High-performance plastic-derived metal-free catalysts for organic pollutants degradation via Fenton-like reaction.

The preparation of waste plastics-derived catalysts is an effective strategy for the waste reclamation. However, plastic-derived material is unsuitable for wastewater purification due to its small specific surface area (SSA) and inadequate active sites (such as N/O sites). Herein, we synthesized graphene-like nanosheets using g-C3N4 as the self-sacrificing soft template and plastic as the carbon precursor. Consequently, this strategy greatly promoted the efficiencies of the emerging organic pollutants degradation with the SSA and N content of the plastic-derived biochar increasing up to 1043.4 m2/g and 17.53 at.%, respectively. In detail, 100 % sulfadiazine (SD) removal could be achieved in 180 s via the activation of peroxymonosulfate (PMS) and the catalytic activity is far higher than previous research. Mechanism experiments corroborated that such a striking performance was attributed to the generation of SO4•-, O2•- and 1O2. Meanwhile, kinds of plastic precursors, even medical waste (i.e., masks, gauze, operating caps and degreasing cotton) were also applicable. And the practical application of the plastic-derived catalyst was further demonstrated by treating pollutants in a continuous flow mode with in situ fabricated membrane. This work provides valuable insights into waste plastics processing and water pollutants removal.

Proximity Proteomics Revealed Aberrant mRNA Splicing Elicited by ALS-Linked Profilin-1 Mutants.

Profilin 1 (PFN1) is a cytoskeleton protein that modulates actin dynamics through binding to monomeric actin and polyproline-containing proteins. Mutations in PFN1 have been linked to the pathogenesis of familial amyotrophic lateral sclerosis (ALS). Here, we employed an unbiased proximity labeling strategy in combination with proteomic analysis for proteome-wide profiling of proteins that differentially interact with mutant and wild-type (WT) PFN1 proteins in human cells. We uncovered 11 mRNA splicing proteins that are preferentially enriched in the proximity proteomes of the two ALS-linked PFN1 variants, C71G and M114T, over that of wild-type PFN1. We validated the preferential interactions of the ALS-linked PFN1 variants with two mRNA splicing factors, hnRNPC and U2AF2, by immunoprecipitation, followed with immunoblotting. We also found that the two ALS-linked PFN1 variants promoted the exonization of Alu elements in the mRNAs of MTO1, TCFL5, WRN and POLE genes in human cells. Together, we showed that the two ALS-linked PFN1 variants interacted preferentially with mRNA splicing proteins, which elicited aberrant exonization of the Alu elements in mRNAs. Thus, our work provided pivotal insights into the perturbations of ALS-linked PFN1 variants in RNA biology and their potential contributions to ALS pathology.

Ultrafast and energy-saving microwave-assisted conversion of inert carbon nanomaterials to highly efficient Fenton-like metal-free catalysts for pollutants degradation.

Carbon-driven persulfate (PDS)-based Fenton-like reactions have been widely viewed as prospective strategies to cope with the water pollution. However, high cost, harsh condition and complex modification processes are usually required to boost the catalytic activities of carbocatalysts. Herein, we proposed an ultrafast, energy-efficient, and convenient approach to convert various low-performance carbon materials into highly efficient catalysts by microwave treatment in just 1 min without any other tedious treatment. This process only requires 57 kJ/g energy input, 5 orders of magnitude lower than the traditional calcination process. The catalytic performance of microwave-treated materials could increase by more than 380 times, which is even better than those of the single-atom catalysts. Moreover, DFT calculations and QSARs analyses reveal that the negatively charged carboxyl group is not conducive to the adsorption of PDS (S2O82-) due to electrostatic repulsion, and also increases the work function of the carbocatalysts, which hinders the electron transfer process.

Au NPs decorated holey g-C3N4 as a dual-mode sensing platform of SERS and SALDI-MS for selective discrimination of L-cysteine.

