Swellable colorimetric microneedles for glucose detection based on glucose oxidase-like gold nanoparticles.

BACKGROUND: Regular blood glucose monitoring is very important for diabetic patients. The composition of skin interstitial fluid (ISF) is similar to that of blood, which can be used for daily blood sugar detection and disease care. However, most methods of ISF extraction have complicated steps, may cause skin damage, and can only extract a limited amount of ISF, resulting in low detection efficiency. Therefore, it is very necessary to develop a detection method that can not only extract a large amount of ISF safely, efficiently, and conveniently, but also realize rapid detection of glucose level in ISF. RESULTS: Here, we developed a gold nanoparticle (AuNP)-based swellable colorimetric MN patch with minimally invasive sampling function and real-time ISF glucose analysis ability. The MN patch could quickly absorb a large amount of skin ISF, and 60.2 mg of ISF was extracted within 10 min in vitro. It was divided into two layers: the tip layer was embedded with AuNPs with glucose oxidase (GOx)-like activity, which catalyzed the oxidation of glucose extracted from ISF and produced hydrogen peroxide (H2O2); horseradish peroxidase (HRP) encapsulated in the backing layer catalyzed the oxidation of 3, 3', 5, 5'-tetramethylbenzidine (TMB) by H2O2 to produce oxTMB, which led to a visible color shift in the backing layer. The ISF glucose level was judged by naked eyes and further quantified by color analysis with Image J software. As a result, the colorimetric MN patch successfully identified the normal blood sugar and hyperglycemia state in vivo. SIGNIFICANCE: The colorimetric MN patch combined in-situ colorimetric sensing based on AuNP nanozyme with MN patch, which detected glucose level without blood drawing, increasing patients' compliance and reducing detection steps and time. Compared with the detection methods based on natural nanozymes, our method had better stability and sensitivity to complex environments (extreme pH and high temperature, etc.) in actual detection.

Development of an Au-anchored Fe Single-atom nanozyme for biocatalysis and enhanced tumor photothermal therapy.

Near-infrared light-induced photothermal therapy (PTT) can achieve effective tumor ablation, but the associated hyperthermic temperatures result in off-target inflammatory damage to proximal tissues. Therefore, killing the tumor at a lower temperature is vital to improving the clinical effect of PTT. In this study, an Au-integrated Fe single-atom nanozyme (FeSAzyme) was developed through the immobilization of an ultrasmall Au nanozyme within a metal-organic framework via an in situ reduction approach. The nanozyme was found to exhibit favorable glucose oxidase- (GOD) like activity and photosensitizing properties to better achieve low-temperature PTT. The Au-carbon nanozyme was able to markedly inhibit tumor growth both in vitro and in vivo due to its GOD-like activity and enhanced photodynamic and photothermal properties. In addition, the integration of the Au nanozyme enhanced the FeSAzyme's peroxidase activity and catalyzed endogenous H2O2 species to generate reactive oxide species, thereby facilitating chemodynamic therapy. Furthermore, its integration markedly enhanced the PTT performance of the FeSAzyme, which achieved pronounced synergistic anti-tumor efficacy. The enzymatic activity and photothermal/photosensitive properties of the Au-FeSAzyme may help to overcome traditional therapeutic limitations, indicating its potential for catalytic cascade nanozymes in biomedical applications.

Au-Au/IrO2@Cu(PABA) Reactor with Tandem Enzyme-Mimicking Catalytic Activity for Organic Dye Degradation and Antibacterial Application.

Herein, a Au-Au/IrO2 nanocomposite with tandem enzyme-mimicking activity was innovatively synthesized, which can show outstanding glucose oxidase (GOx)-like activity and peroxidase-like activity simultaneously under neutral conditions. Moreover, a Au-Au/IrO2@Cu(PABA) reactor was prepared via encapsulation of the Au-Au/IrO2 nanocomposite in a Cu(PABA) metal organic framework. The reactor not only exhibits excellent organic solvent stability, acid resistance, and reusability but also displays better cascade reaction catalytic efficiency (kcat/Km = 148.86 min-1 mM-1) than the natural free enzyme system (GOx/HRP) (kcat/Km = 98.20 min-1 mM-1) and Au-Au/IrO2 nanocomposite (kcat/Km = 135.24 min-1 mM-1). In addition, it is found that the reactor can catalyze glucose or dissolved oxygen to produce active oxygen species (ROS) including HO, 1O2, and O2-· through its enzyme-mimicking activity. Finally, the novel reactor was successfully used in organic dye degradation and antibacterial application. The results show that it can effectively degrade methyl orange, methylene blue, and rhodamine B, which all can reach a degradation rate of nearly 100% after interacting with Au-Au/IrO2@Cu (PABA) for 3.5 h. Furthermore, the reactor also exhibits excellent antibacterial activity, so as to achieve a complete bactericidal effect to Staphylococcus aureus and Escherichia coli at a concentration of 12.5 µg mL-1.

