Efficient photocatalytic nanocrystals with high-ratio exposure of active facets have aroused a great number of research interests in recent years. However, most preparations of such materials need the addition of special capping agents (like surfactants) or harsh reaction conditions (such as hydrothermal reactions). In this work, a controllable synthesis of BiOBr nanosheets with a thickness from 9 nm to 32 nm was easily achieved in a hydrolysis system through adjusting temperature and solvent, without adding any surfactant or capping agents. As the thickness of the nanosheets decreases from 32 nm to 9 nm, the ratio of exposed {001} facets, the active photocatalysis facets in BiOBr crystals, increases from 83% to 94%, along with an increased photocatalytic efficiency over rhodamine B (RhB) under visible-light. Various methods such as SEM, TEM, AFM, DRS and Raman spectroscopy were used to fully characterize the as-obtained BiOBr nanosheets. More importantly, the obtained BiOBr nanosheets exhibit a selective visible-light photocatalytic behavior as the activity over RhB is much higher than that over Methyl Orange (MO) or Methylene Blue (MB). This phenomenon was studied with in situ electron paramagnetic resonance (EPR) measurements and the potential mechanism was explored.
Enzymes, together with the process of self-assembly, constitute necessary components of the foundation of life on the nanometre scale. The exceedingly high efficiency and selectivity exhibited by enzymes for catalyzing biotransformations naturally lead to the exploration of enzyme mimics and the applications of enzymes in industrial biotransformations. While the mimicking of enzymes aims to preserve the essence of enzymes in a simpler system than proteins, industrial biotransformations demand high activity and stability of enzymes. Recent research suggests that small peptide-based nanofibers in the form of molecular hydrogels can provide a general platform to achieve both important goals. This tutorial review will introduce the recent progress of these research activities on small peptide-based nanomaterials for catalysis and hopes to provide a starting point for further explorations that ultimately may lead to practical applications of enzymes and enzyme mimics for addressing important societal problems in energy, environment, and health.
As the first line of innate immune cells to migrate towards tumour tissue, neutrophils, can immediately kill abnormal cells and activate long-term specific adaptive immune responses. Therefore, the enzymes mediated elevation of reactive oxygen species (ROS) bioinspired by neutrophils can be a promising strategy in cancer immunotherapy. Here, we design a core-shell supramolecular hybrid nanogel via the surface phosphatase triggered self-assembly of oligopeptides around iron oxide nanoparticles to simulate productive neutrophil lysosomes. The cascade reaction of superoxide dismutase (SOD) and chloroperoxidase (CPO) within the bioinspired nanogel can convert ROS in tumour tissue to hypochlorous acid (HOCl) and the subsequent singlet oxygen (1O2) species. Studies on both cells and animals demonstrate successful 1O2-mediated cell/tumour proliferation inhibition, making this enzyme therapy capable for treating tumours without external energy activation.
Peroxisome, a special cytoplasmic organelle, possesses one or more kinds of oxidases for hydrogen peroxide (H 2 O 2 ) production and catalase for H 2 O 2 degradation, which serves as an intracellular H 2 O 2 regulator to degrade toxic peroxides to water. Inspired by this biochemical pathway, we demonstrate the reactive oxygen species (ROS) induced tumor therapy by integrating lactate oxidase (LOx) and catalase (CAT) into Fe 3 O 4 nanoparticle/indocyanine green (ICG) co-loaded hybrid nanogels (designated as FIGs-LC). Based on the O 2 redistribution and H 2 O 2 activation by cascading LOx and CAT catalytic metabolic regulation, hydroxyl radical (·OH) and singlet oxygen ( 1 O 2 ) production can be modulated for glutathione (GSH)-activated chemodynamic therapy (CDT) and NIR-triggered photodynamic therapy (PDT), by manipulating the ratio of LOx and CAT to catalyze endogenous lactate to produce H 2 O 2 and further cascade decomposing H 2 O 2 into O 2 . The regulation reactions of FIGs-LC significantly elevate the intracellular ROS level and cause fatal damage to cancer cells inducing the effective inhibition of tumor growth. Such enzyme complex loaded hybrid nanogel present potential for biomedical ROS regulation, especially for the tumors with different redox state, size, and subcutaneous depth.