Colorimetric detection of tetracycline by enhancing peroxidase-like activity of polymerized MnO2@ZIF-67 nanocomposites.

The persistence of tetracycline (TC) antibiotic residues in foodstuffs and aquatic systems poses critical threats to human health and the ecological environment, driving an imperative demand for developing multifunctional platforms capable of simultaneous visual monitoring and high-efficiency elimination of these contaminants. Herein, a simple yet novel colorimetric sensor that integrates detection and degradation of TCs has been constructed based on the excellent peroxidase-like activity of the metal-organic frameworks (MOFs) MIL-101(Fe). Colorless 3,3',5,5'-tetramethylbenzidine (TMB) can be effectively oxidized to generate blue oxidized TMB (ox-TMB) by MIL-101(Fe), which exhibits a characteristic peak at 652 nm. The presence of TCs at varying concentrations can specifically inhibit this oxidation reaction, leading to different degrees of decrease in the intensity of the characteristic peak. Based on this concentration-dependent chromogenic behavior, TCs are quantitative identified by the dual-mode detection of UV-Vis absorbance and with the naked eye. The as-fabricated colorimetric sensor displays superior selectivity toward TCs, with its detection capability in complex matrices being successfully validated in environmental water and commercial milk samples. To avoid accessional antibiotic contamination, MIL-101(Fe) can also be served as a scavenger to degrade TCs efficiently under visible light irradiation, achieving up to 92.01% removal efficiency within 3 h. The developed strategy has the advantages of visual recognition, rapid field detection and no requirement of large-scale instruments. Most critically, it cleverly realizes the integration of antibiotic detection and degradation, which provides a low-cost and high-efficiency solution to fundamentally solve the problem of antibiotic contamination.

Anovel colorimetric aptasensor has been developedfor highly sensitive tetracycline (TC) detection based on the peroxidase-like activity of Fe3O4@Cu nanoparticles and "sandwich" oligonucleotide hybridization. The Fe3O4@Cu nanoparticles with high peroxidase-like activity were successfully synthesized under mild conditions. Then, a "sandwich" oligonucleotide hybridization probe (a short amino-modified complementary sequence of a portion of the TC aptamer (cDNA1), TC aptamers, and a long complementary to 5' terminal TC aptamer sequence (cDNA2)) was created in 96-wells plates via DNA hybridization in the absence of TC from the detection system. The unique "sandwich" oligonucleotide hybridization probe adsorbed large numbers of Fe3O4@Cu nanozymes while further enhancing its peroxidase-like activity. Based on the 3,3',5,5'-tetramethylbenzidine (TMB)-hydrogen peroxide (H2O2) reporting system, the blue color of the solution decreased linearly with the increase ofTC concentration, ranging from 10-3 to 103μg/L with an ultralow limit of detection (LOD) of 0.91ng/L (2pM). Theproposed method was successfully applied to detect TC in spiked milk samples, with recoveries of 81.8 to 112%, demonstrating the excellent potential for highly sensitive TC detection in milk.

Appropriate addition of phosphate salt in food can improve the food quality and taste. However, extensive intake of phosphate salt may lead to some human diseases such as hyperphosphatemia and renal insufficiency. Thus, it is essential to establish a cost-effective, convenient, sensitive, and selective method for monitoring phosphate ion (Pi) to ensure food quality control. In this work, a Co-based metal-organic frameworks (Co-MOF) nanomaterial with dual functions (peroxidase-like activity and specific recognition) was designed for acting as a catalytic chromogenic platform for sensitive detection of Pi. The Co2+ nodes not only provide high enzyme-like activity to catalyze the 3,3′,5,5′--tetramethylbenzidine (TMB) substrate to blue oxTMB (652 nm) but also act as selective sites for Pi recognition. The use of cationic organic ligands (2-methylimidazole) and cationic metal ions (Co2+) endows the Co-MOF with a strong positive surface charge, which is beneficial to the capture of negative-charged Pi and the dramatically suppressed TMB oxidation. When Pi exists, it specifically adsorbs onto the Co-MOF through the Co-O-P bond and the strong electrostatic interaction, leading to the change of surface charge on Co-MOF. The peroxidase-like catalytic activity of Co-MOF is thus restrained, causing a different catalytic effect on TMB oxidation from that without Pi. Based on this principle, a colorimetric assay was established for rapid and sensitive detection of Pi. A good linear relationship was obtained between Pi concentration and the absorbance at 652 nm, with a linear range of 0.009–0.144 mg/L and a detection limit of 5.4 μg/L. The proposed assay was applied to the determination of Pi in actual food samples with recoveries of 92.2–108% and relative standard deviations (RSDs) of 2.7–7.3%, illustrating the promising practicality for actual samples analysis.

