Differential sensitization toward lanthanide metal-organic framework for detection of an anthrax biomarker.

A novel Tb-doped Eu-based metal-organic framework (Eu-MOF@Tb) has been developed by incorporating hexanuclear europium cluster and 2,2'-bipyridine-5,5'-dicarboxylic acid as well as coordination with Tb(III). Owing to the diverse coordination status of Tb(III) and Eu(III) in MOF, antenna effect emission from Tb(III) can be invoked by dipicolinic acid (DPA), but the luminescence originating from Eu(III) remains unchanged. Taking advantage of this phenomenon, a ratiometric luminescent method for detection of DPA, a biomarker for Bacillus subtilis spores, was developed through differential sensitization toward lanthanide ions. This analysis method allowed for the detection of DPA in the 0.2-10 µM concentration range, with a detection limit of 60 nM. It was further validated by spiked recoveries (89.3-110%) of real-world samples with RSD values in the range 3.9-11%. Alongside this, a paper indicator test was prepared for naked-eye detection of DPA via a dose-sensitive color evolution from red to green under UV light. The effectiveness of the proposed approach was explored in the detection of bacterial spores in real biological and environmental samples and indicated great potential for applications as a real-time monitoring system against the anthrax threat.

Flower-like ZIF-8 enhance the peroxidase-like activity of nanoenzymes at neutral pH for detection of heparin and protamine.

The peroxide-like catalytic activity of gold nanoclusters (Au-NCs) is very low under physiological conditions (pH 7.4), which greatly limits its biological detection applications. A new nanoenzyme platform was constructed by self-assembly of Au-NCs and ZIF-8/CQDs. It was found that heparin can significantly promote the peroxidase-like activity of Au-NCs on the nanoenzyme platform at pH 7.4. In the presence of H2O2, the catalytic activity of Au-NCs on the nanoenzyme platform for TMB increased nearly 50 times. Based on this phenomenon, a colorimetric method was developed to determine heparin in the range of 0.0185-9.25 U/mL, with a detection limit of 0.0027 U/mL. When protamine is introduced, heparin and protamine take the lead in specific binding due to antagonism, which makes heparin unable to adsorb on the surface of ZIF-8/CQDS, thus inhibiting the enhancement of the catalytic activity of Au-NCs. Based on this phenomenon, a colorimetric method was developed to determine protamine in the range of 0.01-0.5 µg/mL, with a detection limit of 0.003 µg/mL. Therefore, this method provides a new idea for the visual detection of heparin and protamine under physiological conditions.

A fluorescent and colorimetric dual-channel sensor based on acid phosphatase-triggered blocking of internal filtration effect.

A colorimetric and fluorescent dual-channel detection method for acid phosphatase (ACP) activity has been constructed, based on the internal filtering effect between oxidized 3,3',5,5'-tetramethylbenzidine (oxTMB) and rhodamine B (RB). Au3+, which in situ form gold nanoparticles (AuNPs), can oxidize colorless 3,3',5,5'-tetramethylbenzidine (TMB) to oxTMB (blue color). The fluorescence of RB can be quenched by oxTMB due to the spectral overlap of emission of RB and absorption of oxTMB. By means of the above process, ACP can be determined because ACP promotes the hydrolysis of 2-phospho-L-ascorbic acid trisodium salt (AAP) to generate ascorbic acid (AA), which can inhibit the internal filtering effect between RB and oxTMB. No material preparation was needed for the determination of ACP. The colorimetric and fluorimetric methods can quantify ACP in the range 0.06-5.0 mU/mL and 0.03-5.0 mU/mL, respectively. Furthermore, a smartphone-assisted sensing platform has been constructed for on-site monitoring of ACP in the range 0.75-50 mU/mL, and the detection limit is 0.3 mU/mL. The methods developed can measure ACP in human serum successfully.

One-step self-assembly of magnetic supramolecular metal-organic coordination functionalized MoS2 complex as nanoenzyme-reactor.

In the present study, a kind of magnetic supramolecular metal-organic coordination complex (SMOCC) functionalized MoS2 was prepared with one-step in aqueous solution for enzyme immobilization. As possessing a protective nanocoating of PDA/PEI/Cu2+ (polydopamine: PDA, polyethyleneimine: PEI), the proposed material can provide biocompatible microenvironment and flexible adhesion force on particle interface, which is conductive to loading laccase (170.0 ± 1.8 mg/g) with high activity (93.0 ± 1.1 %). Compared with the free laccase, the immobilized laccase has higher stability in a broader range of pH (3-10), temperature (20-80 °C), storage time (1-18 days) and reusability (1-16 cycles). The removal of carcinogenic persistent organic pollutant malachite green in the water with the immobilized laccase shows a higher efficiency (89.4 ± 1.2 %) than free laccase (16.2 ± 0.2 %). The Fe3O4@MoS2@(PDA/PEI/Cu2+) nanocomposites can also be used successfully to immobilize trypsin, lipase and catalase respectively, showing a satisfactory enzyme loading (157.0 ± 0.1 mg/g, 151.6 ± 1.4 mg/g, 162.6 ± 1.6 mg/g, respectively) and activity (95.0 ± 0.5 %, 90.0 ± 0.8 %, 91.0 ± 0.9 %, respectively). The MoS2 can be replaced by carbon material and similar results can be obtained.

