[Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials].

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 µm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 µg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 µg/L and 0.03-0.42 µg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 µg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.

Metal-Organic Framework-Based Composites for the Adsorption Removal of Per- and Polyfluoroalkyl Substances from Water.

The increasing health risks posed by per- and polyfluoroalkyl substances (PFASs) in the environment highlight the importance of implementing effective removal techniques. Conventional wastewater treatment processes are inadequate for removing persistent organic pollutants. Recent studies have increasingly demonstrated that metal-organic frameworks (MOFs) are capable of removing PFASs from water through adsorption techniques. However, there is still constructive discussion on the potential of MOFs in adsorbing and removing PFASs for large-scale engineering applications. This review systematically investigates the use of MOFs as adsorbents for the removal of PFAS in water treatment. This primarily involved a comprehensive analysis of existing literature to understand the adsorption mechanisms of MOFs and to identify factors that enhance their efficiency in removing PFASs. We also explore the critical aspects of regeneration and stability of MOFs, assessing their reusability and long-term performance, which are essential for large-scale water treatment applications. Finally, our study highlights the challenges of removing PFASs using MOFs. Especially, the efficient removal of short-chain PFASs with hydrophilicity is a major challenge, while medium- to long-chain PFASs are frequently susceptible to being captured from water by MOFs through multiple synergistic effects. The ion-exchange force may be the key to solving this difficulty, but its susceptibility to ion interference in water needs to be addressed in practical applications. We hope that this review can provide valuable insights into the effective removal and adsorption mechanisms of PFASs as well as advance the sustainable utilization of MOFs in the field of water treatment, thereby presenting a novel perspective.

Portable smartphone-assisted highly sensitive detection of mercury ions based on gold nanoparticle-modified NH2-UiO-66 metal-organic framework.

A novel portable smartphone-assisted colorimetric method was reported for the determination of Hg2+ with good analytical performance. A Zr(IV)-based metal-organic framework functionalized with amino groups (NH2-UiO-66) has been adopted as a supporting platform to anchor gold nanoparticles (AuNPs), avoiding the migration and aggregation of AuNPs. With the addition of Hg2+, the formation of gold amalgam proved possible to enhance peroxidase-like activity of the composite (AuNPs/NH2-UiO-66), accelerating the oxidization of zymolyte 3,3',5,5'-tetramethylbenzidine (TMB). In the meantime, the color of the reaction solution turned a vivid blue, and the red, green, and blue (RGB) values of the solution color changed accordingly. On account of this strategy, the quantitative detection of Hg2+ could be achieved. After the optimization of the experiment conditions, the average color intensity (Ic) resulting from RGB values was linear related to the concentration of Hg2+ from 10 to 100 nM, accompanied with a detection limit (LOD) down to 5.4 nM calculated by 3σ/S. The successful application of the designed method has been promoted to detect Hg2+ in some water samples, displaying a great potential in practical application. Furthermore, the use of a smartphone made our proposed method simple and accurate, and thus puts forward a possible way for in situ and real-time monitoring.

MOF-On-MOF Dual Enzyme-Mimic Nanozyme with Enhanced Cascade Catalysis for Colorimetric/Chemiluminescent Dual-Mode Aptasensing.

A novel metal-organic framework (MOF)-on-MOF dual enzyme-mimic nanozyme was designed as enhanced cascade signal amplification for the colorimetric and chemiluminescent (CL) dual-mode aptasensing. The MOF-on-MOF hybrid is composed of MOF-818 with catechol oxidase-like activity and iron porphyrin MOF [PMOF(Fe)] with peroxidase-like activity, called MOF-818@PMOF(Fe). MOF-818 can catalyze the 3,5-di-tert-butylcatechol substrate and produce H2O2 in situ. Subsequently, PMOF(Fe) catalyzes H2O2 to produce reactive oxygen species, which oxidize 3,3',5,5'-tetramethylbenzidine or luminol to produce color or luminescence. Thanks to the nano-proximity effect and the confinement effect, the efficiency of the biomimetic cascade catalysis is greatly improved, which in turn generates enhanced colorimetric and CL signals. Taking the detection of chlopyrifos as an example, the prepared dual enzyme-mimic MOF nanozyme is combined with the aptamer with specific recognition ability to develop a colorimetric/CL dual-mode aptasensor for highly sensitive and selective detection of chlorpyrifos. The proposed MOF-on-MOF dual nanozyme-enhanced cascade system may provide a new pathway for the further development of a biomimetic cascade sensing platform.

