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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.

A novel portable smartphone-assisted colorimetric method was reported for the determination of Hg 2+ with good analytical performance. A Zr(IV)-based metal-organic framework functionalized with amino groups (NH 2 -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 Hg 2+ , the formation of gold amalgam proved possible to enhance peroxidase-like activity of the composite (AuNPs/NH 2 -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 Hg 2+ could be achieved. After the optimization of the experiment conditions, the average color intensity (I c ) resulting from RGB values was linear related to the concentration of Hg 2+ 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 Hg 2+ 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., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

The identification of an increasing number of aryl organophosphate esters (aryl-OPEs) in environmental samples has led to growing attention recently. Due to the potential adverse effects on human health and environment, development of new analytical methods for sensitive and selective determination of aryl-OPEs in complex matrices is urgently needed. Here, a novel analytical method for the identification and determination of trace amounts of aryl-OPEs in water samples is developed by using melamine sponge@heteropore covalent organic framework (MS@HCOF) based on vortex-assisted extraction (VAE) prior to UHPLC-MS/MS analysis. The MS@HCOF was rationally designed and synthesized through an in-situ growth strategy and exhibited superior selectivity toward aryl-OPEs compared with that of MS@single-pore COF (MS@SCOF) due to steric effect. A systematic optimization was conducted on important parameters of VAE, resulting in the successful extraction of nine aryl-OPEs in just 6 min. Under optimized conditions, the limits of detection (S/N = 3) and quantification (S/N = 10) were within the ranges of 0.001-0.027 and 0.005-0.091 ng/L for nine aryl-OPEs, respectively. The validated method was proven applicable to real water samples, i.e., the recoveries were 65.3-119.5 % for seawater, 59.4-112.9 % for effluent, and 76.0-117.4 % for tap water. Furthermore, the adsorption mechanisms were explored through density functional theory (DFT) calculations. DFT results revealed that a notable selective enrichment capacity of MS@HCOF towards aryl-OPEs stems from π-π conjugation and hydrogen bonding. The established method benefits from the advantages of high selectivity and sensitivity for the ultra-trace determination of aryl-OPEs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

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 H 2 O 2 in situ. Subsequently, PMOF(Fe) catalyzes H 2 O 2 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.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

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., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

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 (HD 50  = 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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

To discover effective analgesics, we summarize the synthesis, optimization, and pharmacological anti-nociceptive effects of a novel series of benzoxazole derivatives targeting H 3 receptor (H 3 R). The new benzoxazoles were assayed in vitro for histamine H 3 R and H 1 R binding affinity. The best compound 8d (2-methyl-6-(3-(4-methylpiperazin-1-yl)propoxy)benzo[d]oxazole) exhibited high affinity for H 3 R (K i  = 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, ED 50  = 6.0 mg/kg; Phase II, ED 50  = 7.8 mg/kg) and CCI-induced neuropathic pain (chronic constriction injury, ED 50  = 15.6 mg/kg). Furthermore, compound 8d showed an excellent safety profile in acute toxicity test (LD 50  > 2000 mg/kg) with a therapeutic index (TI = LD 50 /ED 50 ) > 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., (Copyright © 2022 Elsevier Inc. All rights reserved.)

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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 ED 25 = [4.41 (3.13-5.82)] mg/kg, theoretical ED 25 = [8.50 (6.62-10.32)] mg/kg; MEL-PGB, experimental ED 25 = [3.96 (2.62-5.46)] mg/kg, theoretical ED 25 = [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.

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.

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%., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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 (S QP-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 S QP-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 S QP-PEI also demonstrated excellent reusability, which shows the potential of S QP-PEI for real applications., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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.

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 m 2 /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.

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.

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.

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 (S BET ), 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 S BET , 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, R 2 > 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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A molecularly imprinted polymer (MIP) for highly selective solid-phase extraction (SPE) of bisphenol A (BPA) was prepared using phenolphthalein (PP) as the novel dummy template by bulk polymerization. A particle diameter distribution of 40⁻60 μm, a specific surface area of 359.8 m²·g -1 , and a total pore volume of 0.730 cm³·g -1 for the prepared PP-imprinted polymer (PPMIP) were obtained. Good selectivity and specific adsorption capacity for BPA of the prepared PPMIP were also demonstrated by the chromatographic evaluation and sorption experiments. The PPMIP as a SPE sorbent was evaluated for the selective extraction and clean-up of BPA from complex biological, environmental, and food samples. Meanwhile, an accurate and sensitive analytical method based on the PPMIP-SPE purification procedure coupled with high performance liquid chromatography-diode array detector (HPLC-DAD) detection has been successfully developed for the rapid determination of BPA from these samples, with detection limits of 1.3 ng·mL -1 for bovine serum and milk, 2.6 ng·mL -1 for human urine and edible oil, 5.2 ng·mL -1 for soybean sauce, and 1.3 ng·g -1 for sediment. The BPA recoveries at two different spiking levels were in the range of 82.1⁻106.9%, with relative standard deviation (RSD) values below 7.7%.