Nanozyme-based colorimetric and smartphone imaging advanced sensing platforms for tetracycline detection and removal in food

A spatial-potential-color-resolved bipolar electrode electrochemiluminescence biosensor (BPE-ECL) using a CuMoOx electrocatalyst was constructed for the simultaneous detection and imaging of tetracycline (TET) and lincomycin (LIN). HOF-101 emitted peacock blue light under positive potential scanning, and CdSe quantum dots (QDs) emitted green light under negative potential scanning. CuMoOx could catalyze the electrochemical reduction of H2O2 to greatly increase the Faradic current of BPE and realize the ECL signal amplification. In channel 1, CuMoOx-Aptamer II (TET) probes were introduced into the BPE hole (left groove A) by the dual aptamer sandwich method of TET. During positive potential scanning, the polarity of BPE (left groove A) was negative, resulting in the electrochemical reduction of H2O2 catalyzed by CuMoOx, and the ECL signal of HOF-101 was enhanced for detecting TET. In channel 2, CuMoOx-Aptamer (LIN) probes were adsorbed on the MXene of the driving electrode (DVE) hole (left groove B) by hydrogen-bonding and metal-chelating interactions. LIN bound with its aptamers, causing CuMoOx to fall off. During negative potential scanning, the polarity of DVE (left groove B) was negative and the Faradic current decreased. The ECL signal of CdSe QDs was reduced for detecting LIN. Furthermore, a portable mobile phone imaging platform was built for the colorimetric (CL) detection of TET and LIN. Thus, the multiple mode-resolved detection of TET and LIN could be realized simultaneously with only one potential scan, which greatly improved detection accuracy and efficiency. This study opened a new technology of BPE-ECL sensor application and is expected to shine in microchips and point-of-care testing (POCT).

A competitive dual-mode for tetracycline antibiotics sensing based on colorimetry and surface-enhanced Raman scattering.

Adenosine triphosphate (ATP) is produced mainly in the mitochondrion, and its primary task is to function as a ubiquitous energy currency to meet the cellular metabolic demands in biological system...

The greater advantages and wide applications of zero-dimensional nanodots inspire researchers to develop new materials. Therefore, novel borophene quantum dots (QDs) were prepared by a hydrothermal liquid exfoliation technique using water medium. The borophene QDs proved to be highly stable in water medium for more than 120 days. The synthesized borophene QDs revealed intrinsic peroxidase mimetic activity using two chromogenic substrates, 3,3',5,5'-tetramethylbenzidine (TMB) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt (ABTS). The excellent intrinsic peroxidase activity toward TMB and ABTS substrates was executed using optimal reaction conditions (pH, borophene QDs' concentration, incubation time, and temperature). The formation of hydroxyl radicals in the presence of H2O2 upon TMB and ABTS oxidation played a significant role in the peroxidase reaction. The borophene QDs further proved to be successful for the colorimetric detection of antibiotics (oxytetracycline and tetracycline) using both TMB and ABTS peroxidase substrates. The limit of detection (LOD) for oxytetracycline and tetracycline was found to be 1.10 and 1.02 μM using TMB and 1.03 and 1.02 μM using ABTS chromogenic substrates, respectively. In addition, the fluorescence sensing of oxytetracycline and tetracycline over borophene QDs was also examined. The high fluorescence of borophene QDs (turn ON) was quenched (turn OFF) by oxytetracycline and tetracycline through the inner filter effect mechanism. The LOD of the fluorescence sensing of oxytetracycline and tetracycline was 1.14 and 1.08 μM, respectively. Interestingly, the borophene QDs could be used for the sensitive and selective colorimetric and fluorometric sensing of oxytetracycline and tetracycline after 120 days of storage. The synthesized borophene QDs with long-term stability and real sample analysis provide new insight as nanozymes with higher peroxidase mimetic and fluorescence performance and can be further exploited for medical diagnosis and environmental toxicants' detection.