Pregabalin can interact synergistically with Kv7 channel openers to exert antinociception in mice.

Chronic pain is a common public health problem and remains an unmet medical need. Currently available analgesics usually have limited efficacy for the treatment of chronic pain, including neuropathic pain and persistent inflammatory pain, or they are accompanied by many adverse side effects. The voltage-gated calcium channel blocker (pregabalin) and potassium channel openers (flupirtine and retigabine) have been widely used for the management of chronic pain, but their effectiveness in combination is unclear. In this research, we evaluated the antinociceptive effects of pregabalin in combination with flupirtine or retigabine in carrageenan-induced inflammatory pain and paclitaxel-induced peripheral neuropathy in mice using the von Frey test. Isobolographic analysis indicated that pregabalin exerted synergistic antinociceptive effects when combined with flupirtine or retigabine in neuropathic and inflammatory pain models. Furthermore, the antinociceptive effects of pregabalin, flupirtine/retigabine, and their combinations were significantly attenuated by the Kv7 channel blocker XE991. The favored dose ratio between pregabalin and flupirtine/retigabine in combinations was also investigated. Finally, we evaluated the motor coordination of their combinations using the rotarod test, and the outcomes underpinned their safety. Collectively, our results support the potential use of pregabalin in combination with flupirtine or retigabine to alleviate chronic pain.

An electrochemical sensor based on synergistic enhancement effects between nitrogen-doped carbon nanotubes and copper ions for ultrasensitive determination of anti-diabetic metformin.

Metformin (MET) is the primary medicine for type II diabetes, which produces carcinogenic byproducts during chlorine disinfection, so the detection of MET in aqueous environment is crucial. In this work, an electrochemical sensor based on nitrogen-doped carbon nanotubes (NCNT) has been constructed for ultrasensitive determination of MET in the presence of Cu(II) ions. The excellent conductivity and rich π-conjugated structure of NCNT facilitate the electron transfer rate of fabricated sensor and benefit the adsorption of cation ions. Cu(II) ions can chelate with MET to form MET-Cu(II) complex, which are easily accumulated on the surface of NCNT through cation-π interaction. Attributing to the synergistic enhancement effects of NCNT and Cu(II) ions, the fabricated sensor exhibits excellent analytical performances with a low detection limit of 9.6 nmol L-1, high sensitivity of 64.97 A mol-1 cm-2 and wide linear range of 0.3-10 µmol L-1. The sensing system has been successfully applied for rapid (20 s) and selective determination of MET in real water samples with satisfactory recoveries (90.2 %-108.8 %). This study provides a robust strategy for MET detection in aqueous environment and holds great promise for rapid risk assessment and early warning of MET.

Flupirtine and antihistamines exert synergistic anti-nociceptive effects in mice.

RATIONALE: Drug combinations are commonly used in pain management, which can produce potent analgesic effects with reduced dosage and adverse effects. OBJECTIVE: This study was designed to evaluate the anti-nociceptive effects and adverse effects of new combinations of flupirtine (a Kv7 potassium channel opener) and antihistamines (promethazine, fexofenadine) on acute and chronic pain in mice, and the possible mechanisms behind the synergistic analgesic effects were preliminarily investigated. METHODS: In acetic acid writhing test, carrageenan-induced inflammatory pain model, and paclitaxel-induced neuropathic pain model, the interaction indexes (γ) between flupirtine and antihistamines were determined by isobolographic analysis. Furthermore, the Kv7 channel blocker XE991 was used to determine whether the effects of single agents and drug combinations on paclitaxel- and carrageenan-induced mechanical allodynia were mediated by Kv7 channels. Finally, hepatotoxicity markers, liver histopathology, and the rotarod test were used to investigate the adverse effects of drugs in combination doses. RESULTS: The interaction indexes of flupirtine-promethazine and flupirtine-fexofenadine in all the above three pain models were lower than 1. The analgesic effects of flupirtine (13 mg/kg), promethazine (5 mg/kg), fexofenadine (20 mg/kg), and their combinations were antagonized significantly by XE991 (3 mg/kg). And the adverse effects of flupirtine and antihistamines in combination doses were not significantly different from the vehicle group. CONCLUSIONS: Flupirtine and antihistamines produced synergistic analgesic effects in all the above pain models. The analgesic effects of antihistamines were partially mediated by Kv7/M channels, and the activation of Kv7/M channels may be partly responsible for the synergistic analgesic effects between flupirtine and antihistamines.

