Triple-synergistic MOF-nanozyme for efficient antibacterial treatment.

The abuse of antibiotics makes bacterial infection an increasingly serious global health threat. Reactive oxygen species (ROS) are the ideal alternative antibacterial approach for quick and effective sterilization. Although various antibacterial strategies based on ROS have been developed, many of them are still limited by insufficient antibacterial efficiency. Here, we have developed an acid-enhanced dual-modal antibacterial strategy based on zeolitic imidazolate frameworks-8 (ZIF8) -derived nanozyme. ZIF8, which can release Zn2+, is chosen as the carrier to integrate glucose oxidase (GOx) and gold nanoparticles (Au NPs) which can produce ROS via a cascade catalytic reaction. Thus, the bactericidal capability of ROS and Zn2+ have been integrated. More importantly, gluconic acid, a "by-product" of the catalytic reaction, can generate an acidic environment to promote both the ROS-producing and Zn2+-releasing, enhancing the overall antibacterial performance further. This triple-synergistic strategy exhibits extraordinary bactericidal ability at a low dosage of 4 µg/mL (for S. aureus) and 8 µg/mL (for E. coli), which shows a great potential of MOF-derived nanozyme for efficient bacterial eradication and diverse biomedical applications.

Antibacterial Cascade Catalytic Glutathione-Depleting MOF Nanoreactors.

Nanozymes with peroxidase-like activity have great application potential in combating pathogenic bacterial infections and are expected to become an alternative to antibiotics. However, the near-neutral pH and high glutathione (GSH) levels in the bacterial infection microenvironment severely limit their applications in antibacterial therapy. In this work, a metal-organic framework (MOF)-based cascade catalytic glutathione-depleting system named MnFe2O4@MIL/Au&GOx (MMAG) was constructed. The MMAG cascade-catalyzed glucose to provide H+ and produces a large amount of toxic reactive oxygen species. In addition, MMAG consumed GSH, which can result in bacterial death more easily. Systematic antibacterial experiments illustrated that MMAG has superior antibacterial effects on both Gram-positive bacteria and Gram-negative bacteria.

Natural Alpha-Glucosidase Inhibitors Rapid Fishing from Cyperus Rotundus Using Immobilized Enzyme Affinity Screening Combined with UHPLC-QTOF MS.

An efficient and rapid affinity-based screening method for directly fishing out natural alpha-glucosidase inhibitors from Cyperus rotundus extract by using immobilized enzyme technology combined with UHPLC-QTOF MS analysis was established. As a result without time-consuming and laborious isolation workload and false positive interference, five natural alpha-glucosidase inhibitors were successfully recognized and identified from only 400 uL of C. rotundus extracts within only a couple of hours, which suggested that the screening method was rapid, economical, sensitive and feasible. In addition, the captured compounds were isolated and characterized as stilbenoids oligomers, and were proved to be strong alpha-glucosidase inhibitors by inhibitory assay in-vitro. Among them, 3 stilbenoids trimers were reported to be potent α-glucosidase inhibitors for the first time. This method could be modified and have the potential for rapidly screening of active compounds extracts against some new targets by immobilizing some other biomacromolecules.

Screening of α-glucosidase inhibitors from green tea extracts using immobilized enzymes affinity capture combined with UHPLC-QTOF MS analysis.

An applicable affinity capture-based method was developed for screening of enzyme inhibitors from complex plant extracts directly. By elimination of false positives, three non-competitive α-glucosidase inhibitors were fished out from 400 µL green tea extract rapidly, using affinity capture of immobilized α-glucosidase combined with UHPLC-QTOF MS analysis.

Hollow fiber liquid phase microextraction combined with electrothermal atomic absorption spectrometry for the speciation of arsenic (III) and arsenic (V) in fresh waters and human hair extracts.

A new method of hollow fiber liquid phase microextraction (HF-LPME) using ammonium pyrrolidine dithiocarbamate (APDC) as extractant combined with electrothermal atomic absorption spectrometry (ETAAS) using Pd as permanent modifier has been described for the speciation of As(III) and As(V). In a pH range of 3.0-4.0, the complex of As(III)-APDC complex can be extracted using toluene as the extraction solvent leaving As(V) in the aqueous layer. The post extraction organic phase was directly injected into ETAAS for the determination of As(III). To determine total arsenic in the samples, first As(V) was reduced to As(III) by l-cysteine, and then a microextraction method was performed prior to the determination of total arsenic. As(V) assay was based on subtracting As(III) form the total arsenic. All parameters, such as pH of solution, type of organic solvent, the amount of APDC, stirring rate and extraction time, affecting the separation of As(III) from As(V) and the extraction efficiency of As(III) were investigated, and the optimized extraction conditions were established. Under optimized conditions, a detection limit of 0.12ngmL(-1) with enrichment factor of 78 was achieved. The relative standard deviation (R.S.D.) of the method for five replicate determinations of 5ngmL(-1) As(III) was 8%. The developed method was applied to the speciation of As(III) and As(V) in fresh water and human hair extracts, and the recoveries for the spiked samples are 86-109%. In order to validate the developed method, three certified reference materials such as GBW07601 human hair, BW3209 and BW3210 environmental water were analyzed, and the results obtained were in good agreement with the certified values provided.

