Magnetic targeting and pH-microwave dual responsive Janus mesoporous silica nanoparticles for drug encapsulation and delivery.

In this paper, a new Janus-structured nano drug delivery carrier Fe3O4@TiO2&mSiO2 was designed and synthesized, which consisted of a spherical head and a closely connected rod. The head was a nanocomposite of core/shell structure with magnetic spinel ferric tetraoxide core and anatase titanium dioxide shell (Fe3O4@TiO2), and the rod was ordered mesoporous silica (mSiO2). The nanocarriers showed excellent magnetic targeting capability (saturation magnetization, 25.18 emu g-1). The core/shell heads endowed the carriers with fine microwave responsiveness. The pore volume of mesoporous nanocarriers was 0.101 cm3 g-1, and the specific surface area was 489.0 m2 g-1. Anticancer drug doxorubicin could be loaded in the mesoporous of the carriers to form Fe3O4@TiO2&mSiO2-DOX. The drug loading capacity was 10.4%. Fe3O4@TiO2&mSiO2-DOX exhibited acid-sensitive and microwavesensitive release properties along with good bio-compatibility. Fe3O4@TiO2&mSiO2 Janus nanoparticles are expected to be ideal drug carriers. .

Fabrication of imidazoline-linked cationic covalent triazine framework for enrichment of environmental estrogens.

Imidazoline-linked cationic covalent triazine framework (IM-iCTF) was facilely prepared through the Debus-Radziszewski reaction, involving 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline, formaldehyde and methylglyoxal. The IM-iCTF was applied as a sorbent for cartridge solid-phase extraction (SPE). It provided good adsorption performance for estrogen and estrogen mimics including bisphenol F, bisphenol A, 7ß-estradiol, bisphenol B and estrone. The adsorption isotherm, adsorption kinetic model, thermodynamic calculations and adsorption mechanism were investigated to reveal the adsorption behavior. The IM-iCTF was employed for the extraction of the estrogens and estrogen mimics from water, fish and shrimp (fish and shrimp samples were extracted with acetonitrile before the SPE). The analytes were then determined by high-performance liquid chromatography with diode array detection. The limits of detection were 0.008-0.05 ng mL-1 for water, 0.015-0.11 µg g-1 for fish, and 0.012-0.10 µg g-1 for shrimp samples. This research not only offers a new approach to construct cationic covalent triazine framework, but also provides a reliable strategy for the adsorption/enrichment trace level of organic pollutants.

Post-synthetic modification of covalent organic framework for efficient adsorption of organochlorine pesticides from cattle's milk.

Analysis of organochlorine pesticides (OCPs) residues in milk faces a significant challenge. Herein, a sea urchin structured covalent organic framework bearing boric acid groups named COF-B(OH)2 was synthesized and applied as a coating material for solid-phase microextraction (SPME) of the OCPs in cattle's milk. Its performance was superior to that of three commonly used commercial SPME fibers, which could be due to the coexistence of hydrogen bonding, halogen bonding, π-stacking and electrostatic interactions. Besides, the fiber coating displayed good stability and reusability. After optimization, a COF-B(OH)2 based SPME coupled with gas chromatography-electron capture detection was established for the sensitive detection of the OCPs from milk samples. The limits of detection (S/N = 3) were between 0.04 and 1.00 µg kg-1. Satisfactory accuracy was achieved with the method recoveries in the range of 87.5 % to 112.5 %. These results manifest the feasibility of the COF-B(OH)2 coated fiber for the enrichment of the trace OCPs from milk samples.

Fluorine-functionalized covalent organic framework as efficient solid phase extraction sorbent for adsorption of aflatoxins in nuts.

In this study, a new fluorine-functionalized covalent organic framework (F-COF) was designed and fabricated by the direct polycondensation of tris(4-aminophenyl)amine and 2,3,5,6-tetra-fluoroterephthaldehyde for the first time. F-COF exhibited a remarkably enhanced adsorption capability compared with that of the fluorine-free COF. The favorable adsorption of aflatoxins was attributed to multiple interactions including pseudo hydrogen bond, F-O, π-π, F-π interactions and hydrophobic interactions between F-COF and aflatoxins. By coupling F-COF based solid phase extraction with high-performance liquid chromatography equipped with fluorescence detector, a rapid and sensitive method for determining aflatoxins (aflatoxin B1, B2, G1 and G2) in nuts (peanuts and pistachios) was established. Under optimal conditions (35 mg F-COF, 100 mL sample solution, 3 mL min-1 as sample loading rate, pH<7, 0.2 mL acetonitrile as desorption solvent), the limits of detection for aflatoxins were 0.02-0.30 ng g-1. The linear range was 0.08-16.0 ng g-1 and the recoveries of the F-COF-based method were 83.5-114 % with relative standard deviations less than 8.0 %.