Design, synthesis and evaluation of heterocyclic 2-phenylacetate derivatives as water-soluble rapid recovery hypnotics.

In this work, a series of novel heterocyclic 2-phenylacetate derivatives were designed and synthesized as water-soluble and rapid recovery hypnotic agents. After introducing heterocyclic ring to the amide group of propanidid, the obtained propanidid derivatives showed greatly improved hydrophilicity and good anesthetic activity. In three animal experiments (mice, rats, and rabbits), compounds 13-15 showed potent hypnotic potency (HD50 = 7.6, 6.5, 7.4 mg/kg in rabbits, respectively) and higher therapeutic indexes (TI = 17.3, 16.6, 15.2 in rabbits, respectively) than propanidid (TI = 14.7 in rabbits) or propofol (TI = 5.4 in rabbits). Moreover, the recovery time of compounds 13-15 (time to walk, 96.6, 79.6, 81.4 s in rabbits, respectively) were shorter than that of propanidid (124.5 s in rabbits) or propofol (425.3 s in rabbits). The experimental results suggested the potential of compounds 13-15 as water-soluble anesthetics with rapid recovery profile.

Identification of differentially expressed long non-coding RNAs and messenger RNAs involved with muscle development in Dazu black goats through RNA sequencing.

This study aimed to explore the genetic basis of muscle development in goats. The transcriptome dataset for differentially expressed lncRNAs (DELs) and differentially expressed genes (DEGs) of goat muscle at different developmental stages were obtained using RNA-Seq. A total of 447,806,481 and 587,559,465 clean reads in the longissimus dorsi muscle of Dazu black goats between 75d embryonic stage and 1d after birth were generated through Illumina paired-end sequencing, and their mapping rates were 89.82 and 90.99%, respectively. Moreover, 4517 DEGs and 648 DELs were identified, and 4784 lncRNA-mRNA targeting relationships were predicted. Gene function annotation results showed that 4101 DEGs were significantly enriched to 1098 GO terms, and 2014 DEGs were significantly enriched to 40 KEGG pathways, including many GO terms and pathways related to muscle development, such as cell differentiation and Wnt signaling pathway. Then, 10 DELs and 20 DEGs were randomly selected for RT-qPCR verification, and the agreement rate between the verification and RNA-Seq results was 90%, indicating the high reliability of the RNA-Seq data analysis. In conclusion, this study obtained several mRNAs and lncRNAs related to the muscle development of Dazu black goats and identified several targeted regulatory pairs of lncRNA-mRNA. This study may serve as a reference to understand the genetic basis and molecular mechanism of muscle development in goats.

Discovery of a novel class of benzoxazole derivatives as histamine H3 receptor ligands for the treatment of neuropathic pain.

To discover effective analgesics, we summarize the synthesis, optimization, and pharmacological anti-nociceptive effects of a novel series of benzoxazole derivatives targeting H3 receptor (H3R). The new benzoxazoles were assayed in vitro for histamine H3R and H1R binding affinity. The best compound 8d (2-methyl-6-(3-(4-methylpiperazin-1-yl)propoxy)benzo[d]oxazole) exhibited high affinity for H3R (Ki = 19.7 nM), high selectivity for ten other off-target receptors, and negligible effects on human ether-a-go-go-related gene (hERG, cardiac ion channel). In rodent animals, compound 8d dose-dependently reversed formalin-evoked pain (Phase I, ED50 = 6.0 mg/kg; Phase II, ED50 = 7.8 mg/kg) and CCI-induced neuropathic pain (chronic constriction injury, ED50 = 15.6 mg/kg). Furthermore, compound 8d showed an excellent safety profile in acute toxicity test (LD50 > 2000 mg/kg) with a therapeutic index (TI = LD50/ED50) > 250 and showed a desirable drug-like pharmacokinetic profile. Above characteristics indicate that compound 8d represents a promising candidate analgesic for the treatment of neuropathic pain.

