Strategies and Applications for Supramolecular Protein Self-Assembly.

Supramolecular chemistry achieves higher-order molecular self-assembly through non-covalent interactions. Utilizing supramolecular methods to explore the polymorphism of proteins, the building blocks of life, from a "bottom-up" perspective is essential for constructing diverse and functional biomaterials. In recent years, significant progress has been achieved in the design strategies and functional applications of supramolecular protein self-assembly, becoming a focal point for researchers.

Current Advances of Atomically Dispersed Metal-Centered Nanozymes for Tumor Diagnosis and Therapy.

Nanozymes, which combine enzyme-like catalytic activity and the biological properties of nanomaterials, have been widely used in biomedical fields. Single-atom nanozymes (SANs) with atomically dispersed metal centers exhibit excellent biological catalytic activity due to the maximization of atomic utilization efficiency, unique metal coordination structures, and metal-support interaction, and their structure-activity relationship can also be clearly investigated. Therefore, they have become an emerging alternative to natural enzymes.

Recent development in the design of artificial enzymes through molecular imprinting technology.

Enzymes, a class of proteins or RNA with high catalytic efficiency and specificity, have inspired generations of scientists to develop enzyme mimics with similar capabilities. Many enzyme mimics have been developed in the past few decades based on small molecules, DNA, and nanomaterials. These artificial enzymes are of great interest because of their low cost and high stability.

"On/Off" Switchable Sequential Light-Harvesting Systems Based on Controllable Protein Nanosheets for Regulation of Photocatalysis.

A controllable protein nanostructures-based "On/Off" switchable artificial light-harvesting system (LHS) with sequential multistep energy transfer and photocatalysis was reported herein for mimicking the natural LHS in both structure and function. Single-layered protein nanosheets were first constructed via a reversible covalent self-assembly strategy using cricoid stable protein one (SP1) as building blocks to realize an ordered arrangement of pigments. Fluorescent chromophores like carbon dots (CDs) can be precisely distributed on the protein nanosheets superficially via electrostatic interactions and make the ratio between donors and acceptors adjustable.

Biocompatible Diselenide-Containing Protein Hydrogels with Effective Visible-Light-Initiated Self-Healing Properties.

Smart hydrogels are typical functional soft materials, but their functional and mechanical properties are compromised upon micro- or macro-mechanical damage. In contrast, hydrogels with self-healing properties overcome this limitation. Herein, a dual dynamic bind, cross-linked, self-healing protein hydrogel is prepared, based on Schiff base bonds and diselenide bonds.

Hierarchical protein self-assembly into dynamically controlled 2D nanoarrays host-guest chemistry.

A dynamically reversible two-dimensional (2D) protein assembly system was designed based on host-guest interactions and was triggered to disassemble a competition mechanism. The artificially tunable and reversible protein assembly architectures hold great potential for on/off switches in bio-systems.

Rational Design and Biological Application of Antioxidant Nanozymes.

Nanozyme is a type of nanostructured material with intrinsic enzyme mimicking activity, which has been increasingly studied in the biological field. Compared with natural enzymes, nanozymes have many advantages, such as higher stability, higher design flexibility, and more economical production costs. Nanozymes can be used to mimic natural antioxidant enzymes to treat diseases caused by oxidative stress through reasonable design and modification.

Difunctionalized pillar[5]arene-based polymer nanosheets for photodynamic therapy of infection.

Bacterial infections pose severe threats to global public health security. Developing antibacterial agents with both high efficiency and safety to handle this problem has become a top priority. Here, highly stable and effective polymer nanosheets have been constructed by the covalent co-assembly of a pillar[5]arene derivative and metalloporphyrin for photodynamic antibacterial therapy (PDAT).

Construction of Ultralarge Two-Dimensional Fluorescent Protein Arrays via a Reengineered Rhodamine B-Based Molecular Tool.