Glucose oxidase-like activity of cerium oxide nanoparticles: use for personal glucose meter-based label-free target DNA detection.

Recently, personal glucose meter (PGM) has been utilized for the detection of non-glucose targets for point-of-care (POC) testing. Aimed at this goal, we herein developed a new PGM-based label-free read-out method for polymerase chain reaction (PCR) based on our novel finding that cerium oxide nanoparticles (CeO2 NPs) exhibit glucose oxidase-like activity comparable to the natural glucose oxidase enzyme. Methods: In principle, DNA amplicons produced by PCR in the presence of target DNA electrostatically bind to CeO2 NPs, leading to their aggregation and reducing the efficiency for CeO2 NP-catalyzed glucose oxidation reaction. Thus, glucose is hardly oxidized to gluconic acid, resulting in the maintenance of initial high glucose level. On the contrary, in the absence of target DNA or presence of non-target DNA, DNA amplicons are not produced and glucose is effectively oxidized by the glucose oxidase-like activity of CeO2 NPs, leading to the significant reduction of glucose level. Finally, the resulting glucose level is simply measured by using PGM. Results: With this strategy, DNA amplicons were quantitatively examined within 5 min, realizing ultrafast analysis of PCR results without any cumbersome and labor-intensive procedures. In addition, the target genomic DNA derived from Escherichia coli (E. coli) was sensitively determined down to 10 copies with high selectivity. Conclusion: Importantly, the use of PGM as a detection component enables its direct application in POC settings. Based on the meritorious features of PGM such as rapidity, simplicity, and cost-effectiveness, we expect that the devised system could serve as a core platform for the on-site read-out of PCR amplification.

CeO2 -Encapsulated Hollow Ag-Au Nanocage Hybrid Nanostructures as High-Performance Catalysts for Cascade Reactions.

Inspired by bio-enzymes, multistep cascade reactions are highly attractive in catalysis. Despite extensive research in recent years, it remains a challenge to promote the stability and activity of catalysts. Here, well-defined core-shell structured Ag-Au nanocage@CeO2 (Ag-Au NC@CeO2 ) are designed by a simple and facile self-assembly method. The results indicate that the Ag-Au NC@CeO2 has glucose oxidase-like activity and intrinsic peroxidase-like activity at the same time. As expected, Ag-Au NC@CeO2 hybrid nanomaterials exhibit cascade reactions activity. Moreover, the hybrid materials are promising to detect glucose without bio-enzymes. This research has potential applications in biomedicine and biomimetic catalysis.

"Non-Naked" Gold with Glucose Oxidase-Like Activity: A Nanozyme for Tandem Catalysis.

It has been widely reported that "naked" gold nanoparticles (Au NPs) without protectors have glucose oxidase (GOx)-like activity, and the use of protectors can inhibit the GOx-like activity. Here, "non-naked" Au NPs with GOx-like activity are synthesized by using protein as protector. Although "naked" Au NPs have peroxidase-like activity and GOx-like activity, the optimal pH ranges of the both activities are obviously different. Fortunately, as-synthesized "non-naked" Au NPs show the dual enzyme-like activities at the same pH. So, "non-naked" Au NPs can be described as "tandem nanozyme." As another bonus, the participation of protein protector can stabilize the GOx-like activity and make Au NPs modifiable. Even though Au NPs are connected with graphene oxide (GO), the GOx-like activity is still not changed. Further, Au NPs-GO nanocomposites are applied on the one-pot nonenzymatic glucose colorimetric detection. The "non-naked" gold not only broadens the species of tandem nanozymes, but also facilitates the functionalization of nanozymes, which is promising for immunoassay, biosensor, and medical treatment.