Development of reliable sensing strategy combining surface-enhanced Raman scattering (SERS) and surface-assisted laser desorption/ionization-mass spectrometry (SALDI-MS) is of significant interest to distinguish cysteine enantiomers in body fluid for understanding their physiological roles and toxicity hazards. In this work, a SERS/SALDI-MS dual-mode sensing platform of gold nanoparticles (Au NPs) decorated holey carbon nitride (hg-C3N4) was fabricated for sensitive detecting cysteine. The designed Au@hg-C3N4 matrix featured a uniform distribution of Au NPs with the help of anchoring effect of hg-C3N4 holey structure, which was conducive to produce highly repeatable signals. Moreover, the combination of Au NPs and holey g-C3N4 endowed this matrix with superior enrichment capacity, enhanced charge transfer and strong UV absorption. These merits allowed the matrix to acquire high sensitivity and enhanced reproducibility for l-cysteine by means of SERS/SALDI-MS. Likewise, reliable detection of l-cysteine and efficient recognition of d-cysteine in human serum jointly revealed its prospect for detecting cysteine enantiomers in body fluids. This work offers a reliable SERS/SALDI-MS strategy for determining L/D-cysteine enantiomers, and the designed Au@hg-C3N4 matrix becomes a potential application candidate for selective detection of bio-enantiomers.

Double-side effect of B/C ratio on BDD electrode detection for heavy metal ion in water.

BDD (Boron-doped Diamond) electrode may hold a promising application to detect heavy metal ions for actual water monitoring and early warning, but a poor understanding of influence mechanism of B/C ratio on detection performance is in the way of its fabrication and application. This work is intended to reveal the double-side effect of B/C ratio on detection performance of BDD electrode so as to facilitate its actual application. SBDD (Self-supported Boron-doped Diamond) electrode is introduced for the first time to get rid of the interference factors such as substrate. A systematic investigation is conducted for the influence of B/C ratio on microstructure and electrochemical behavior of SBDD electrodes. With the increase of B/C ratio, the grain size continuously increases, and the preferred orientation gradually changes from plane (220) to (111). The gradual increasing of impurity phase content indicates a deterioration of diamond phase quality. In addition, the electrode electrochemical behavior initially gets better then worse. SBDD electrode with a B/C ratio of 1/500 has the largest active surface area of 2.1 cm2, the smallest diffusion resistance and the highest signal response. Under optimal parameter set, the SBDD electrode enjoys a sensitivity of 0.42 µA L µg-1 cm-2 and a detection limit of 1.12 µg L-1 in a wide linear range of 5-120 ppb. The phase quality and grain morphology jointly contribute to the double-side effect. A suitable B-sp3-C content, preferred orientation of (111) and small particle size may make the performance improvement of BDD electrode available.

Graphene Oxide-Supported Lanthanide Metal-Organic Frameworks with Boosted Stabilities and Detection Sensitivities.

The photoluminescent (PL) properties of lanthanide metal-organic frameworks (Ln-MOFs) are intrinsically subtle to water molecules, which remains the major challenge that severely limits their applications as fluorescent probes in aqueous samples. Herein novel composite fluorescent probes were prepared by growing Ln-MOFs (Tb-MOF, Eu-MOF, and Tb/Eu-MOF) on carboxylated porous graphene oxide (PGO-COOH). The 3D thorny composites presented significantly longer fluorescent lifetimes and higher quantum yields than that of the bare Ln-MOFs and exhibited long-term PL stabilities in aqueous samples up to 15 days. The stable and improved PL properties demonstrated that the highly hybrid composite structures protected the MOF components from the adverse effects of water. Furthermore, the unexpected antenna effect of the PGO-COOH substrate on Ln3+ was supposed to be another reason for the improved PL properties. The composites present ultralow detection limits as low as 5.6 nM for 2,4-dinitrotoluene and 2.3 nM for dipicolinic acid as turn-off and ratiometric fluorescent probes, respectively, which was attributed to the incoporation of PGO-COOH that dramatically enahnced inner filter effects and effectively protected the energy transfer process in the MOF components from the interference of the surrounding water. This work presents an effective strategy for creating ultrasensitive and stable fluorescent probes based on Ln-MOFs for applications in aqueous samples.

