Effective extraction of fluoroquinolones from water using facile modified plant fibers.

In this study, ecofriendly and economic carboxy-terminated plant fibers (PFs) were used as adsorbents for the effective in-syringe solid phase extraction (IS-SPE) of fluoroquinolone (FQ) residues from water. Based on the thermal esterification and etherification reaction of cellulose hydroxy with citric acid (CA) and sodium chloroacetate in aqueous solutions, carboxy groups grafted onto cotton, cattail, and corncob fibers were fabricated. Compared with carboxy-terminated corncob and cotton, CA-modified cattail with more carboxy groups showed excellent adsorption capacity for FQs. The modified cattail fibers were reproducible and reusable with relative standard deviations of 3.2%-4.2% within 10 cycles of adsorption-desorption. A good extraction efficiency of 71.3%-80.9% was achieved after optimizing the extraction condition. Based on carboxylated cattail, IS-SPE coupled with ultra-performance liquid chromatography with a photodiode array detector was conducted to analyze FQs in environmental water samples. High sensitivity with limit of detections of 0.08-0.25 µg/L and good accuracy with recoveries of 83.8%-111.7% were obtained. Overall, the simple and environment-friendly modified waste PFs have potential applications in the effective extraction and detection of FQs in natural waters.

Ferric iron loaded porphyrinic zirconium MOFs on corncob for the enhancement of diuretics extraction.

Herein, corncob waste was used as a scaffold for the fabrication of effective adsorbents. Porphyrinic zirconium metal-organic frameworks (MOFs) PCN-223 and PCN-224 constructed by different numbers of Zr6 cluster nodes were grown on the surface of the corncob. Fe (Ш) ions were implanted in the porphyrin ring by post-synthesis modification. The results showed that the extraction capacity of diuretics on PCN-224@corncob containing suitable pore size was larger than that of PCN-223@corncob. The adsorption of diuretics was further enhanced because of the electrostatic effect caused by implantation of Fe (Ш) ions. PCN-224-Fe@corncob was recyclable and selective for the extraction of furosemide (Fur) and bumetanide (Bum). Coupled in-syringe solid phase extraction (IS-SPE) with ultra-performance liquid chromatography (UPLC), an efficient, sensitive, and stable method was established. With a sensitivity between 0.6 and 1.0 µg/L and a recovery between 83.2% and 119.2%, it is used for the analysis of trace amounts of Fur and Bum in weight loss products and environmental water. The functionalized corncob has potential application for the adsorption of diuretics, and the metal ions implantation in MOFs provides a promising strategy for enhancing extraction capacity.

Novel solid-phase extraction filter based on a zirconium meta-organic framework for determination of non-steroidal anti-inflammatory drugs residues.

In this study, a zirconium-based metal-organic framework UiO-66-NH2 modified cotton fiber (CF@UiO-66-NH2) was fabricated for the extraction of five common NSAIDs, namely ketoprofen, naproxen, flurbiprofen, diclofenac sodium, and ibuprofen. UiO-66-NH2 was synthesized and immobilized on the surface of cotton fiber using an environmentally friendly aqueous synthesis method. The prepared CF@UiO-66-NH2 composite of 50 mg was loaded into a 13 mm recessed filter for use as a solid-phase extraction (SPE) adsorbent material. The filter was then used to enrich NSAIDs in fish and shrimp muscle tissues followed by ultra-high performance liquid chromatography (UPLC) detection. Several key parameters were evaluated and optimized, including adsorption flow rate, pH value of sample, desorption flow rate, and the formic acid content of the eluent. Under optimized conditions, linear ranges of ketoprofen, naproxen, flurbiprofen, diclofenac sodium, and ibuprofen were 2.0-300.0 ng/mL, 1.4-280.0 ng/mL, 3.0-400.0 ng/mL, 1.0-500.0 ng/mL, and 14.0-560.0 ng/mL, respectively. The detection limits ranged from 0.12 ng/mL to 3.50 ng/mL with recoveries in the range of 72.95-116.99%, RSDs < 9.90%. The results demonstrated that the homemade filters based on CF@UiO-66-NH2 exhibited good reproducibility, stability and adsorption property for the determination of trace-level NSAIDs in complex matrix.