The self-luminous property of enhanced green fluorescent protein (EGFP) makes it an extremely attractive building block for creating functional biomaterials. A practical challenge in the design of EGFP-based materials, however, stems from the structural and chemical heterogeneity of the EGFP surface. In this study, a maleimide-functionalized rhodamine B molecule (RhGM) was designed as a versatile molecular tool to overcome this obstacle.

Morphological Transformation between Orthogonal Dynamic Covalent Self-Assembly of Imine-Boroxine Hybrid Polymer Nanocapsules and Thin Films via Linker Exchange.

Orthogonal dynamic covalent self-assembly is used as a facile method for constructing polymer hollow nanocapsules (NCs) and thin films. The bifunctional precursor 4-formylphenylboronic acid is symmetrically installed with a boronic acid group for the boroxine linkage, and an aldehyde group for the Schiff base reaction which can react with twofold symmetry linkers ethylenediamine and para phenylenediamine to attain polymer NCs and nanosheets. Owing to the reversibility of the imine linkages, the mutual morphological transformation between polymer NCs and thin films via an amine-imine-exchange strategy is successfully achieved.

Light-responsive vesicles for enantioselective release of chiral drugs prepared from a supra-amphiphilic M-helix.

A kind of light-responsive vesicle was prepared by aqueous self-assembly of α-CD and an azobenzene-containing M-helical foldamer, which displayed dynamic disassembly-reassembly structural transformation when alternately irradiated by UV and visible light. Distinctively, this vesicle also exhibited enantioselective release abilities toward racemic propranolol (a β-blocker), owing to the M-helical building blocks.

Cucurbit[8]uril-based supramolecular nanocapsules with a multienzyme-cascade antioxidative effect.

A supramolecular nanocapsule was constructed by the ternary host-guest complexation of azobenzene (Azo) and methylviologen (MV) to cucurbit[8]uril (CB[8]) and the subsequent self-assembly. The supramolecular nanocapsule with both glutathione peroxidase (GPx) and superoxide dismutase (SOD) activities can mimic the intracellular enzymatic reactive oxygen species (ROS) defense system.

A remote optically controlled hydrolase model based on supramolecular assembly and disassembly of its enzyme-like active site.

A photoresponsive hydrolase model was constructed through the spatial organization of histidine/arginine-containing peptide supra-amphiphiles that are held together by cucurbit[8]uril (CB[8]) methylviologen (MV) azobenzene (Azo) ternary complexation and subsequently self-assemble into highly uniform giant vesicles. The reversible morphological transition of the vesicular structures to non-assembled peptide fragments was triggered by azobenzene photoisomerization. This enables the assembly/disassembly of its enzyme-like active site to cause a dramatic change in hydrolytic activity.

An ultrathin iron-porphyrin based nanocapsule with high peroxidase-like activity for highly sensitive glucose detection.

For the first time, an ultrathin iron-porphyrin based polymer nanocapsule with multiple peroxidase-like catalytic centers was constructed by covalently assembling iron-porphyrin monomers; this nanocapsule with a single molecule thickness shell acted as a highly efficient artificial enzyme for mimicking peroxidase. On the basis of the peroxidase-like activity of Fe-TPyP based nanocapsules (Fe-TPyP NCs), a highly sensitive colorimetric sensor for glucose determination was fabricated, the limit of detection was found to be as low as 0.098 μM.

Reductive-Responsive, Single-Molecular-Layer Polymer Nanocapsules Prepared by Lateral-Functionalized Pillar[5]arenes for Targeting Anticancer Drug Delivery.

Herein, a new reductive-responsive pillar[5]arene-based, single-molecule-layer polymer nanocapsule is constructed for drug delivery. The functionalized system shows good biocompatibility, efficient internalization into targeted cells and obvious triggered release of entrapped drugs in a reducing environment such as cytoplasm. Besides, this smart vehicle loaded with anticancer drug shows excellent inhibition for tumor cell proliferation and exhibits low side effect on normal cells.