In-situ layer-by-layer synthesized TpPa-1 COF solid-phase microextraction fiber for detecting sex hormones in serum.

The secretion disorder of sex hormones is the source that leads to the occurrence of many diseases such as polycystic ovarian syndrome (PCOS), hyperandrogenism and so on. There exist physiological changes in human body when slight fluctuations in concentrations of sex hormones happen. Therefore, it's of great significance for accurate detection of sex hormones in human body. In this work, TpPa-1 COF solid-phase microextraction (SPME) fiber was prepared using high-efficient in-situ synthesis strategy and coupled with HPLC-MS/MS to detect three sex hormones, including Progesterone (P), testosterone (T) and dehydroepiandrosterone (DHEA) in human serum. The thickness of the coating reached 7 µm within 2 h. Under the optimal conditions, the established method presented low limit of detections (LODs, ≤ 0.75 ng/mL), wide linear ranges (0.100-100 ng mL-1) and good reproducibility, and three sex hormones (T, P, DHEA) were successfully detected and quantified in human serum. In conclusion, the established SPME method presented high-efficient fiber preparation and good analytical performances of sex hormone detection, therefore was in great potential for application in clinical.

Facile construction of superhydrophobic hybrids of metal-organic framework grown on nanosheet for high-performance extraction of benzene homologues.

Encapsulating functional nanomaterials within the bulk of metal-organic frameworks (MOFs) offers the opportunity to construct high-performance hybrid coating materials for solid phase microextraction (SPME). In this work, we proposed the facile synthesis of a superhydrophobic MOF composite material (NSZIF-8Si) by growing ZIF-8 on MnxOy nanosheet (NS) and subsequently depositing short-chain polysiloxane on the surface of the composite. A novel SPME fiber was successfully prepared based on the NSZIF-8Si composite. The NSZIF-8Si fiber possessed outstanding thermal stability (up to 450 °C). In headspace SPME of BTEX, the home-made fiber exhibited extraction efficiencies much higher than the commercially available PDMS fiber. This phenomenon was due to the synergetic cooperation of the π-π stacking and the hydrophobic interactions between the NSZIF-8Si coating and the analyte molecules, as well as the increased aspect ratio of the MOF grown on the nanosheet. The established method achieved wide linearity (5-2000 ng L-1) and low LODs (0.02 ng L-1 to 0.21 ng L-1). Satisfactory recoveries were obtained in the analysis of real water samples collected from the Pearl River, indicative of the good reliability of the established method for real-scenario applications. This work might provide critical insights in constructing novel NS/MOF composite materials for the development of high-performance SPME fiber coatings.

Joint effect of nanoplastics and humic acid on the uptake of PAHs for Daphnia magna: A model study.

Nanoplastics (NPs) are emerging pollutants which can adsorb large amounts of hydrophobic organic compounds (HOCs) and be ingested by aquatic organisms. NPs interact with dissolved organic matter (DOM) and result in significant impacts on the bioaccumulation of HOCs in the actual environment. For the first time, the joint effects of two complex matrices on the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) to Daphnia magna (D. magna) were studied by modeling calculation. The complex matrices, nano-sized polystyrene (PS) and/or humic acid (HA), were under environmentally realistic concentrations. A biodynamic model was modified and the uptake fluxes from all exposure pathways were quantified using the experimental data. A flux estimation showed that the bioaccumulation amounts at equilibrium were mostly dependent on dermal uptake (≥99.3 % of the total). The PS matrix would retard the intestinal uptake process in D. magna, especially for the less hydrophobic PAHs; while the HA or the HA-PS matrix would facilitate the mass transfer of PAHs from the matrix to lipids in the gut. Moreover, the biota matrix accumulation factor (BMAF) were calculated to verify the biodynamic model. This work is helpful to clarify the bioaccumulation effects of PAHs in complex environmental systems.

