Jason S. Kahn

Integration of Switchable DNA-Based Hydrogels with Surfaces by the Hybridization Chain Reaction.

A novel method to assemble acrylamide/acrydite DNA copolymer hydrogels on surfaces, specifically gold-coated surfaces, is introduced. The method involves the synthesis of two different copolymer chains consisting of hairpin A, HA, modified acrylamide copolymer and hairpin B, HB, acrylamide copolymer. In the presence of a nucleic acid promoter monolayer associated with the surface, the hybridization chain reaction between the two hairpin-modified polymer chains is initiated, giving rise to the cross-opening of hairpins HA and HB and the formation of a cross-linked hydrogel on the surface. By the cofunctionalization of the HA- and HB-modified polymer chains with G-rich DNA tethers that include the G-quadruplex subunits, hydrogels of switchable stiffness are generated. In the presence of K(+)-ions, the hydrogel associated with the surface is cooperatively cross-linked by duplex units of HA and HB, and K(+)-ion-stabilized G-quadruplex units, giving rise to a stiff hydrogel. The 18-crown-6-ether-stimulated elimination of the K(+)-ions dissociates the bridging G-quadruplex units, resulting in a hydrogel of reduced stiffness. The duplex/G-quadruplex cooperatively stabilized hydrogel associated with the surface reveals switchable electrocatalytic properties. The incorporation of hemin into the G-quadruplex units electrocatalyzes the reduction of H2O2. The 18-crown-6-ether stimulated dissociation of the hemin/G-quadruplex bridging units leads to a catalytically inactive hydrogel.

A Shape-Memory DNA-Based Hydrogel Exhibiting Two Internal Memories.

The synthesis of a shape-memory acrylamide-DNA hydrogel that includes two internal memories is introduced. The hydrogel is stabilized, at pH 7.0, by two different pH-responsive oligonucleotide crosslinking units. At pH 10.0, one of the T-A⋅T triplex DNA bridging units is dissociated, resulting in the dissociation of the hydrogel into a shapeless quasi-liquid state that includes the other oligonucleotide bridges as internal memory. Similarly, at pH 5.0, the second type of bridges is separated, through the formation of C-G⋅C(+) triplex units to yield the shapeless quasi-liquid state that includes the other oligonucleotide bridges as internal memory. By reversible pH triggering of the hydrogel between the values 10.0⇔7.0⇔5.0, the two internal memories cycle the material across shaped hydrogel and shapeless quasi-liquid states. The two memories enable the pH-dictated formation of two different hydrogel structures.

Stimuli‐Responsive DNA‐Functionalized Metal–Organic Frameworks (MOFs)

The synthesis of nucleic acid-functionalized metal-organic frameworks (MOFs) is described. The metal-organic frameworks are loaded with a dye being locked in the structures by means of stimuli-responsive nucleic acid caps. The pH and K+ -ion-triggered release, and switchable release, are demonstrated.

DNA Scaffolds for the Dictated Assembly of Left-/Right-Handed Plasmonic Au NP Helices with Programmed Chiro-Optical Properties

Within the broad interest of assembling chiral left- and right-handed helices of plasmonic nanoparticles (NPs), we introduce the DNA-guided organization of left- or right-handed plasmonic Au NPs on DNA scaffolds. The method involves the self-assembly of stacked 12 DNA quasi-rings interlinked by 30 staple-strands. By the functionalization of one group of staple units with programmed tether-nucleic acid strands and additional staple elements with long nucleic acid chains, acting as promoter strands, the promoter-guided assembly of barrels modified with 12 left- or right-handed tethers is achieved. The subsequent hybridization of Au NPs functionalized with single nucleic acid tethers yields left- or right-handed structures of plasmonic NPs. The plasmonic NP structures reveal CD spectra at the plasmon absorbance, and the NPs are imaged by HR-TEM. Using geometrical considerations corresponding to the left- and right-handed helices of the Au NPs, the experimental CD spectra of the plasmonic Au NPs are modeled by theoretical calculations.

Orthogonal Dual-Triggered Shape-Memory DNA-Based Hydrogels

DNA-based shape-memory hydrogels revealing switchable shape recovery in the presence of two orthogonal triggers are described. In one system, a shaped DNA/acrylamide hydrogel is stabilized by duplex nucleic acids and pH-responsive cytosine-rich, i-motif, bridges. Separation of the i-motif bridges at pH 7.4 transforms the hydrogel into a quasi-liquid, shapeless state, that includes the duplex bridges as permanent shape-memory elements. Subjecting the quasi-liquid state to pH 5.0 or Ag(+) ions recovers the hydrogel shape, due to the stabilization of the hydrogel by i-motif or C-Ag(+) -C bridged i-motif. The cysteamine-induced transformation of the duplex/C-Ag(+) -C bridged i-motif hydrogel into a quasi-liquid shapeless state results in the recovery of the shaped hydrogel in the presence of H(+) or Ag(+) ions as triggers. In a second system, a shaped DNA/acrylamide hydrogel is generated by DNA duplexes and bridging Pb(2+) or Sr(2+) ions-stabilized G-quadruplex subunits. Subjecting the shaped hydrogel to the DOTA or KP ligands eliminates the Pb(2+) or Sr(2+) ions from the respective hydrogels, leading to shapeless, memory-containing, quasi-liquid states that restore the original shapes with Pb(2+) or Sr(2+) ions.

Metal Nanoparticles: Layered Metal Nanoparticle Structures on Electrodes for Sensing, Switchable Controlled Uptake/Release, and Photo-electrochemical Applications (Small 1/2016)

Layered metal nanoparticle structures have been shown to have application across a broad range of fields, notably as a specific and sensitive imprinting matrix for sensing targets, as a substrate for electrochemical reactions, and as a surface with which to control the uptake and release of molecules. On page 51 I. Willner and co-workers review how the synthesis of layered nanoparticles on an electrode provides a means of both recording sensitive responses to changes within the layers and inducing changes through electrochemical triggering.