Synergistic Antinociceptive Effects of Indomethacin-Pregabalin and Meloxicam-Pregabalin in Paclitaxel-Induced Neuropathic Pain.

Neuropathic pain is often closely associated with nerve injury or inflammation, and the role of traditional nonsteroidal anti-inflammatory drugs as adjuvants for treating chemotherapy-induced peripheral neuropathic pain remains unclear. In this study, the potential synergistic antinociceptive effects of indomethacin-pregabalin and meloxicam-pregabalin were evaluated in paclitaxel-induced neuropathic pain and carrageenan-induced inflammatory pain in rodents. Although indomethacin and meloxicam alone only slightly relieved mechanical allodynia in the above two models, isobolographic analysis showed that the combination of indomethacin or meloxicam with pregabalin produced significant synergistic antinociceptive effects for paclitaxel-induced neuropathic pain (IN-PGB, experimental ED25 = [4.41 (3.13-5.82)] mg/kg, theoretical ED25 = [8.50 (6.62-10.32)] mg/kg; MEL-PGB, experimental ED25 = [3.96 (2.62-5.46)] mg/kg, theoretical ED25 = [7.52 (5.73-9.39)] mg/kg). In addition, MEL-PGB dosed via intraplantar injection into the left paw, intragastric injection, or intraperitoneal injection reversed paclitaxel-induced allodynia, indicating that they may act at multiple sites in the neuroaxis and periphery. However, indomethacin-pregabalin and meloxicam-pregabalin exerted antagonistic antiallodynic interactions in carrageenan-induced inflammatory pain in rats. Taken together, coadministration of indomethacin or meloxicam with pregabalin may possess potential therapeutic advantages for treating chemotherapy-induced neuropathic pain.

Simultaneous preconcentration and pre-column derivatization for rapid analysis of nitrilotriacetic acid in environmental waters by high performance liquid chromatography.

A simplified sample pretreatment procedure was developed for quantitative measurement of nitrilotriacetic acid (NTA) in environmental water. On the basis of coordination capacity between NTA and metal ions, aluminum-based metal organic framework (MOF, MIL-53(Al)) was adopted for the adsorption of NTA, followed by stripping with copper sulfate as the eluent. The adsorbed NTA was converted into Cu-NTA during the desorption process, which facilitated the ensuing measurement by high performance liquid chromatography (HPLC). A linear range within 0.10 - 10 mg L-1 was achieved, along with a limit of detection (LOD, S/N=3, n=7) of 0.03 mg L-1 and an enrichment factor of 10.4. The developed method was validated by the analysis of sea water, influent of wastewater treatment plant and industrial wastewater, with satisfactory recoveries (90.2 - 91.1%) obtained.

Genetic Basis of Follicle Development in Dazu Black Goat by Whole-Transcriptome Sequencing.

The follicle development (FD) is an important factor determining litter size in animals. Recent studies have found that noncoding RNAs (ncRNAs) play an important role in FD. In particular, the role of the regulatory mechanism of competing endogenous RNAs (ceRNAs) that drive FD has attracted increasing attention. Therefore, this study explored the genetic basis of goat FD by obtaining the complete follicular transcriptome of Dazu black goats at different developmental stages. Results revealed that 128 messenger RNAs (mRNAs), 4 long noncoding RNAs (lncRNAs), 49 microRNAs (miRNAs), and 290 circular RNAs (circRNAs) were significantly differentially expressed (DE) between large and small follicles. Moreover, DEmRNAs were enriched in many signaling pathways related to FD, as well as GO terms related to molecular binding and enzyme activity. Based on the analysis of the ceRNA network (CRN), 34 nodes (1 DElncRNAs, 10 DEcircRNAs, 14 DEmiRNAs, and 9 DEmRNAs) and 35 interactions (17 DEcircRNAs-DEmRNAs, 2 DElncRNAs-DEmiRNAs, and 16 DEmRNA-DEmiRNAs) implied that the CRN could be involved in the FD of goats. In conclusion, we described gene regulation by DERNAs and lncRNA/circRNA-miRNA-mRNA CRNs in the FD of goats. This study provided insights into the genetic basis of FD in precise transcriptional regulation.