Determination of the mass transfer coefficients in direct immersion solid-phase microextraction.

Diffusion of the analytes across the diffusion boundary layers and subsequently through the fiber coatings determines the extraction kinetics of solid-phase microextraction in aqueous matrices. Besides, the matrix effects can distort the behaviors of the analytes transferring across the diffusion boundary layers. However, these processes were always studied via certain simplification, which often left the mass transfer through the fiber coatings unconsidered and the matrix effects partially investigated. Herein, a comprehensive study on the mass transfer processes in direct immersion solid-phase microextraction was presented. Under different agitation speeds, it was determined that the mass transfer coefficients across the diffusion boundary layers were three to six orders larger than those through the fiber coatings. However, the mass transfer across the diffusion boundary layers was generally the major rate-limiting step. In addition, the shuttle effect and the barrier effect, which were responsible for accelerating and retarding the extraction kinetics, respectively, were found to be the dominant matrix effect alternately under different agitation speeds. This study comprehensively illustrated the major rate-limiting step and the dominant matrix effects through recording the mass transfer coefficients.

Hollow carbon nanobubbles-coated solid-phase microextraction fibers for the sensitive detection of organic pollutants.

Herein, a novel solid-phase microextraction (SPME)fiber based on hollow carbon nanobubbles was developed for the analysis of persistent organic pollutants. The hollow carbon nanobubbles (HCNBs), derived from the nanoscale zeoliticimidazolate framework (ZIF-8), not only possessed the ZIF-8-like microporous shell but also created an internal space for analytes storage. This architecture was beneficial to accelerating the mass transfer process and enhancing the enrichment capacity towards target analytes. As a result, the sensitivity of this HCNBs based SPME fiber toward analytes (e.g., BTEX, PAHs and PCBs) was 2-180 times higher compared with the commercial fibers (100 µm PDMS, 65 µm PDMS/DVB or 85 µm PA). In addition, owing to the size-selectivity of the microporous shell, the HCNBs-based SPME fiber showed high extraction ability towards target analytes with low molecule weight. Furthermore, the lifespan of the homemade fiber was evaluated to be more than 100 times attributing to the hard and stable carbon framework. Under optimal working conditions, analytical performance of the fiber towards PCBs with varying chlorination degrees showed a wide linear range (0.05-1000 ng L-1) and low LODs (0.0017-0.0042 ng L-1). Finally, the established method was successfully applied to the determinations of PCBs in three environmental water samples with good recoveries (84.5-117.1%).

Application of Bionic Technologies on the Fracturing Plug.

The dissolvable bridge plug is one of the most important tools for multi-stage hydraulic fracturing in the field of oil/gas development. The plug provides zonal isolation to realize staged stimulation and, after fracturing, the plug is fully dissolved in produced liquids. A bionic surface was introduced to improve the performance of the plug. Surface dimples in the micron dimension were prepared on the dissolvable materials of the plug. The experimental results showed that the surface dimples changed the hydrophilic and hydrophobic properties of the dissolvable materials. The dissolution rate has a great relation with the parameters of the dimples and can be controlled by choosing the dimples' parameters to some degree.

Energy-efficient construction of thermally stable superhydrophobic nanoscale stacked lamellae based solid-phase microextraction coating for the determination of non-polar compounds.

Herein, through a facile and energy-friendly approach, thermally stable manganese-derived amorphous stacked nanosheet (MASNS) coatings with controlled wetting property ranging from superhydrophilicity to superhydrophobicity were synthesized. The superhydrophobic MASNS coating exhibited remarkable selectivity and sensitivity in the solid phase microextraction (SPME) of non-polar aromatic analytes, even amid the abundance of polar compounds, due to the superhydrophobic effect and the stacked lamellar structures. The established method was applied to the determination of polycyclic aromatic hydrocarbons (PAHs), featuring low LODs (i.e., 0.14-0.24 ng L-1) and wide linear ranges (e.g., 10-10000 ng L-1). Extraction and desorption conditions were optimized to unleash the potential of the fiber before it was applied to the analysis of target analytes in real water samples, where satisfactory recoveries were obtained (81.7%-114.2%). This work might provide critical insights for the scalable production of superhydrophobic nanosheets as affordable and high-performance adsorbents.