A mesoporous silica Santa Barbara Amorphous-15 (SBA-15) has been first functionalized with 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (a silane with three amines) and then reacted with an excess of phenyl glycidyl ether to generate a mixed-mode anion-exchanger containing both anion-exchange (three amines) and reversed-phase (multiple ether-linked phenyls) functionalities in a single branched ligand. The resulting material has been characterized by scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier-transform infrared spectroscopy, and elemental analysis. The results obtained indicated a BET specific surface area (S BET ) of 362.5m 2 g -1 , a pore volume of 0.70cm 3 g -1 with a narrow pore size distribution centered at 6.6nm, and carbon and nitrogen contents of 28.30% and 2.84%, respectively. The dimensions of these particles (∼5μm diameter, ∼60μm length), their large surface areas, their high-density functionalities and anion-exchange mixed-mode characteristics make them very attractive for highly effective solid phase extraction (SPE) of acidic nonsteroidal anti-inflammatory drugs (NSAIDs). The important parameters on extraction efficiency including sample pH, breakthrough volume, type and volume of eluent were optimized. A simple and sensitive analytical method based on mixed-mode SPE coupled to high-performance liquid chromatography with ultraviolet detection (HPLC-UV) was developed and successfully applied to the analysis of four NSAIDs (ketoprofen, naproxen, diclofenac, and ibuprofen) in spiked real water samples with satisfactory recoveries (80.6-110.9%) and repeatability (relative standard deviation <11.3%, n=3). The limit of detections of four NSAIDs were 0.006-0.070μgL -1 for tap water, and 0.014-0.16μgL -1 for river water and wastewater, with the enrichment factors of 806-1109-fold., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The present work represents a simple and effective preparation of a novel mixed-mode anion-exchange (MAX) sorbent based on porous poly[2-(diethylamino)ethyl methacrylate-divinylbenzene] (poly(DEAEMA-DVB)) spherical particles synthesized by one-step Pickering emulsion polymerization. The poly(DEAEMA-DVB) particles were quaternized with 1,4-butanediol diglycidyl ether (BDDE) followed by triethylamine (TEA) via epoxy-amine reaction to offer strong anion exchange properties. The synthesized MAX sorbent was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, nitrogen adsorption-desorption measurements and elemental analysis. The MAX sorbent possessed regular spherical shape and narrow diameter distribution (15-35μm), a high IEC of 0.54meq/g, with carbon and nitrogen contents of 80.3% and 1.62%, respectively. Compared to poly(DEAEMA-DVB), the MAX sorbent exhibited decreased S BET (390.5 vs. 515.3m 2 g -1 ), pore volume (0.74 vs. 0.85cm 3 g -1 ) and pore size (16.8 vs. 17.3nm). Moreover, changes of N content for producing the MAX sorbent reveal a successful two-step quaternization, which can be highly related to such a high IEC. Finally, the MAX sorbent was successfully evaluated for selective isolation and purification of some selected acidic pharmaceuticals (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBP) from neutral (hydrocortisone, HYC), basic (carbamazepine, CAZ; amitriptyline, AMT) pharmaceuticals and other interferences in water samples using solid phase extraction (SPE). An efficient analytical method based on the MAX-based mixed-mode SPE coupled with HPLC-UV was developed for highly selective extraction and cleanup of acidic KEP, NAP and IBP in spiked wastewater samples. The developed method exhibited good sensitivity (0.009-0.085μgL -1 limit of detection), satisfactory recoveries (82.1%-105.5%) and repeatabilities (relative standard deviation < 7.9%, n=3)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The dummy molecularly imprinted polymers were prepared by Pickering emulsion polymerization. 4,4'-(1-Phenylethylidene) bisphenol was selected as the dummy template to avoid the leakage of the target bisphenols. The microsphere particles were characterized by scanning electron microscopy and nitrogen adsorption-desorption measurements, demonstrating that the regular-shaped and medium-sized particles (40-70 μm) were obtained with a specific surface area of 355.759 m(2) /g and a total pore volume of 0.561 cm(3) /g. The molecular imprinting properties of the particles were evaluated by static adsorption and chromatographic evaluation experiments. The association constant and maximum adsorption amount of bisphenol A were 0.115 mmol/L and 3.327 μmol/g using Scatchard analysis. The microsphere particles were then used as a solid-phase extraction sorbent for selective extraction of seven bisphenols. The method of dummy molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography and diode array detection was successfully established for the extraction and determination of seven bisphenols from environmental sediment samples with method detection limits of 0.6-1.1 ng/g. Good recoveries (75.5-105.2%) for sediment samples at two spiking levels (500 and 250 ng/g) and reproducibility (RSDs < 7.7%, n = 3) were obtained., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This work reports the preparation of molecularly imprinted polymer particles for the selective extraction and determination of four benzophenones from aqueous media. The polymer was prepared by using 4-vinylpridine as functional monomer, ethylene glycol dimethacrylate as cross-linker, acetonitrile as porogenic solvent and 2,2',4,4'-tetrehydroxybenzophenone as template. Good specific adsorption capacity (Qmax = 27.90 μmol/g) for 2,2',4,4'-tetrehydroxybenzophenone was obtained in the sorption experiment and good class selectivity for 2,2',4,4'-tetrehydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dehydroxy-4,4'-dimethoxybenzophenone was demonstrated by the chromatographic evaluation experiment. Factors affecting the extraction efficiency of the molecularly imprinted solid-phase extraction procedure were investigated systematically. An accurate and sensitive analytical method based on the molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography and diode array detection has been successfully developed for the simultaneous determination of four benzophenones from tap water and river water with method detection limits of 0.25-0.72 ng/mL. The recoveries of benzophenones for water samples at two spiking levels (500 and 5000 ng/mL for each benzophenone) were in the range of 86.9-103.3% with relative standard deviations (n = 3) below 9.2%., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The bisphenol A (BPA) imprinted polymer microspheres were prepared by simple Pickering emulsion polymerization. Compared to traditional bulk polymerization, both high yields of polymer and good control of particle sizes were achieved. The characterization results of scanning electron microscopy and nitrogen adsorption-desorption measurements showed that the obtained molecularly imprinted polymer microsphere (MIPMS) particles possessed regular spherical shape, narrow diameter distribution (30-60 μm), a specific surface area (S(BET)) of 281.26 m(2) g(-1) and a total pore volume (V(t)) of 0.459 cm(3) g(-1). Good specific adsorption capacity for BPA was obtained in the sorption experiment and good class selectivity for BPA and its seven structural analogs (bisphenol F, bisphenol B, bisphenol E, bisphenol AF, bisphenol S, bisphenol AP and bisphenol Z) was demonstrated by the chromatographic evaluation experiment. The MIPMS as solid-phase extraction (SPE) packing material was then evaluated for extraction and clean-up of these bisphenols (BPs) from human urine samples. An accurate and sensitive analytical method based on the MIPMS-SPE coupled with HPLC-DAD has been successfully established for simultaneous determination of eight BPs from human urine samples with detection limits of 1.2-2.2 ng mL(-1). The recoveries of BPs for urine samples at two spiking levels (100 and 500 ng mL(-1) for each BP) were in the range of 81.3-106.7% with RSD values below 8.3%., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A new dendrimer-functionalized mesoporous silica material based on large-pore 3D cubic Korea Advanced Institute of Science and Technology-6 (KIT-6) was synthesized by the growing of dendritic branches inside the mesopores of aminopropyl functionalized KIT-6. Detailed physical characterizations using transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier transform infrared (FTIR) spectroscopy, and elemental analysis reveal that the multifunctional dendrimers have been grown successfully within the confined spaces of mesopores. Although the 3D ordered mesoporous architecture of KIT-6 was well preserved, there was a significant and continuous decrease in pore size, specific surface area (SBET) and pore volume when increasing dendrimer generation up to six. In order to get a compromise between the SBET, pore size and density of functionalities, the dendrimer-functionalized KIT-6 (DF-KIT-6) for generation 2 (SBET, 314.2 m(2) g(-1); pore size, 7.9 nm; carbon and nitrogen contents, 19.80% and 1.92%) was selected for solid phase extraction (SPE) applications. The DF-KIT-6 was then evaluated as a reversed-phase/anion-exchange mixed-mode sorbent for extraction of the selected acidic drugs (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBU), since the dendrimers contained both hydrocarbonaceous and amine functionalities. The effective parameters on extraction efficiency such as sample pH and volume, type and volume of eluent and wash solvents were optimized. Under the optimized experimental conditions, the DF-KIT-6 based SPE coupled with HPLC-UV method demonstrated good sensitivity (0.4-4.6 ng mL(-1) detection of limits) and linearity (R(2)>0.990 for 10-2000 ng mL(-1) of KEP and IBU, and 1-200 ng mL(-1) of NAP). The potential use of DF-KIT-6 sorbent for preconcentration and cleanup of acid drugs in human urine samples was also demonstrated. Satisfactory recoveries at two spiking levels (30 and 300 ng mL(-1) for KEP and IBU, 3 and 30 ng mL(-1) for NAP) were obtained in the range of 85.7-113.9% with RSD values below 9.3% (n=3)., (Copyright © 2015 Elsevier B.V. All rights reserved.)