Programmable Transient Supramolecular Chiral G-quadruplex Hydrogels by a Chemically Fueled Non-equilibrium Self-Assembly Strategy.

The temporal and spatial control of natural systems has aroused great interest for the creation of synthetic mimics. By using boronic ester based dynamic covalent chemistry and coupling it with an internal pH feedback system, we have developed a new chemically fueled reaction network for non-equilibrium supramolecular chiral G-quadruplex hydrogels with programmable lifetimes from minutes, to hours, to days, as well as high transparency and conductivity, excellent injectability, and rapid self-healing properties. The system can be controlled by the kinetically controlled in situ formation and dissociation of dynamic boronic ester bonds between the cis-diol of guanosine (G) and 5-fluorobenzoxaborole (B) in the presence of chemical fuels (KOH and 1,3-propanesultone), thereby leading to a precipitate-solution-gel-precipitate cycle under non-equilibrium conditions. A combined experimental-computational approach showed the underlying mechanism of the non-equilibrium self-assembly involves aggregation and disaggregation of right-handed helical G-quadruplex superstructures. The proposed dynamic boronic ester-based non-equilibrium self-assembly strategy offers a new option to design next-generation adaptive and interactive smart materials.

Supramolecular G4 Eutectogels of Guanosine with Solvent-Induced Chiral Inversion and Excellent Electrochromic Activity.

Supramolecular eutectogels, an emerging class of materials that have just developed very recently, offer a new opportunity for generating functional supramolecular gel materials in biocompatible anhydrous or low-water media. As the first example of supramolecular G4 eutectogels, complexes of natural guanosine and H3 BO3 exhibited excellent gelation capacity in choline chloride/alcohol deep eutectic solvents. The as-prepared supramolecular eutectogels displayed unexpected solvent-induced chiral inversion and significantly high ionic conductivity (up to 7.78 mS cm-1 ), as well as outstanding thixotropic/injectable properties, high thermal stability and excellent electrochromic activity. These features make these versatile supramolecular G4 eutectogels promising candidates for developing next-generation flexible electronics with low environmental impact.

Self-healing mechanism and bioelectrochemical interface properties of core-shell guanosine-borate hydrogels.

The self-healing mechanism and bioelectrochemical interface properties of supramolecular gels have been rarely explored. In this context, we propose a constitutive "fibril-reorganization" model to reveal the self-healing mechanism of a series of core-shell structured guanosine-borate (GB) hydrogels and emphasize that interfibrillar interactions at the supramolecular polymer scale (G-quadruplex nanowires) drive the self-healing process of GB hydrogels. Structure-electrochemical sensing performance studies reveal that GB hydrogel nanofibers with relatively strong biomolecular affinity such as -SH modified GB hydrogel (GB-SH) show a high sensitivity of response and low limit of detection for tumour marker alpha-fetoprotein sensing (AFP; 0.076 pg mL-1). Guanosine/ferroceneboronic acid (GB-Fc) hydrogel nanofibers with superior conductivity and redox activity display the widest linear detection range for AFP (0.0005-100 ng mL-1). Structure-property correlations of GB hydrogels provide useful insight for the future design of advanced self-healing materials and electrochemical biosensors.

Super-stretchable and extreme temperature-tolerant supramolecular-polymer double-network eutectogels with ultrafast in situ adhesion and flexible electrochromic behaviour.

The current tough and stretchable gels with various integrated functions are mainly based on polymer hydrogels. By introducing a non-covalent supramolecular self-assembled network into a covalently cross-linked polymer network in the presence of eco-friendly and cost-effective deep eutectic solvents (DESs), we developed a new small molecule-based supramolecular-polymer double-network (SP-DN) eutectogel platform. This exciting material exhibits high stretchability and toughness (>18 000% areal strain), spontaneous self-healing ability, ultrafast (∼5 s) in situ underwater and low-temperature (-80 °C) adhesion, and unusual boiling water-resistance, as well as strong base-, strong acid- (even aqua regia), ultra-low-temperature- (liquid nitrogen, -196 °C), and high-temperature- (200 °C) resistance. All these outstanding properties strongly recommend the SP-DN eutectogels as a quasi-solid electrolyte for soft electrochromic devices, which exhibited exceptional flexibility and consistent electrochromic behaviours in harsh mechanical or temperature environments. The experimental and simulation results uncovered the assembly mechanism of the SP-DN eutectogels. Unlike polymer hydrogels, the obtained SP-DN eutectogels showed high molecular design freedom and structural versatility. The findings of this work offer a promising strategy for developing the next generation of mechanically robust and functionally integrated soft materials with high environmental adaptability.

Functional degradation of visual cortical cells in aged rats.

Functional degradation of mammalian visual cortex is associated with aging. It has been hypothesized that much of the decline might be mediated by a degradation of cortical inhibitory system during senescence. In the present work, we compared the properties of adaptation, onset latency and signal-to-noise ratio in primary visual cortex of young and old rats using extracellular single-unit techniques. The short-term synaptic plasticity of young and old rats was also studied using field potential recording techniques. We found significant increased adaptation, prolonged onset latency, lower signal-to-noise ratio and decreased short-term synaptic plasticity in aged rats. The results are in accordance with previously reported functional declines in old monkeys and old cats, indicating a universal mechanism of degradation in cortical function that accompanies old age in different mammalian species.

Short-term synaptic plasticity in the rat geniculo-cortical pathway during development in vivo.

The critical period for visual system development in rats normally peaks at postnatal three weeks and ends at postnatal five weeks. However, the change of short-term synaptic plasticity during this period has rarely been investigated. In the present study, we compared the short-term plasticity of visual cortical responses to lateral geniculate nucleus stimulation in rats at different development stages (P20, P30 and adult) in vivo. The results show that paired-pulse depression (PPD) and frequency-dependent depression of evoked field potentials (FP) are present in P20 rats and increase in magnitude with development. The time course of this maturation of synaptic depression parallels that of the visual critical period. The weak synaptic depression observed in juvenile rats may be important in enhancing excitatory neurotransmission at a time when synapses are immature; this could endow immature synapses with wide integrative capabilities. In contrast, suppressive temporal interactions could provide an important substrate for neuronal processing of visual information in the mature cortex.

Short-term depression of synaptic transmission from rat lateral geniculate nucleus to primary visual cortex in vivo.

Two forms of short-term synaptic plasticity, paired-pulse depression (PPD) and frequency depression, were prominent in the adult rat geniculo-cortical visual pathway in vivo. Iontophoresis of GABAa receptor antagonist (bicuculline methiodide) or GABAb receptor antagonist (2-hydroxy-saclofen) in the primary visual cortex significantly reduced the short-term synaptic depression. When NMDA or AMPA/kainate receptors were blocked, no obvious change of synaptic depression was observed. Application of high [Ca(2+)] enhanced the short-term synaptic depression. Our results suggest that the presynaptic Ca(2+)-dependent neurotransmitter depletion and postsynaptic GABAergic inhibition may be crucial for short-term synaptic depression in the geniculo-cortical pathway.