Tribology Performance of Surface Texturing Plunger.

Plunger pumps are widely used in oil pumping units around the world. The water content of the wellbore is increasing along with the development progress, so the lubricating capacity of the well fluids between the plunger and barrel is decreasing correspondingly. Commonly, the substrate material of the plunger and barrel are stainless steel, and the plunger surface is usually covered with nickel-based coating. Therefore, the performance of the plunger and barrel has been affected due to poor lubrication and eccentric wear. Non-smooth surfaces have been proven to improve the tribology performance in many cases. A surface texturing plunger covered with specific dimples has been prepared by using laser surface texturing technology. The morphology of the surface texturing plunger was characterized and analyzed. The tribology performance of surface texturing plunger samples was tested using standard friction and wear test machines with oil and water lubrication, respectively. The results indicated that surface texturing could effectively reduce the coefficient of friction, and the wear resistance of the surface textured samples has been improved to some extent.

Sorption properties of hydrophobic organic chemicals to micro-sized polystyrene particles.

It has been reported that microplastics (MPs) have strong affinity for hydrophobic organic chemicals (HOCs) and can be ingested accidentally by aquatic organisms, posing a potential threat to the environment. To date, the sorption data used in modelling to clarify the mechanism were mostly obtained in varied sampling durations and regions from different works, which might cause inevitable deviation in modelling results. The current study aimed to illustrate the sorption properties of HOCs to the micro-sized polystyrene (PS). The sorption behaviors of HOCs to the PS were investigated at a certain pre-equilibrium status, and the theoretical analysis was taken into consideration. A bottle-shaped passive dosing system was designed to measure the concentration ratio of HOCs in different phases of the exposure suspension at a certain time (logaMP), including polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) with logKow ranging from 3.17 to 10.20, between water and PS MPs with different dimensions (diameters of 100 nm, 1 µm and 2 µm, respectively). The calculated logaMP ranged from 3.73 to 8.34, and a positive correlation was found between logaMP and log1r0 (r0 is the MP radius). The results indicated that HOCs would diffuse into the PS particles, but the mass transfers inside the particles were slow and would be negligible in some environmental cases. Under theoretical considerations, the diffusion through the boundary layer of the particle was considered as the dominating process because it was fast, and the contributions of absorbed amounts on the particle surface were larger for smaller PS particles (i.e. 100-nm PS). This study could provide applicable data for further exploring the effects of micro-sized plastics on the HOCs in environmental samples.

Boosting loading capacities of shapeable metal-organic framework coatings by closing the interparticle spaces of stacked nanocrystals.

Herein, an intriguing strategy is presented for preparing monolithic metal-organic framework (MOF) coatings through compactly filling up the interparticle spaces in the stacked architectures of nanocrystals. The monolithic coatings exhibited remarkably enhanced performance (double to triple compared to the MOF powders) for analyte extraction, due to the increased volumetric BET areas.

Investigating the toxicities of different functionalized polystyrene nanoplastics on Daphnia magna.

Nanoplastics (NPs) spread widely with water and air current, and they can accumulate in aquatic organisms, even penetrating biofilms, which may cause persistent toxicity and potential hazards. This current study aimed to reveal the toxicological mechanism of different functionalized polystyrene (PS) NPs on Daphnia magna (D. magna) by investigating toxicity endpoints in individual level and biochemical level. In this study, acute toxicity, behavioral parameters and biomarker responses of D. magna was measured in the exposure of different functionalized PS NPs (plain PS, PS-p-NH2, PS-n-NH2 and PS-COOH). The results indicated that when exposed to the plain PS, ROS induction would activate MAPKs, thereby causing lethality and adverse behavior effects on D. magna; while the functionalized PS NPs were less toxic than the plain PS, especially for PS-p-NH2 which was severely flocculated after exposure, thus showing no immobilization at the investigated concentrations. Also, the antioxidant system was mainly stimulated due to the direct interaction with the cell surface receptor, which was different from the plain PS. Consequently, this work suggests significant effects of functional groups on NPs for environmental toxicity studies, and provides a better understanding of the toxicological mechanism on the toxicity of PS NPs toward D. magna.

