Micro-matrix cartridge extraction followed by online micro-solid phase extraction based on polystyrene@hydroxypropyl-ß-cyclodextrin nanofibers for selective determination of fipronil and its metabolites in soil.

Micro-matrix cartridge extraction coupled on-line to micro-solid phase extraction-high performance liquid chromatography-mass spectrometry (µ-MCE-online-µ-SPE-HPLC-MS) is presented. Micro-matrix cartridge extraction (µ-MCE) was applied to highly efficient desorption of adsorbed pesticides from contaminated soil with favorable extraction efficiency (100%). Novel polystyrene@hydroxypropyl-ß-cyclodextrin (PS@HPCD) electrospun nanofibers with 3D network structure were prepared to selectively capture fipronil and its metabolites. High selectivity was obtained with adsorption efficiency ≥ 86.64% via complexation, hydrophobic affinity, and π-π interactions. PS@HPCD nanofibers exhibited remarkable advantages such as excellent enrichment factors (24-55), superior permeability, and long service life (> 65 times). Under the optimum conditions, wide linear range (0.1-1000 ng g-1), low detection limits (0.0032-0.0067 ng g-1), high recoveries (84-124.5%), favorable repeatability (RSD ≤ 10.4%, n = 5), and reproducibility (RSD ≤ 7.2%, n = 3) were acquired for fipronil and three metabolites. The developed method was applied to the pesticide determination in actual soils and the ISO-certified soil with satisfactory recoveries (96.5%). The method developed provides a green, efficient, and miniaturized method for the determination of trace pesticide residues in soil.

Anchoring Group Mediated Radiolabeling for Achieving Robust Nanoimaging Probes.

Radiolabeling counts for much in the functionalization of inorganic nanoparticles (NPs) because it endows NPs with high-sensitive imaging capacities apart from providing accurate pharmacokinetic information on the labeled particles, which makes the development of relevant radiolabeling chemistry highly desirable. Herein, a novel Ligand Anchoring Group MEdiated RAdioLabeling (LAGMERAL) method is reported, in which a polyethylene glycol (PEG) ligand with a diphosphonate (DP) terminal group plays a key role. It offers possibilities to radiolabel NPs through the spare coordination sites of the DP anchoring group. Through X-ray absorption spectroscopy studies, the coordination states of the foreign metal ions on the particle surface are investigated. In addition, radioactive Fe3 O4 NPs are prepared by colabeling the particles with 125 I at the outskirt of the particles through a phenolic hydroxyl moiety of the PEG ligand, and 99m Tc at the root of the ligand, respectively. In this way, the stabilities of these types of radiolabeling are compared both in vitro and in vivo to show the advantages of the LAGMERAL method. The outstanding stability of probe and simplicity of the labeling process make the current approach universal for creating advanced NPs with different combinations of functionalities of the inorganic NPs and radioactive properties of the metal radioisotopes.

Dynamic release of siloxanes in the form of biogas from simulated municipal-solid-waste landfill and the corresponding driving mechanism.

Simulated landfill bioreactors were established and operated for 635 days to investigate the dynamic release of seven siloxanes in landfill biogas (denoted by octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6)). In total, 259.45, 252.73, 233.30, 80.40, 4.35, 1.67 and 1.10 mg of D5, D3, D4, D6, L4, L5 and L3 were discharged from 57 kg of municipal solid waste (MSW). More than 70 % of the siloxanes were released before day 119, indicating that the peak period of siloxane discharge occurred during the hydrolysis and acid production stage. The cyclosiloxanes (D3, D4, D5 and D6) were the dominant siloxane species in the biogas. The mass load of discharged cyclosiloxanes was more than 98 % of that of the total siloxanes. In addition to the variation in the concentration distribution profiles of the different siloxane species in the MSW, transformations among species may have an important effect on the release of siloxanes. The main transformation products were D3 and D4 with high release rates (>20 %) and high measured contents of trimethylsilanol (TMSOH) and functional microorganisms (Pseudomonas) were observed during landfilling. These results suggested that MSW degradation and transformation of siloxanes both drive the dynamic release of siloxanes during long-term landfilling.

Integrating genomics, molecular docking, and protein expression to explore new perspectives on polystyrene biodegradation.

Faced with the escalating challenge of global plastic pollution, this study specifically addresses the research gap in the biodegradation of polystyrene (PS). A PS-degrading bacterial strain was isolated from the gut of Tenebrio molitor, and genomics, molecular docking, and proteomics were employed to thoroughly investigate the biodegradation mechanisms of Pseudomonas putida H-01 against PS. Using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (ATR-FTIR), and contact angle analysis, significant morphological and structural changes in the PS films under the influence of the H-01 strain were observed. The study revealed several potential degradation genes and ten enzymes that were specifically upregulated in the PS degradation environment. Additionally, a novel protein with laccase-like activity, LacQ1, was purified from this strain for the first time, and its crucial role in the PS degradation process was confirmed. Through molecular docking and molecular dynamics (MD) simulations, the interactions between the enzymes and PS were detailed, elucidating the binding and catalytic mechanisms of the degradative enzymes with the substrate. These findings have deepened our understanding of PS degradation.

A clinically translatable kit for MRI/NMI dual-modality nanoprobes based on anchoring group-mediated radiolabeling.