3-Aminophenylboronic acid-mediated aggregation of gold nanoparticles for colorimetric sensing of iohexol in environmental and biological samples.

Iohexol (IHO), as one of iodinated X-ray contrast, is often used as not only a chemical marker for tracking wastewater contamination in aquatic environment, but also an ideal glomerular filtration rate marker for explorating kidney disease. To these aims, it is important to establish reliable, fast, and cheap methods to detect IHO in environmental and biological samples. This work describes for the first time the development of a selective, sensitive and reliable colorimetric sensing assay for the fast determination of IHO in environmental and biological samples based on 3-aminophenylboronic acid (3-APBA) mediated aggregation of gold nanoparticles (AuNPs). In this approach, 3-APBA can assemble on the AuNPs surface through electrostatic interaction between its amino groups with the negatively charged citrate stabilizer of AuNPs to form AuNP@3-APBA. Subsequently, the aggregation and visual color change of the assembled AuNP@3-APBA are induced by the covalent reaction between boronic acid ligands of 3-APBA and cis-diols of IHO. The developed assay presented a very simple operating procedure and a rapid analysis time of around 10 min. The developed assay also exhibited good selectivity and a low limit of detection (LOD) of 0.005 mM for detecting IHO. Moreover, the developed assay showed comparable accuracy and precision to the high-performance liquid chromatography-diode array detector (HPLC-DAD) method when used for the rapid determination of IHO in river water and human urine samples. The recoveries of IHO at three spiking levels were in the range of 91.5-106.3% with relative standard deviation (RSD) values below 6.39%.

Underwater suspended bifunctionalized polyethyleneimine-based sponge for selective removal of anionic pollutants from aqueous solution.

Highly selective and efficient removal of ionic pollutants, including ionic organic compounds and heavy metal ions from water, is still a huge challenge due to the complex nature of polluted water. To meet this challenge, we presented the synthesis of bifunctionalized polyethyleneimine-based sponges through cryo-polymerization via BDDE as the crosslinker followed by bifunctional modification with glycidyl trimethylammonium chloride (GTAC) and phenyl glycidyl ether (PGE), which simultaneously afford quaternary ammonium cation (strongly basic and hydrophilic) and phenyl (hydrophobic) functionalities, respectively. As a result, a hybrid hydrophilic-hydrophobic sponge is generated that could stably be suspended underwater due to the co-operative effect of the water-absorbing hydrophilic domain and the hydrophobic domain generating buoyancy. The quaternized and phenyl-functionalized PEI-based sponge (SQP-PEI) demonstrated highly selective and efficient removal of anionic pollutants from water, including diclofenac sodium (DIC), methyl orange (MO) and chromium (Cr(VI)) with co-existing interferences. The Langmuir isotherms revealed the maximum adsorption capacities of 342.7 mg/g, 491.9 mg/g, and 242.7 mg/g for DIC, MO, and Cr(VI), respectively. The studies of adsorption mechanism suggested that the bifunctional SQP-PEI sponge indeed afford both strong anion-exchange interaction and π-π interaction toward organic pollutants DIC and MO, and the strong anion-exchange interaction can be the dominated adsorption mechanism for anionic DIC, MO and Cr(VI) species. The suspended SQP-PEI also demonstrated excellent reusability, which shows the potential of SQP-PEI for real applications.

Cost-effectiveness Analysis of Trastuzumab Emtansine as Second-line Therapy for HER2-Positive Breast Cancer in China.