Fabricating the Superhydrophobic Nickel and Improving Its Antifriction Performance by the Laser Surface Texturing.

The superhydrophobic surface can change the friction property of the material, reduce the adhesion of the friction interface, and produce a certain slip, thereby reducing the friction coefficient. The laser has high energy, high density, and is especially suitable for the surface treatment of materials. The laser surface texturing is a good way to construct superhydrophobic surfaces. The experiment uses a nanosecond pulse laser to construct the groove texture on the nickel surface. The contact area between the air and the droplets retained on the rough surface is increased, effectively preventing the water droplets from entering the gully of the surface microstructure, reducing the water droplets and the solid surface. The contact area ultimately makes the surface exhibit excellent superhydrophobicity. A superhydrophobic nickel surface having an apparent contact angle of water (ACAW) of 160° and a sliding angle (SA) of less than 10° was prepared. The MM-W1B vertical universal friction and wear tester was used to test the groove texture samples with different depths. The surface texture can capture the wear debris generated by the wear and store the lubricant, which is beneficial to the formation of fluid dynamic pressure lubrication and improve the load. The friction coefficient is reduced from 0.65 of the unprocessed surfaces to 0.25 after the texturing, and the friction performance is greatly improved.

A Convenient and Versatile Amino-Acid-Boosted Biomimetic Strategy for the Nondestructive Encapsulation of Biomacromolecules within Metal-Organic Frameworks.

Herein, an amino-acid-boosted biomimetic strategy is reported that enabled the rapid encapsulation, or co-encapsulation, of a broad range of proteins into microporous metal-organic frameworks (MOFs), with an ultrahigh loading efficiency. It relies on the accelerated formation of prenucleation clusters around proteins via a metallothionein-like self-assembly. The encapsulated proteins maintained their native conformations, and the structural confinement within porous MOFs endowed enzymes with excellent bioactivity, even in harsh conditions (e.g. in the presence of proteolytic or chemical agents or at high temperature). Furthermore, owing to the merits of nondestructive and protein surface charge-independent encapsulation, the feasibility of this biomimetic strategy for biostorage, enzyme cascades, and biosensing was also verified. It is believed that this convenient and versatile encapsulation strategy has great promise in the important fields of biomedicine, catalysis, and biosensing.

Fabrication of a polymeric composite incorporating metal-organic framework nanosheets for solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples.

In this contribution, it was discovered that even distribution of a metal-organic framework (MOF) [e.g. copper 1,4-benzenedicarboxylate (CBDC)] within polymeric matrixes (e.g. polyimide) resulted in a high-efficient coating material on the surface of a stainless steel wire (SSW). Consequently, a home-made solid phase microextraction (SPME) fiber was fabricated for fast determination of target analytes in real water samples. Scanning electron microscope images indicated that the coating possessed homogenously porous surface. Coupled with gas chromatography-mass spectrometry (GC-MS) and direct immersion SPME (DI-SPME) technique, the fiber was evaluated through the analysis of five polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Under optimized extraction and desorption conditions, the established method based on the home-made fiber exhibited good repeatability (4.2-12.7%, n = 6) and reproducibility (0.9-11.7%, n = 3), low limits of detection (LODs, 0.11-2.10 ng L-1), low limits of quantification (LOQs, 0.36-6.99 ng L-1) and wide linear ranges (20-5000 ng L-1). Eventually, the method was proven applicable in the determination of PAHs in real samples, as the recoveries were in a satisfactory range (81.7-116%).