Manganese-doped iron coordination polymer nanoparticles with enhanced peroxidase-like activity for colorimetric detection of antioxidants.

A convenient and sensitive antioxidant assay with high performance is essential for assessing food quality and monitoring the oxidative stress level of biological matrices. Although coordination polymer nanoparticles (CPNs)-based nanozymes have emerged as candidates in the analytical field, strategies to improve the catalytic activity of CPNs have been scarcely revealed and studied. Herein, we demonstrate a manganese (Mn) doping strategy to enhance the peroxidase-mimetic activity of Fe-based CPNs. By tuning the Mn doping amounts and selecting 2,5-dihydroxyterephthalic acid (H4DHTP) as ligands, the produced nanozymes in amorphous state followed the catalytic activity order of Fe5Mn-DHTP > Fe8Mn-DHTP > Fe2Mn-DHTP > Fe-DHTP > Mn-DHTP. Ulteriorly, benefitting from the best catalytic performance and definite catalytic mechanism of Fe5Mn-DHTP, versatile colorimetric assays for ultrasensitive detection of one exogenous antioxidant (ascorbic acid, AA) and two endogenous antioxidants (glutathione, GSH; cysteine, Cys) have been deftly devised based on the inhibition of the 3,3',5,5'-tetramethylbenzidine chromogenic reaction in presence of H2O2. It was found that mercaptan (GSH and Cys) and AA exhibited different inhibition mechanisms. Practically, such a colorimetric assay was viable to determine the total antioxidant capacity of drugs and foods with desirable results. This work proposes a feasible strategy for embellishing CPN nanozymes used for designing sensitive and convenient assays for various antioxidants based on an explicit detection mechanism.

Ultrathin PdCu alloy nanosheet-assembled 3D nanoflowers with high peroxidase-like activity toward colorimetric glucose detection.

Enzyme-mimetic properties of nanomaterials can be efficiently tuned by controlling their size, composition, and structure. Here, ultrathin PdCu alloy nanosheet-assembled three-dimensional (3D) nanoflowers (Pd1Cux NAFs) with tunable surface composition are obtained via a generalized strategy. In presence of H2O2, the as-synthesized Pd1Cux NAFs can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to the oxidized form of TMB (oxTMB) with a characteristic absorption peak at 652 nm. Interestingly, Pd1Cux NAFs show obviously composition-dependent peroxidase-like catalytic activities because of the synergistic interaction of nanoalloy. Additionally, different from 2D Pd nanosheets, the distinctive 3D superstructures are featured with rich approachable sites and proper layer spacing, which are in favor of fast mass transport and electron transfers during the catalytic process. Among the studied Pd1Cux NAFs, the Pd1Cu1.7 NAFs show the highest enzyme-like activities and can be successfully applied for the colorimetric detection of glucose with a low detection limit of 2.93 ± 0.53 µM. This work provides an efficient avenue to fabricate PdCu NAF nanozymes in biosensing toward glucose detection. Two-dimensional (2D) PdCu ultrathin nanosheet-assembled 3D nanoflowers (Pd1Cux NAFs) with tunable surface composition exhibit substantially enhanced intrinsic peroxidase-like catalytic activities. The Pd1Cu1.7 NAFs are successfully used as peroxidase mimic catalyst for the colorimetric detection of glucose with low detection limit of 2.93 µM.

Fluorescence assay for alkaline phosphatase based on ATP hydrolysis-triggered dissociation of cerium coordination polymer nanoparticles.

Alkaline phosphatase (ALP) is a significant biomarker for diagnostics. Simple, selective and sensitive detection of ALP activity is thus of critical importance. In this study, an artful fluorescence assay for ALP is proposed based on adenosine triphosphate (ATP) hydrolysis-triggered disassociation and fluorescence quenching of cerium coordination polymer nanoparticles (CPNs). ATP, a recognized natural substrate of phosphatase, can serve as a superb "antenna" to sensitize the luminescence of Ce3+ with the aid of tris(hydroxymethyl) aminomethane (Tris), forming Ce3+-ATP-Tris CPNs. In the presence of ALP, ATP will be catalytically converted into adenosine and inorganic orthophosphate, however neither of them can sensitize Ce3+ in alkaline media. As a result, the obtained CPNs are disassociated, inducing the quenching of the fluorescence. On this basis, a straightforward fluorescence assay for ALP activity is rationally developed. The fluorescence quenching efficiency shows a linear relationship for ALP within the activity range from 0.1 to 10 mU mL-1 with a detection limit of 0.09 mU mL-1 under the optimal experimental conditions. Moreover, this facile yet effective fluorescence method featured simplicity, cost-effectiveness, high sensitivity and high selectivity and can be successfully utilized for the quantitative detection of ALP in human serum samples.

Malathion detection based on polydopamine enhanced oxidase-mimetic activity of palladium nanocubes.

Nowadays, fabricating simple and efficient pesticide detection methods become a research focus due to the great threat pesticide residues posed to human health and environment. Herein, we constructed a high-efficiency and sensitive colorimetric detection platform for malathion detection based on polydopamine-dressed Pd nanocubes (PDA-Pd/NCs). The Pd/NCs coated with PDA exhibited excellent oxidase-like activity, which was attributed to the substrates accumulation and accelerated electron transfer induced by PDA. What's more, we successfully achieved sensitive detection of acid phosphatase (ACP) using 3,3',5,5'-tetramethylbenzidine (TMB) as the chromogenic substrate, relying on the satisfactory oxidase activity from PDA-Pd/NCs. However, the addition of malathion could inhibit the activity of ACP and limit the production of medium AA. Therefore, we constructed a colorimetric assay for malathion based on PDA-Pd/NCs + TMB + ACP system. The wide linear range (0-8 µM) and low detection limit (0.023 µM) indicate excellent analytical performance, which is superior to most malathion analysis methods previously reported. This work not only provides a new idea for dopamine coated nano-enzyme to improve its catalytic activity, but also creates a new tactics for the detection of pesticides such as malathion.

X-ray-Triggered CO Release Based on GdW10/MnBr(CO)5 Nanomicelles for Synergistic Radiotherapy and Gas Therapy.

Carbon monoxide (CO) therapy has become a hot topic in the field of gas therapy because of its application prospect in the treatment of various diseases. Due to the high affinity for human hemoglobin, the main challenge of CO-loaded nanomedicine is the lack of selectivity and toxicity in the delivery process. Although many commercial CO-releasing molecules (CORMs) have been widely developed because of their ability to deliver CO, CORMs still have some disadvantages, including difficult on-demand controlled CO release, poor solubility, and potential toxicity, which are limiting their further application. Herein, an X-ray-triggered CO-releasing nanomicelle system (GW/MnCO@PLGA) based on GdW10 nanoparticles (NPs) (GW) and MnBr(CO)5 (MnCO) encapsulating in the poly(lactic-co-glycolic acid) (PLGA) polymer was constructed for synergistic CO radiotherapy (RT). The production of strongly oxidative superoxide anion (O2-•) active species can lead to cell apoptosis under the X-ray sensitization of GW. Moreover, strongly oxidative O2-• radicals further oxidize and compete with the Mn center, resulting in the on-demand release of CO. The radio/gas therapy synergy to enhance the efficient tumor inhibition of the nanomicelles was investigated in vivo and in vitro. Therefore, the establishment of an X-ray-triggered controlled CO release system has great application potential for further synergistic RT CO therapy in deep tumor sites.