Hydrophilic carboxyl supported immobilization of UiO-66 for novel bar sorptive extraction of non-steroidal anti-inflammatory drugs in food samples.

Herein, the preparation of UiO-66 on frosted glass rod (FGR) was proposed through the coordination interaction of Zr-OH groups and carboxyl sites on FGR. The relative standard deviations (RSDs) of intra-batch and inter-batch were below 8.0% (n = 7). UiO-66-modified FGR (UiO-66@FGR) was applied to the extraction and monitoring of five non-steroidal anti-inflammatory drugs (NSAIDs) by coupling to novel bar sorptive extraction (BSE) with ultra-high performance liquid chromatography (UPLC). Sample volume, stirring rate, extraction time, sample pH value, desorption solvent, and desorption time were investigated. NSAIDs (ketoprofen, flurbiprofen, ibuprofen, naproxen, and diclofenac sodium) were determined at a low limit of detection (0.92 ng/mL) over a wide linear range (10-1500 ng/mL). The developed method was used to analyze NSAIDs in sheep muscle, chicken wing, and milk with recoveries of 80.8%-117.2%, RSDs < 6.5%. Fabricated UiO-66@FGR exhibited excellent reproducibility, stability, and good adsorption property towards NSAIDs in food samples.

Screening of the active compound from Tetradium ruticarpum fruits and analysis of its binding characteristics to the α1A adrenoceptor by high expression α1A adrenoceptor cell membrane chromatography.

The dried fruit of the Tetradium ruticarpum (Wu Zhu Yu) tree is commonly used in traditional Chinese medicine, and its decoction can be used for treating conditions such as headaches and hypotension. In the present study, an offline two-dimensional combination method of α1A/HEK293 cell membrane chromatography (α1A/CMC) and UHPLC-MS/MS was established to screen and identify the active compound from the Tetradium ruticarpum fruits. The binding characteristics between this active compound and the α1A receptor were also analyzed by an α1A/CMC method. By this process, dehydroevodiamine was identified as the potential active compound. Equilibrium dissociation constant (Kd) values between α1A receptor and dehydroevodiamine, obtained by both stepwise frontal analysis and zonal elution analysis, were (5.18 ± 0.50) × 10-6 mol/L and (2.70 ± 0.74) × 10-6 mol/L, respectively. Our results indicate that the α1A/CMC method can not only screen active compounds from complex sample, but can also be used to calculate the binding parameters of the identified compound.

Physiological and proteomic analyses of salt stress response in the halophyte Halogeton glomeratus.

Very little is known about the adaptation mechanism of Chenopodiaceae Halogeton glomeratus, a succulent annual halophyte, under saline conditions. In this study, we investigated the morphological and physiological adaptation mechanisms of seedlings exposed to different concentrations of NaCl treatment for 21 d. Our results revealed that H. glomeratus has a robust ability to tolerate salt; its optimal growth occurs under approximately 100 mm NaCl conditions. Salt crystals were deposited in water-storage tissue under saline conditions. We speculate that osmotic adjustment may be the primary mechanism of salt tolerance in H. glomeratus, which transports toxic ions such as sodium into specific salt-storage cells and compartmentalizes them in large vacuoles to maintain the water content of tissues and the succulence of the leaves. To investigate the molecular response mechanisms to salt stress in H. glomeratus, we conducted a comparative proteomic analysis of seedling leaves that had been exposed to 200 mm NaCl for 24 h, 72 h and 7 d. Forty-nine protein spots, exhibiting significant changes in abundance after stress, were identified using matrix-assisted laser desorption ionization tandem time-of-flight mass spectrometry (MALDI-TOF/TOF MS/MS) and similarity searches across EST database of H. glomeratus. These stress-responsive proteins were categorized into nine functional groups, such as photosynthesis, carbohydrate and energy metabolism, and stress and defence response.