Headspace single drop microextraction combined with HPLC for the determination of trace polycyclic aromatic hydrocarbons in environmental samples.

A new method by combining headspace single drop microextraction (HS-SDME) with HPLC fluorescence detection for the determination of trace polycyclic aromatic hydrocarbons (PAHs) in environmental samples was developed. Aqueous solution of saturated beta-cyclodextrin was used as extraction solvent and five PAHs were employed as target analytes. The factors affecting the extraction efficiency were studied in detail and the optimal extraction conditions were established. Beta-cyclodextrin was found to play two important roles, one is the improvement of extraction efficiency of target analytes and the other is the enhancement of their fluorescence intensities in HPLC fluorescence detection. The detection limits for the target analytes were found to be in the range of 0.004-0.247ng/ml and the relative standard deviations (R.S.D.s) of 5.1-7.1% were obtained. The proposed method was applied to the analysis of trace PAHs in environmental samples with satisfactory results.

Hollow fiber-based liquid-liquid-liquid microextraction combined with high-performance liquid chromatography for the speciation of organomercury.

A novel and extremely highly sensitive method for the speciation of organomercury in sea food and environmental water samples was developed by hollow fiber liquid-liquid-liquid microextraction (LLLME) coupled to high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection at 254 nm. By the use of toluene filled the pores of the hollow fiber wall as the organic phase and Na(2)S(2)O(3) aqueous solution in the lumen of hollow fiber as acceptor phase, the simultaneous preconcentration of methylmercury (MeHg), ethylmercury (EtHg), and phenylmercury (PhHg) could be realized, and the target mercury species in the post-extraction acceptor phase were directly injected into HPLC for their separation. The factors affecting on the liquid-liquid-liquid microextraction of three organomercury species, including organic solvent, the pH of donor phase, the concentration of complexing agent, extraction time and stirring rate were investigated and the optimal extraction conditions were established. With the consumption of 3.8 mL of sample solution, the enrichment factors were about 120, 215 and 350 for MeHg, EtHg, and PhHg, respectively. The limits of detection were in the range of 0.3-3.8 ng mL(-1) (as Hg) with precisions (RSDs (%), c=30 ng mL(-1) (as Hg), n=7) ranging from 6.4 to 8.9%. The developed technique was validated by analyzing a certified reference material (DORM-2, dogfish-muscle, NRCC) and an environmental water sample, and the analytical results were satisfactory.

Hollow-fiber liquid-phase microextraction prior to low-temperature electrothermal vaporization ICP-MS for trace element analysis in environmental and biological samples.

A new method of hollow-fiber liquid-phase microextraction (HF-LPME) prior to electrothermal vaporization (ETV) inductively coupled plasma mass spectrometry (ICP-MS) determination of trace Cu, Zn, Pd, Cd, Hg, Pb and Bi, based on gaseous compounds introduction into the plasma as their diethyldithiocarbmate (DDTC) chelates, was developed. The use of the reagent DDTC as chemical modifier could not only enhance the analytical signals, but also decrease the vaporization temperature. At a temperature of 1300 degrees C, trace Cu, Zn, Pd, Cd, Hg, Pb and Bi can be vaporized completely into the ICP. The factors affecting the formation of the chelates and their vaporization behaviors were investigated in detail, and the microextraction conditions were optimized. Under the optimized conditions, the detection limits of the proposed method were 12.4, 28.7, 7.9, 4.5, 3.3, 4.8 and 1.6 pg ml(-1) for Cu, Zn, Pd, Cd, Hg, Pb and Bi, respectively. Enrichment factors of 305, 284, 24, 29, 20, 73 and 43 could be achieved within 15 min of extraction time, and the relative standard deviations (RSDs) for the seven determinations of 0.5 ng ml(-1) of target analytes were 8.8, 6.9, 7.1, 9.4, 10.2, 6.1 and 10.8%, respectively. The newly developed method has been applied to the determination of trace Cu, Zn, Pd, Cd, Hg, Pb and Bi in environmental water and human serum samples, and the recoveries for the spiked samples were in the range of 88-116%. In order to validate this method, two certified reference materials, GBW08501 peach leaves and GBW(E)080040 seawater, were analyzed, and the determined values were in good agreement with the certified values.

Optimization of a single-drop microextraction procedure for the determination of organophosphorus pesticides in water and fruit juice with gas chromatography-flame photometric detection.