Endogenous NO-release multi-responsive hollow mesoporous silica nanoparticles for drug encapsulation and delivery.

Novel multi-responsive drug delivery vehicles (CDs/PNVCL@HMSNs) were prepared by grafting amino-terminated poly (N-vinyl caprolactam) (PNVCL-NH2) and amino-rich carbon dots (CDs) on the surface of aldehyde-functionalized HMSNs (HMSNs-CHO) via Schiff base reaction. The CDs were prepared from L-arginine and their surfaces were rich in guanidine. Doxorubicin (DOX) was loaded into the nanoparticles to form drug loaded vehicles (CDs/PNVCL@HMSNs-DOX) and the drug loading efficiency was 58.38%. The drug release behaviors of CDs/PNVCL@HMSNs-DOX showed temperature and pH responsiveness due to the poly (N-vinyl caprolactam) (PNVCL) and Schiff base bond. The high concentration of NO released in high concentration H2O2 of tumor site could induce tumor cells apoptosis. The multi-responsive CDs/PNVCL@HMSNs are intriguing drug carriers, which combine drug delivery and NO release in one.

Preparation of magnetic hyper-crosslinked polymer for high efficient preconcentration of four aflatoxins in rice and sorghum samples.

Aflatoxins have carcinogenic effect on human health, developing effective adsorbents for their enrichment and detection is particularly required. A magnetic hyper-crosslinked polymer (MHCP-TPE) was prepared and used as a magnetic sorbent to adsorb and isolate aflatoxins from rice and sorghum samples prior to high performance liquid chromatography-fluorescence detection. MHCP-TPE exhibited good magnetic separation ability and reusability, with fast adsorption kinetics and quite good adsorption efficiency for the aflatoxins. At optimized conditions, a sensitive and reliable method was established for the determination of four aflatoxins (B1, B2, G1 and G2) in rice and sorghum samples. The limits of detection were 0.003-0.075 ng g-1 and 0.01-0.25 ng g-1 for rice and sorghum, respectively. Good method recoveries ranging from 83.0 % to 117 % were obtained, with relative standard deviations less than 8.0 %. This method offered a superior alternative to determine trace level of aflatoxins in cereal foods. MHCP-TPE holds great potential in separation science.

Aryl ketones-derived porous organic polymer for enrichment and sensitive detection of phenylurea herbicides in water, tea drink and mushroom samples.

Three aryl ketones-derived porous organic polymers (ATP-POPM, ATP-POPP and ATP-POPO) were fabricated through the aldol condensation reaction of acetylated triphenylsilane precursor (ATP) with different aromatic aldehydes for the first time. The ATP-POPM exhibited superior extraction capacity toward phenylurea herbicides (PUHs). A sensitive method for the simultaneous determination of six PUHs in water, tea drink and mushroom samples was developed with ATP-POPM as solid phase extraction adsorbent prior to high performance liquid chromatography ultraviolet detection. Under the optimized conditions, the linear response of PUHs was 0.09-80.0 ng mL-1 for water, 0.18-100.0 ng mL-1 for tea drinks and 4.50-200.0 ng g -1 for mushroom samples. The detection limits (S/N=3) of the method were 0.03-0.10 ng mL-1, 0.06-0.18 ng mL-1, 1.50-4.50 ng g -1 for water, tea drink and mushroom, respectively. The method recoveries for spiked samples were in the range of 80.7%-116.0%, with relative standard deviations less than 10.3%. The results proved that the established method was sensitive and suitable to detect PUHs with acceptable accuracy and precision. This work provided a powerful tool to synthesize promising adsorbent by aldol condensation reaction for detecting six PUHs simultaneously in real samples.

Simvastatin Inhibits Endometrial Cancer Malignant Behaviors by Suppressing RAS/Mitogen-Activated Protein Kinase (MAPK) Pathway-Mediated Reactive Oxygen Species (ROS) and Ferroptosis.

