Transparent self-standing supramolecular hydrogels were readily prepared by the potassium-ion-mediated self-organization of guanosine and 8-bromoguanosine whilst the individual components precipitated within a few hours. VT-NMR spectroscopy showed that bromoguanosine was a superior gelator compared to guanosine. XRD analysis showed that gel formation was caused by stacked G-quartets. AFM analysis revealed dendritic architectures of the nanofibers in the two-component hydrogel network. DSC profiles showed that the hybrid hydrogels underwent sol-gel transition at lower temperature than the pure guanosine and bromoguanosine hydrogels. Interestingly, bioactive dyes, such as rose bengal, rhodamine-6-G, and fluorescein, could be diffused and released in a controlled manner. UV/Vis absorption and fluorescence spectroscopy and CLSM were used to investigate the diffusion behavior of dyes in the hydrogel network. These dyes exhibited strong birefringence in the gel network (0.07-0.1) as a result of the anisotropic organization.
We
herein report that hydrogels can be prepared from guanosine
and boronic acids in the presence of K+ and Pb2+ ions. These supramolecular hydrogels are formed via G-quartet like
self-assembly of guanosine and its boronate esters. The potential
of this hydrogel construct in mimicking enzyme-like activity has been
demonstrated for the first time. We have observed that the self-assembled
structure present in K+ stabilized hydrogel binds to iron(III)-hemin
and shows peroxidase activity, catalyzing oxidation of 3,3′,5,5′-tetramethylbenzidine
(TMB) in the presence of H2O2. Furthermore,
the conformation of the G-quartet assemblies in the hydrogel can be
altered by varying the stabilizing cations K+ and Pb2+. This conformational switching has been used to devise a
molecular logic gate for sensing of toxic Pb2+ ions.
The selective transport of ions across cell membranes, controlled by membrane proteins, is critical for a living organism. DNA-based systems have emerged as promising artificial ion transporters. However, the development of stable and selective artificial ion transporters remains a formidable task. We herein delineate the construction of an artificial ionophore using a telomeric DNA G-quadruplex (h-TELO) and a lipophilic guanosine (MG). MG stabilizes h-TELO by non-covalent interactions and, along with the lipophilic side chain, promotes the insertion of h-TELO within the hydrophobic lipid membrane. Fluorescence assays, electrophysiology measurements and molecular dynamics simulations reveal that MG/h-TELO preferentially transports K +-ions in a stimuli-responsive manner. The preferential K +-ion transport is presumably due to conformational changes of the ionophore in response to different ions. Moreover, the ionophore transports K +-ions across CHO and K-562 cell membranes. This study may serve as a design principle to generate selective DNA-based artificial transporters for therapeutic applications.
A dinucleoside containing guanosine and cytidine at the end groups has been prepared using a modular one-pot azide-alkyne cycloaddition. Single channel analysis showed that this dinucleoside predominantly forms large channels with 2.9 nS conductance for the transport of potassium ions across a phospholipid bilayer. Transmission electron microscopy, atomic force microscopy, and circular dichroism spectroscopy studies reveal that this dinucleoside can spontaneously associate through Watson-Crick canonical H-bonding and π-π stacking to form stable supramolecular nanostructures. Most importantly, the ion channel activity of this G-C dinucleoside can be inhibited using the nucleobase cytosine.
Magnetic nanocomposites based on polyaniline (PANI) and magnetite nanoparticles (Fe 3 O 4 NPs) have been prepared by an in situ self-assembly method in presence of dodecylbenzene sulfonic acid (DBSA) as dopant as well as surfactant. Influence of the aniline to DBSA molar ratio on morphology, magnetic properties, and thermal stability of PANI/Fe 3 O 4 NPs composites has been investigated. Spectroscopic results indicated the interaction between PANI nanorods and Fe 3 O 4 NPs. Scanning electron microscopy and transmission electron microscopy images indicated that PANI rods were decorated with Fe 3 O 4 NPs. Morphologies of nanocomposites were found to be critically dependent on molar ratios of organic acid to monomer. PANI nanorod/Fe 3 O 4 NPs composites showed superparamagnetism and higher thermal stability with small mass fraction of Fe 3 O 4 NPs.
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