BACKGROUND AND OBJECTIVE: Trastuzumab emtansine (T-DM1) is the standard second-line option for the treatment of patients with human epidermal growth factor receptor-2 (HER2)-positive breast cancer for its superior clinical efficacy in prolonging progression-free survival. The objective of this study was to evaluate the cost effectiveness of T-DM1 from the Chinese healthcare perspective. Capecitabine (Cap), capecitabine + lapatinib (Cap + Lap), capecitabine + trastuzumab (Cap + Tra), capecitabine + trastuzumab + pertuzumab (Cap + Tra + Per) were selected as comparators. METHODS: A three-state Markov simulation model was performed. The state transition probabilities were estimated based on the results of a published network meta-analysis, and utilities were derived from the published literature. The costs populated in the model were acquired from the local charge or previously published studies. One-way sensitive analysis and probabilistic sensitivity analyses were performed to test the robustness of the results. RESULTS: Compared with Cap, Cap + Lap, Cap + Tra, and Cap + Tra + Per, T-DM1 was estimated to increase the cost by US$109,699.1, $106,019.1, $97,506.3, and $67,121.9, respectively, and yield a gain of 0.544 quality-adjusted life years (QALYs), 0.383 QALYs, 0.367 QALYs, 0.087 QALYs, respectively. Corresponding incremental cost-effectiveness ratios (ICERs) were $201,652.9, $276,812.5, $265,685.0, and $771,516.1 per QALY. The probabilities of T-DM1 as the dominant option were 0% at the willingness-to-pay (WTP) threshold of $31,245.1/QALY. CONCLUSIONS: T-DM1, as second-line therapy in the treatment of HER2-positive breast cancer, is not a cost-effective option in China. Given the significant clinical efficacy, an appropriate price reduction of T-DM1 is required to benefit more HER2-positive breast cancer patients.

Facile Synthesis of Mixed-Mode Weak Anion-Exchange Microspheres via One-Step Pickering Emulsion Polymerization for Efficient Simultaneous Extraction of Strongly and Weakly Acidic Drugs from Reservoir Water.

Poly(2-(diethylamino)ethyl methacrylate-co-divinylbenzene) (poly(DEAEMA-co-DVB)) microspheres with mixed-mode weak anion-exchange (WAX) character were successfully fabricated for the first time via facile one-step Pickering emulsion polymerization. The obtained poly(DEAEMA-co-DVB) particles had good spherical geometry, uniform particle size in the range of 30-40 µm, a large specific surface area of 575 m2/g, and a pore size range of 5-30 nm, according to the SEM and nitrogen adsorption-desorption results. Using these mixed-mode WAX microspheres as packing material, a reliable and robust analytical method based on solid phase extraction and high performance liquid chromatography with ultraviolet detection (SPE-HPLC-UV) was developed for simultaneous determination of six strongly and weakly acidic nonsteroidal anti-inflammatory drugs (NSAIDs, niflumic acid, diflunisal, naproxen, ketoprofen, mefenamic acid, and diclofenac) in reservoir water. Under optimized conditions, it was applicable to preconcentrate up to 500 mL of reservoir water samples on the WAX cartridges with satisfying recoveries (88-96%) for all the NSAIDs tested. The limits of detection were in the range of 0.002-0.025 µg L-1, respectively. Our results showed that the developed mixed-mode WAX poly(DEAEMA-co-DVB) phase containing a tertiary amine with a pKa value of approximately 10.7 could be used for simultaneous clean-up and preconcentration of strongly and weakly acidic organic pollutants in real environmental water, which could not be achieved by single use of quaternary ammonium strong anion-exchange phase or weaker primary and secondary amine anion-exchange.

[Analytical methods for urinary biomarkers of human exposure to phthalates].

Phthalates (PAEs) are a class of endocrine-disrupting chemicals. In recent years, the harmful effects of PAEs on human health, in particular their toxicity toward the reproductive system and development, have received significant attention because of their increasing production and usage. PAEs are ubiquitous in the environment and food products, resulting in unavoidable and long-term exposure in humans. Therefore, exposure and risk assessments of PAEs in humans are necessary. Screening and quantification of phthalate metabolites in urine is an important method for evaluating PAEs exposure, and establishing accurate analytical methods for this purpose has become a high priority. Phthalate monoesters and secondary metabolites are the most commonly targeted biomarkers of exposure to short-and long-chain PAEs, respectively. The combination of off-line or on-line solid phase extraction (SPE) with high performance liquid chromatography-tandem mass spectrometry has become the preferred method for the determination of phthalate metabolites. This paper reviews the analytical methods available for the detection of urinary phthalate metabolites and discusses the advantages, limitations, and challenges presented by each method in practical applications.

