Meta-DNA Strand Displacement for Sub-Micron-Scale Autonomous Reconfiguration.

Dynamic molecular interactions in chemical reaction networks lead to complex behaviors in living systems. Whereas recent advances in programming DNA molecular reactions have reached a high level of complexity at molecular and nanometer scales, achieving programmable autonomous behavior at submicron or even larger scales remains challenging. Here, we present a mechanism of meta-DNA strand displacement reactions (M-SDRs) that is mediated solely by meta-toehold (M-toehold) using versatile submicron building blocks of meta-DNA (M-DNA). M-SDR emulates the toehold binding and branch migration processes of conventional strand displacement. Importantly, the kinetics of M-SDR can be modulated over a range of five orders of magnitude reaching a maximum rate of about 1.62 × 105 M-1 s-1. Further, we demonstrate the use of M-SDR to program autonomous reconfiguration in information transmission and logical computation systems. We envision that M-SDR serves as a versatile mechanism for emulating autonomous behavior approaching the cellular level.

Janus Nanoparticle Coupled Double-Network Hydrogel.

For double network (DN) hydrogels, their performance can be tuned by adjusting the interaction between their two networks. A novel DN hydrogel toughening approach is proposed by employing Janus nanoparticles (JNs) as crosslinkers to gain a conjoined-network hydrogel. First, a kind of JNs modified by amino groups and quaternary ammonium salt is synthesized, named R3 N+ -JN-NH2 . The DN hydrogel is fabricated based on ionic coordination between calcium chloride (CaCl2 ) and sodium alginate (Alg), as well as covalent (benzoic imine) between glycol chitosan (GC) and benzaldehyde-capped poly(ethylene oxide) (BzCHO-PEO-BzCHO). Based on the same covalent and ionic dynamic crosslinking mechanism, the added R3 N+ -JN-NH2 interacts with two networks to promote crosslinking to form a dually crosslinked structure. The R3 N+ -JN-NH2 effectively provides more energy dissipation, and the hydrogel with conjoined networks shows better compression resistance.

One-Step Nanosurface Self-Assembly of d-Peptides Renders Bubble-Free Ultrasound Theranostics.

The surface bioinspired modification of particles and films is a mainstream direction in biomaterial design and application. The interfacial coating of extracellular-matrix-like hydrogel can endow functional inorganic nanoparticles high circulation stability and biocompatibility but remains challenging due to large surface tension difference between organic gelators and solid nanosurfaces. Herein, the supramolecular hydrogel of NapGdFdFdK around gold nanorods (Au NRs-Gel) has been constructed by the amidation-grafting modification and the protonation-induced interface-assistant assembly of peptide precursors. As a proof of concept study, the acoustic cavitation experiments and in vitro ultrasound imaging have proved that the abundant hydrophobic microdomains as well as the water-rich network in the supramolecular hydrogel can serve as valid sites to efficiently generate and stabilize nanobubbles as cavitation seeds to realize bubble-free ultrasound imaging. In vivo augmented ultrasound imaging and imaging-guided high intensity focused ultrasound (HIFU) therapy based on the Balb/c mice bearing HeLa tumor model have been conducted. As the first example of using nanosurface hydrogelation to endow nanoparticles with bubble-free ultrasound theranostic ability, this work offers a simple approach to design multifunctional nanovehicles for ultrasound-guided drug/protein/gene delivery.

Nanogel Multienzyme Mimics Synthesized by Biocatalytic ATRP and Metal Coordination for Bioresponsive Fluorescence Imaging.

The design of enzyme mimics from stable and nonprotein systems is especially attractive for applications in highly specific cancer diagnosis and treatment, and it has become an emerging field in recent years. Herein, metal crosslinked polymeric nanogels (MPGs) were prepared using FeII ion coordinated biocompatible acryloyl-lysine polymer brushes obtained from an enzyme-catalyzed atomic transfer radical polymerization (ATRPase) method. The monoatomic and highly dispersed Fe ions in the MPGs serve as efficient crosslinkers of the gel network, and also as active centers of multienzyme mimics of superoxide dismutase (SOD) and peroxidase (POD). The catalytic activities were compared to those of conventional Fe-based nanozymes. Studies on both cells and animals verify that efficient reactive oxygen species (ROS) responsive biofluorescence imaging can be successfully realized using the MPGs.

Strength-tunable printing of xanthan gum hydrogel via enzymatic polymerization and amide bioconjugation.

Amide bioconjugation and interfacial enzyme polymerization are designed to provide a general strategy for regulating the mechanical strength (storage modulus from 3 kPa to 100 kPa) of printable hydrogel inks.