A single-drop microextraction (SDME) procedure was developed for the analysis of organophosphorus pesticides (OPPs) in water and fruit juice by gas chromatography (GC) with flame photometric detection (GC-FPD). The significant parameters affecting the SDME performance such as selection of microextraction solvent, solvent volume, extraction time, stirring rate, sample pH and temperature, and ionic strength were studied and optimized. Two types of SDME mode, static and cycle-flow SDME, were evaluated. The static SDME procedure provided more sensitive analysis of the target analytes. Therefore, static SDME with tributyl phosphate (TBP) as internal standard was selected for the real sample analysis. The limits of detection (LODs) in water for the six studied compounds were between 0.21 and 0.56ng/mL with the relative standard deviations ranging from 1.7 to 10.0%. Linear response data was obtained in the concentration range of 0.5-50ng/mL (except for dichlorvos 1.0-50ng/mL) with correlation coefficients from 0.9995 to 0.9999. Environmental water sample collected from East Lake and fruit juice samples were successfully analyzed using the proposed method, but none of the analytes in both lake water and fruit juice were detected. The recoveries for the spiked water and juice samples were from 77.7 to 113.6%. Compared with the conventional methods, the proposed method enabled a rapid and simple determination of organophosphorus pesticides in water and fruit juice with minimal solvent consumption and a higher concentration capability.

Determination of trace Cd and Pb in environmental and biological samples by ETV-ICP-MS after single-drop microextraction.

A method based on single-drop microextraction (SDME) combined with electrothermal vaporization (ETV)-ICP-MS was proposed for the determination of trace Cd and Pb. 8-Hydroxyquinoline (8-HQ) was employed as extractant dissolved in several microliters of chloroform and then an organic microdrop was formed at the tip of the microsyringe needle to extract the interest analytes. The vaporization behavior of the metal-8-HQ chelates in graphite furnace was investigated, and the ETV temperature program was optimized. The factors that influenced the extraction efficiency of target analytes (including pH value, flow rate of sample, extraction time and organic microdrop volume) were studied. Under the optimum conditions, the detection limits of the Cd and Pb were 4.6 and 2.9pgmL(-1) with the enrichment factor of 140-fold for Cd and 190-fold for Pb, respectively. The proposed method was applied successfully to the determination of trace Cd and Pb in environmental and biological samples. In order to validate the developed method, a certified reference material of GBW 08501 peach leaves was analyzed and the determined values obtained were in a good agreement with the certified values.

Single-drop microextraction combined with low-temperature electrothermal vaporization ICPMS for the determination of trace Be, Co, Pd, and Cd in biological samples.

A new method of single-drop microextraction combined with low-temperature electrothermal vaporization (LTETV)-ICPMS was proposed for the determination of trace Be, Co, Pd, and Cd with benzoylacetone (BZA) as both extractant and chemical modifier. Several factors that influence the microextraction efficiency, such as sample flow rate, microdrop volume, and extraction time, were investigated and the optimized microextraction conditions were established. Be, Co, Pd, and Cd in the postextraction organic phase were directly determined by LTETV-ICPMS with the use of BZA as chemical modifier. The chemical modification of BZA in LTETV-ICPMS was studied, and the factors affecting the formation of chelates and vaporization/transportation of chelates were investigated. Under the optimized conditions, the detection limits of the method were 0.12, 0.99, 1.5, and 0.27 pg/mL for Be, Co, Pd, and Cd, and the relative standard deviations for 0.1 ng/mL Be, Co, Pd, and Cd were 16, 14, 14, and 11%, respectively. After 10 min of extraction, the enrichment factors were 160 (Be), 125 (Co), 40 (Pd), and 180 (Cd). The proposed method was applied to the determination of trace Be, Co, Pd, and Cd in biological reference materials, and the determined values were in good agreement with the certified values.

Selective separation of La3+ and lanthanum organic complexes with nanometer-sized titanium dioxide and their detection by using fluorination-assisted electrothermal vaporization ICP-AES with in-situ matrix removal.

A new method for the determination of free La3+ and La organic complexes in solution using a nanometer-sized titanium dioxide as solid-phase extractant and fluorination-assisted electrothermal vaporization (FETV)-ICP-AES as sensitive detector has been developed. The effect of pH on the adsorption characteristics of La3+ and La complexes of citric acid, 2-hydroxyisobutyric acid (HIBA), and humic acid on nanometer-sized TiO2 was investigated and optimized. On the basis of the difference in volatility between fluoride of analyte (lanthanum) and the fluoride of matrix (titanium), an in-situ removal of the adsorbent matrix (TiO2) from a graphite furnace was realized. Therefore, the free La3+ and adsorbed La complexes on nanometer-sized titanium dioxide could be determined respectively by FETV-ICP-AES without any other chemical pretreatment. The proposed method was applied for the determination of free ion (La3+) and La complexes in synthetic solutions and soil extracts with satisfactory results.