A novel molybdenum disulfide nanosheet self-assembled flower-like monolithic sorbent for solid-phase extraction with high efficiency and long service life.

A novel material consisting of molybdenum disulfide (MoS2) nanosheet that self-assemble into flower-like microspheres which aggregate to form a monolithic matrix with a micro or nano-scaled mesopore structure was successfully synthesized and used as an efficient sorbent for solid-phase extraction (SPE) due to its large specific adsorption area and good stability. The extraction properties of the as-prepared sorbent were evaluated by high-performance liquid chromatography with variable wavelength detection (HPLC-VWD) by analyzing four flavonoids (apigenin, quercetin, luteolin, and kaempferol). Under optimal conditions, the LODs and LOQs were found to be in the ranges of 0.1-0.25 and 0.4-0.5µgL-1, respectively, and wide linear ranges were obtained with correlation coefficients (R) ranging from 0.9991 to 0.9996. Compared with commercial C18 and Alumina-N sorbents, the as-prepared sorbent showed high extraction efficiency at different concentrations of flavonoids. After 100 uses, the extraction ability of the self-assembled MoS2 nanosheet monolithic sorbent had no evident decline, denoting a long service life. Finally, the SPE-HPLC-VWD method using the as-prepared sorbent was applied to flavonoid analysis in beverage samples with satisfactory results.

A chromium(III) oxide-coated steel wire prepared by arc ion plating for use in solid-phase microextraction of aromatic hydrocarbons.

The authors introduce an arc ion plating method for the deposition of chromium oxide (Cr2O3) on a steel wire substrate, and its use as a coating for solid phase microextraction. The coating has a micro- and nano-scaled structure after annealing at 700 °C. It is found that Cr2O3 exhibits a good extraction capability for the aromatic hydrocarbons naphthalene, anthracene, fluorene, fluoranthene, and biphenyl. Following desorption by high temperature at 300 °C, the analytes were quantified by gas chromatography (GC). The limits of detection are in the range between 20 and 200 ng·L-1, and calibration plots are linear within a wide range (0.2 to 400 µg·L-1). The coating has excellent mechanical properties, with a hardness is as high as 31.7 GPa, and the adhesion strength between coating and substrate reaches 20.1 N (corresponding to the critical Hertzian contact stress of 10 GPa). This, along with the chemical and thermal stability of the Cr2O3 coating, endows the wire with a long operational life. It was used for at least 100 times without any obvious decline of extraction capability. Graphical abstract An arc ion plating method was introduced for the deposition of chromium oxide (Cr2O3) on a steel wire substrate, and its use as a coating for solid phase microextraction with high mechanical strength, stability, and long operational lifetime.

A highly thermal stable solid phase microextraction fiber prepared by an inorganic binder.

An easy method to prepare solid phase microextraction fibers by introducing an inorganic binder was demonstrated in this study, where MoS2 was selected as the extraction phase material because of its graphite-like layered structure with large specific adsorption area and good stability, and was then adhered to a stainless steel wire by acid aluminum phosphate binder with the spraying method. The as-prepared solid phase microextraction fiber coupled with gas chromatography was then used to extract some polycyclic aromatic hydrocarbons target analytes including the low-volatile benzo(a)pyrene etc. from a standard sample. Comparing with the MoS2-epoxy resin and commercial polyacrylate fibers, the MoS2-acid aluminum phosphate fiber has a higher thermal stability because of highly thermal stable acid aluminum phosphate, which is durable for a long service life at a high temperature (320 °C), and has the advantage in the extraction of low-volatility analytes. After the optimization of adsorption and desorption factors (ionic strength, adsorption time and temperature, and desorption temperature), method detection limits of <0.1 µg L(-1) were achieved, and the calibration curves were all linear (R(2) ≥ 0.9981) within the range of 0.1-100 µg L(-1). The satisfying repeatability was also achieved, the RSD values of single-fiber were 3.49-5.81%, and the ones of fiber-to-fiber were 5.32-7.22%. As a result, the present fiber with good thermal stability can work at high temperature for a long service life, which is useful for the detection of low-volatility target analytes in practical applications.