While nanoparticle solutions cannot freeze in general, they may remain stable in the presence of polymer stabilizers. We herein communicate that gold nanoparticles (AuNPs) are stable in the presence of thiolated DNA after a freeze–thaw cycle. The DNA is conjugated to AuNPs during freezing without additional reagents and the conjugation can be completed in a few minutes. More importantly, the DNA density is 20–30% higher than that prepared by the typical salt-aging method. By lowering temperature, DNA hybridization is also promoted, allowing the construction of better nanoflares with doubled probe density and signaling sensitivity. This freezing method works for AuNPs from 5 to 100 nm and all tested DNA sequences. The mechanism was studied by separating the effect of temperature, freezing and thawing, where the exclusion of salt and AuNPs by the growing ice crystals is deemed critical. In addition to developing a simple method, this study articulates unique physical processes during freezing with important fundamental surface science implications, and it could be extended to other systems.

Nanoparticles and proteins are similar in a number of aspects, and using nanoparticles to mimic the catalytic function of enzymes is an interesting yet challenging task. Impressive developments have been made over the past two decades on this front. The term nanozyme was coined to refer to nanoparticlebased enzyme mimics. To date, many different types of nanozymes have been reported to catalyze a broad range of reactions for chemical, analytical, and biomedical applications. Since chemical reactions happen mainly on the surface of nanozymes, an interesting aspect for investigation is surface modification. In this review, we summarize three types of nanozyme materials catalyzing various reactions with a focus on their surface chemistry. For metal oxides, cerium oxide and iron oxide are discussed as they are the most extensively studied. Then, gold nanoparticles and graphene oxide are reviewed to represent metallic and carbon nanomaterials, respectively. Types of modifications include ions, small molecules, and polymers mainly by physisorption, while in a few cases, covalent modifications were also employed. The functional aspect of such modification is to improve catalytic activity, substrate specificity, and stability. Future perspectives of this field are speculated at the end of this review.

Hydrogen peroxide (H₂O₂) is a key molecule in biology. As a byproduct of many enzymatic reactions, H₂O₂ is also a popular biosensor target. Recently, interfacing H₂O₂ with inorganic nanoparticles has produced a number of nanozymes showing peroxidase or catalase activities. CeO₂ nanoparticle (nanoceria) is a classical nanozyme. Herein, a fluorescently labeled DNA is used as a probe, and H₂O₂ can readily displace adsorbed DNA from nanoceria, resulting in over 20-fold fluorescence enhancement. The displacement mechanism instead of oxidative DNA cleavage is confirmed by denaturing gel electrophoresis and surface group pK_a measurement. This system can sensitively detect H₂O₂ down to 130 nM (4.4 parts-per-billion). When coupled with glucose oxidase, glucose is detected down to 8.9 μM in buffer. Detection in serum is also achieved with results comparable with that from a commercial glucose meter. With an understanding of the ligand role of H₂O₂, new applications in rational materials design, sensor development, and drug delivery can be further exploited.