–protein conjugates was demonstrated using DNA microarrays on flat, transparent mica substrates. Owing to their programmable orientation and addressability over a broad dynamic range from the nanometer to the millimeter length scale, such supramolecular architecture might be used for presenting biomolecules on surfaces, for instance, in biosensor applications.     

Unusual Length Dependence of the Conductance in Cumulene Molecular Wires

Cumulenes are sometimes described as “metallic” because an infinitely long cumulene would have the band structure of a metal. Herein, we report the single‐molecule conductance of a series of cumulenes and cumulene analogues, where the number of consecutive C=C bonds in the core is n=1, 2, 3, and 5. The [n]cumulenes with n=3 and 5 have almost the same conductance, and they are both more conductive than the alkene (n=1). This is remarkable because molecular conductance normally falls exponentially with length. The conductance of the allene (n=2) is much lower, because of its twisted geometry. Computational simulations predict a similar trend to the experimental results and indicate that the low conductance of the allene is a general feature of [n]cumulenes where n is even. The lack of length dependence in the conductance of [3] and [5]cumulenes is attributed to the strong decrease in the HOMO–LUMO gap with increasing length.     

High‐Performance,Stretchable, Wire‐Shaped Supercapacitors

A general approach toward extremely stretchable and highly conductive electrodes was developed. The method involves wrapping a continuous carbon nanotube (CNT) thin film around pre‐stretched elastic wires, from which high‐performance, stretchable wire‐shaped supercapacitors were fabricated. The supercapacitors were made by twisting two such CNT‐wrapped elastic wires, pre‐coated with poly(vinyl alcohol)/H₃PO₄ hydrogel, as the electrolyte and separator. The resultant wire‐shaped supercapacitors exhibited an extremely high elasticity of up to 350 % strain with a high device capacitance up to 30.7 F g⁻¹, which is two times that of the state‐of‐the‐art stretchable supercapacitor under only 100 % strain. The wire‐shaped structure facilitated the integration of multiple supercapacitors into a single wire device to meet specific energy and power needs for various potential applications. These supercapacitors can be repeatedly stretched from 0 to 200 % strain for hundreds of cycles with no change in performance, thus outperforming all the reported state‐of‐the‐art stretchable electronics.     

Site‐Specific Pre‐Swelling‐Directed Morphing Structures of Patterned Hydrogels

Morphing materials have promising applications in various fields, yet how to program the self‐shaping process for specific configurations remains a challenge. Herein we show a versatile approach to control the buckling of individual domains and thus the outcome configurations of planar‐patterned hydrogels. By photolithography, high‐swelling disc gels were positioned in a non‐swelling gel sheet; the swelling mismatch resulted in out‐of‐plain buckling of the disc gels. To locally control the buckling direction, masks with holes were used to guide site‐specific swelling of the high‐swelling gel under the holes, which built a transient through‐thickness gradient and thus directed the buckling during the subsequent unmasked swelling process. Therefore, various configurations of an identical patterned hydrogel can be programmed by the pre‐swelling step with different masks to encode the buckling directions of separate domains.     

Remote Regulation of Membrane Channel Activity by Site‐Specific Localization of Lanthanide‐Doped Upconversion Nanocrystals

The spatiotemporal regulation of light‐gated ion channels is a powerful tool to study physiological pathways and develop personalized theranostic modalities. So far, most existing light‐gated channels are limited by their action spectra in the ultraviolet (UV) or visible region. Simple and innovative strategies for the specific attachment of photoswitches on the cell surface without modifying or genetically encoding channel structures, and more importantly, that enable the remote activation of ion‐channel functions within near‐infrared (NIR) spectral window in living systems, remain a challenging concern. Herein, metabolic glycan biosynthesis is used to achieve site‐specific covalent attachment of near‐infrared‐light‐mediated lanthanide‐doped upconversion nanocrystals (UCNs) to the cell surface through copper‐free click cyclization. Upon irradiation with 808 nm light, the converted emission at 480 nm could activate a light‐gated ion channel, channelrhodopsins‐2 (ChR2), and thus remotely control the cation influx. This unique strategy provides valuable insights on the specific regulation membrane‐associated activities in vivo.     

Imprinted Photonic Hydrogels for the Size‐ and Shell‐Selective Recognition of Nanoparticles

Sensors based on responsive photonic hydrogels have recently attracted considerable attention for visual medical diagnostics, pharmaceutical bioassays, and environmental monitoring. However, the use of these promising materials for the detection of nanoparticles (NPs) has never been explored so far, although the sensing of nanoobjects is a rapidly evolving area of research. To address this issue, we have combined the concepts of inverse‐opal hydrogels and nanoparticle‐imprinted polymers. In this way, we could obtain a NP‐imprinted photonic hydrogel consisting of a three‐dimensional, highly ordered poly(methacrylic acid) macroporous array, in which nanocavities complementary to the target NPs, in this case colloidal quantum dots, are distributed. This novel type of NP‐imprinted photonic hydrogel sensor was shown to display high sensitivity and selectivity, thus opening new prospects for the development of equipment‐free and cost‐efficient sensing devices for NPs.