Controlled Manipulation of Metal-Organic Framework Layers to Nanometer Precision Inside Large Mesochannels of Ordered Mesoporous Silica for Enhanced Removal of Bisphenol A from Water.

Considerable attention has been paid on the design of hierarchical porous metal-organic framework (MOF) composites, which not only enhances the performance but also broadens the applications of MOFs. So far, controlled manipulation of nanometer-thick MOF layers in ordered mesochannels, while retaining their respective intrinsic properties, is still a main challenge because of the difficulty of growing MOFs in confined space. Herein, using a step-by-step coordination method, the formation of a hierarchical micro-mesoporous hybrid with a wall (channel wall and coating layer) thickness of up to 8.0 nm and open pore size down to 7.7 nm has been achieved based on large mesoporous SBA-15, and the wall thickness with nanometer precision can be controlled by adjusting the growth cycles of zeolite imidazolate framework-8 (ZIF-8) coating layers. Compared to pure ZIF-8, the obtained ZIF-8@SBA-15 composites showed more than 2-fold enhancement in adsorption capacity and approximately 20-fold improvement in the adsorption rate constant for bisphenol A in water, which could be ascribed to the synergistic effects of the high adsorption ability from ZIF-8 and the fast diffusion property from SBA-15. More importantly, the degraded ZIF-8@SBA-15 composite can be completely restored by a simple immersion into 2-methylimidazole solution. The easy restorability and good reusability further enable ZIF-8@SBA-15 as a promising adsorbent for effectively removing organic contaminants from water.

Hyperbranched mixed-mode anion-exchange polymeric sorbent for highly selective extraction of nine acidic non-steroidal anti-inflammatory drugs from human urine.

This paper describes the poly(divinylbenzene) (PDVB) supported synthesis of quaternized hyperbranched macromolecules (QHMs) and its use as a highly selective, high-capacity mixed-mode anion-exchange (MAX) sorbent. In detail, the aminated PDVB support was firstly synthesized by copolymerization of divinylbenzene and 2-(diethylamino)ethyl methacrylate via Pickering emulsion polymerization. The QHMs were then grafted on PDVB by a divergent synthesis involving consecutive reactions of resorcinol diglycidyl ether with methylamine (N, N-dimethylethanolamine for terminal epoxides), which brought in a high density of quaternary ammonium functionalities. The changes of specific surface area (SBET), pore volume and ion exchange capacity (IEC) with generation number reveal that the QHMs have been grown successfully within the large meso-channels of the porous aminated PDVB. The best compromise between the SBET, pore volume and IEC was obtained at the 4th generation (G4). Due to the highest IEC (0.47 meq/g), the G4-QHMs was successfully applied for mixed-mode solid phase extraction (SPE) of acidic non-steroidal anti-inflammatory drugs (NSAIDs). An efficient approach based on the mixed-mode SPE coupled with HPLC-UV was developed for highly selective extraction and cleanup of nine NSAIDs (tolmetin, TLM; ketoprofen, KEP; naproxen, NAP; flurbiprofen, FLB; diclofenac, DIC; indomethacin, INM; ibuprofen, IBP; mefenamic acid, MFA; tolfenamic acid, TFA) in human urine samples. Under the optimized conditions, the method exhibited satisfactory recoveries ranging from 81.9% to 104.0% with relative standard deviation (RSD) values below 8.5%, good sensitivity (0.004-0.009 µg mL-1 limit of detection) and good linearity (coefficient of determination, R2 > 0.997, 0.01-0.2 µg mL-1 for NAP, 0.05-1.0 µg mL-1 for FLB, DIC, INM, MFA, TFA, 0.1-2.0 µg mL-1 for TLM, KEP, IBP). The hyperbranched MAX sorbent is superior to Oasis HLB and comparable to Oasis MAX in obtaining clean chromatographic profiles. Our results demonstrate the potential application of the hyperbranched MAX for complex sample analysis.