Magnetic resonance imaging (MRI)/nuclear medicine imaging (NMI) dual-modality imaging based on radiolabeled nanoparticles has been increasingly exploited for accurate diagnosis of tumor and cardiovascular diseases by virtue of high spatial resolution and high sensitivity. However, significant challenges exist in pursuing truly clinical applications, including massive preparation and rapid radiolabeling of nanoparticles. Herein, we report a clinically translatable kit for the convenient construction of MRI/NMI nanoprobes relying on the flow-synthesis and anchoring group-mediated radiolabeling (LAGMERAL) of iron oxide nanoparticles. First, homogeneous iron oxide nanoparticles with excellent performance were successfully obtained on a large scale by flow synthesis, followed by the surface anchoring of diphosphonate-polyethylene glycol (DP-PEG) to simultaneously render the underlying nanoparticles biocompatible and competent in robust labeling of radioactive metal ions. Moreover, to enable convenient and safe usage in clinics, the DP-PEG modified nanoparticle solution was freeze-dried and sterilized to make a radiolabeling kit followed by careful evaluations of its in vitro and in vivo performance and applicability. The results showed that 99mTc labeled nanoprobes are effectively obtained with a labeling yield of over 95% in 30 minutes after simply injecting Na[99mTcO4] solution into the kit. In addition, the Fe3O4 nanoparticles sealed in the kit can well stand long-term storage even for 300 days without deteriorating the colloidal stability and radiolabeling yield. Upon intravenous injection of the as-prepared radiolabeled nanoprobes, high-resolution vascular images of mice were obtained by vascular SPECT imaging and magnetic resonance angiography, demonstrating the promising clinical translational value of our radiolabeling kit.

Bisolute sorption and thermodynamic behavior of organic pollutants to biomass-derived biochars at two pyrolytic temperatures.

The bisolute sorption and thermodynamic behavior of organic pollutants on low temperature biochars (LTB) at 300 °C and high temperature biochars (HTB) at 700 °C were determined to elucidate sorptive properties of biochar changed with pyrolytic temperatures. The structural characteristics and isotherms shape of the biochar were more dependent on the pyrolytic temperature than on the biomass feedstocks, which included orange peel, pine needle, and sugar cane bagasse. For LTB, the thermally altered organic matter colocalized with the carbonized matter, and the visible fine pores of the fixed carbons were plugged by the remaining volatile carbon. For HTB, most of the volatile matter was gone and the fixed matter was composed of fully carbonized adsorptive sites. Monolayer adsorption of 1-naphthol to HTB was dominant but was suppressed by phenol. In comparison, LTB displayed exceptional sorption behavior where partition and adsorption were concurrently promoted by a cosolute and elevated temperature. In addition to monolayer surface coverage, pore-filling mechanisms may contribute to the increase of adsorption fraction. Moreover, the entropy gain was a dominant force driving the partition and adsorption processes in LTB. Thus, the colocalizing partition phase and adsorptive sites in LTB are proposed to be in interencased states rather than in physical separation.

Phosphoric acid pretreatment enhances the specific surface areas of biochars by generation of micropores.

Biochars are being increasingly applied in soil for carbon sequestration, fertility improvement, as well as contamination remediation. Phosphoric acid (H3PO4) pretreatment is a method for biochar modification, but the mechanism is not yet fully understood. In this work, biochars and the raw biomass were treated by H3PO4 prior to pyrolysis. Due to an acid catalysis and crosslink, the micropores of the pretreated particles were much more than those without H3PO4 pretreatment, resulting in the dramatical enhancement of specific surface areas of the pretreated particles. Crystalline cellulose (CL) exhibited a greater advantage in the formation of micropores than of amorphous lignin (LG) with H3PO4 modification. The formation mechanisms of micropores were: (a) H+ from H3PO4 contributes to micropores generation via H+ catalysis process; (b) the organic phosphate bridge protected the carbon skeleton from micropore collapse via the crosslinking of phosphate radical. The sorption capacities to carbamazepine (CBZ) and bisphenol A (BPA) increased after H3PO4 modification, which is ascribed to the large hydrophobic surface areas and more abundant micropores. Overall, H3PO4 pretreatment produced biochars with large surface area and high abundance of porous structures. Furthermore, the H3PO4 modified biochars can be applied as high adsorbing material as well as P-rich fertilizer.

Simultaneous removal of multi-pollutants in an intimate integrated flocculation-adsorption fluidized bed.

A novel intimate integrated flocculation-adsorption fluidized bed (IFAFB) was designed based on the hydraulic classification theory, and the operation, performance, characterization, and mechanisms of the novel process were developed. In this system, 150 mg · L(-1) kaolin clay and 100 mg · L(-1) phenol were used to simulate multi-pollutants in synthetic influent; resin beads and silica beads were the solid phases for the fluidized flocculator, and polymer aluminum chloride (PAC) and granular activated carbon were the flocculant and the adsorbent, respectively. The results showed that the Euler numeral was the most suitable dynamic parameter for flocculation in the fluidized bed when compared with the velocity gradient (G), Reynolds number (Re), and GRe (-1/2) . Additionally, the adsorption capacities of the fluidized regime were 8.77 and 24.70 mg · g(-1) greater than those of the fixed regime at superficial velocities of 6 and 8 mm · s(-1), respectively. In the IFAFB, the removal efficiencies of kaolin clay and phenol in the IFAFB reached 95 and 80 % simultaneously at total initial bed height of 35 mm. Flocs size, fractal dimension, and scanning electron microscopy (SEM) confirmed that the relationship of flocculation and adsorption in the IFAFB was mutually beneficial. Adsorption favored continuous growth of flocs and protected flocs from breakage, while flocculation removed fine particles as the first stage to prevent the adsorption of kaolin clay.