As tetracycline antibiotics were used in the poultry sector, their residue in edible animal products may adversely affect food safety and human health. The development of selective and sensitive tetracycline sensors has garnered a lot of interest due to the complexity of food samples. Therefore, a fluorescent sensing probe based on chromium(III)-metal–organic framework was developed for the rapid detection of tetracycline. After the addition of tetracycline, blue emission at λem 410 nm was effectively quenched by the interaction between TC and Cr(III)-metal–organic framework material. Under optimized conditions (sensor concentration: 30 mg/L and pH: 10.0), the sensing probe showed a fast response time (1 min), and low detection limit (0.78 ng/mL) with a linear range (5–45 ng/mL). Interestingly, the Cr(III)-metal–organic framework was successfully applied to quantity tetracycline residue in chicken meat and egg samples with recoveries of 95.17–06.93%. To deduce, our work can provide a new strategy for the direct detection of tetracycline in food samples.

A novel core-shell coordination assembled hybrid via postsynthetic metal exchange for simultaneous detection and removal of tetracycline

A peroxidase-like nanoenzyme based on strontium(II)-ion-exchanged Prussian blue analogue derivative SrCoO3/Co3O4 nanospheres and carbon quantum dots for the colorimetric detection of tigecycline in river water

Differential identification of GSH for acute coronary syndrome using a colorimetric sensor based on nanoflower-like artificial nanozymes

As a typical antibiotic pollutant, tetracycline (TC) is producing increasing threats to the ecosystem and human health, and exploring convenient means for monitoring of TC is needed. Here, we proposed alkali-etched imprinted Mn-based Prussian blue analogues featuring superior oxidase-mimetic activity and precise recognition for the colorimetric sensing of TC. Simply etching Mn-based Prussian blue analogues (Mn-PBAs) with NaOH could expose the sites and surfaces to significantly improve their catalytic activity. Density functional theory calculations were employed to screen the molecularly imprinted polymer (MIP) layer for target identification. Consequently, the designed Mn-PBANaOH@MIP possessed the rich channels for substrates to get in touch with the active Mn-PBANaOH core, showing an excellent catalytic capacity to trigger the chromogenic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) without the use of H2O2. If TC was introduced, it would be recognized selectively by the MIP shell and masked the channels for TMB access, resulting in the obstruction of the chromogenic reaction. According to this mechanism, selective optical detection of TC was achieved, and performance stability, reusability, and reliability as well as practicability were also verified, promising potential for TC monitoring in complex matrices. Our work not only presents an effective way to enhance the enzyme-like activity of Prussian blue analogues but also provides a facile approach for TC sensing. Additionally, the work will inspire the exploration of molecularly imprinted nanozymes for various applications.

A novel “On-Off” colorimetric sensor for ascorbic acid and hydrogen peroxide based on peroxidase activity of CeO2/Co3O4 hollow nanocubes

Tetracycline antibiotics (TCs) are commonly used antibiotics in the treatment of infections, but their overuse has a negative impact on human health and ecosystems. Thus, the development of a facile and on-site visualization method for TC detection is necessary. Here, we propose the potential of using lanthanide-functionalized metal-organic framework (MOF) composites (Ag+/Tb3+@UiO-66-(COOH)2, ATUC) as a probe for the rapid detection of tetracycline (TC), chlortetracycline (CTC), oxytetracycline (OTC), and doxycycline (DOX) residues, in which UiO-66-(COOH)2 (UC) could be utilized to provide an interaction microenvironment, Tb3+ as recognition units and Ag+ as a fluorescence enhancer. Upon exposure to TCs, significant luminescence quenching of ATUC excited at 255 nm was observed due to the inner filter effect (IFE) and photo-induced electron transfer (PET), and the established strategy has a detection limit (LOD) of 11.0, 20.1, 9.1, and 22.5 nM for TC, CTC, OTC, and DOX, respectively. More importantly, given its portability and conspicuous luminescence color gradation variation, a portable test strip based on ATUC was manufactured and the results could be distinguished immediately by the naked eye and smartphone analysis, allowing for on-site rapid quantitative assay of TCs, not only in the laboratory but also in a point-of-care setting.