This paper was designed to explore the function of simvastatin as a chemotherapeutic drug on the endometrial cancer (EC) cell proliferation, invasion, and ferroptosis. Firstly, a number of in vitro experiments were conducted to determine the impact of different treatments of simvastatin on the Ishikawa cell invasion, proliferation, and colony formation. The concentration of DCFH-DA-labeled reactive oxygen species (ROS) in cells was assessed by flow cytometry. Enzyme-linked immunosorbent assay (ELISA) was performed to examine the intracellular contents of Fe2+, malondialdehyde (MDA), and glutathione (GSH). Additionally, Western blot was utilized to measure the expression level of RAS/mitogen-activated protein kinase (MAPK)-related proteins and ferroptosis-related proteins in cells. The results showed that simvastatin at 10 µM and 15 µM apparently suppressed the proliferation of Ishikawa cells, colony formation, and invasion ability of Ishikawa cells, and upregulated the level of MDA and ROS, but downregulated the level of GSH. Besides, 10 µM and 15 µM of simvastatin promoted cell ferroptosis (up-regulation of Fe2+ and TRF 1 protein level; down-regulation of SLC7A11 and FPN protein level) and lowered the RAS, p-MEK, and ERK protein level. Furthermore, experiments also revealed that the inhibitory effects of simvastatin on Ishikawa cell proliferation, colony formation, and invasion, as well as the promoting effects on oxidation and ferroptosis were reversed. All in all, simvastatin reduces the RAS/MAPK signaling pathway to inhibit Ishikawa cell proliferation, colony formation, and invasion, and promote cell oxidation and ferroptosis. This paper demonstrates the potential of simvastatin as a new anticancer drug for EC.

Amino-functionalized hypercrosslinked polymer as sorbent for effective extraction of nitroimidazoles from water, drink and honey samples.

The three hypercrosslinked polymers (HCP) materials, designated as OPD-HCP, MPD-HCP and PPD-HCP, were synthesized by using o-phenylenediamine (OPD), m-phenylenediamine (MPD) and p-phenylenediamine (PPD) as monomers. They were characterized by infrared spectroscopy, powder X-ray diffraction, nitrogen sorption isotherms, and scanning electron microscopy. Then, the HCPs were explored as solid-phase extraction (SPE) adsorbent for the extraction of five nitroimidazoles (NDZs) (metronidazole, ronidazole, secnidazole, dimetridazole and ornidazole). Among the three HCPs, the MPD-HCP has the best adsorption performance for the NDZs. With the help of high-performance liquid chromatography with ultraviolet detection (HPLC-UV), good linear response range (0.07-40.0 ng mL-1), high method recovery (86.8%-113.3%), low limits of detection (0.02-0.15 ng mL-1) and good precision with the relative standard deviations of less than 8.1% were achieved for the determination of the NDZs in water samples. The effective determination of the NDZs in peach juice, honey tea, and honey samples were also realized by the developed method with satisfactory results. Based on both the experimental results and density functional theory calculation, the adsorption mechanism can be attributed to multiple interactions between the MPD-HCP and the NDZs, including hydrogen bonding, hydrophilic, and electrostatic interactions. The method provides a new alternative of choice for the determination of some NDZs in real samples.

Poly(lactic acid)/Poly(butylene succinate) (PLA/PBS) Layered Composite Gas Barrier Membranes by Anisotropic Janus Nanosheets Compartibilizers.

Poly(lactic acid) (PLA), one of the most promising biodegradable polymer products, has achieved wide applications for its relatively good mechanical properties and moderate degradability. Here we report an environment-friendly filler, the organic-inorganic composite Janus nanosheets (PLA/PBS JNs), which can jam at the interface of the PLA/PBS blend with a low threshold as the compatibilizer and can simultaneously toughen the composites and improve the gas barrier performance due to better interfacial interaction and tortuous path effect. With 0.3 wt % of PLA/PBS JNs added, the tensile strength and elongation at break of the PLA/PBS blend can be improved by 37% and 224%, respectively. After a further hot-pressing process, the barrier performance of the PLA/PBS composite membranes can be significantly enhanced since PLA, PLA/PBS JNs, and PBS are arranged in a nearly lamellar structure with oxygen permeability of 0.63 × 10-15 cm3 cm·cm-2 s-1 Pa-1 with only 0.5 wt % of PLA/PBS JNs.

Novel N-riched covalent organic framework for solid-phase microextraction of organochlorine pesticides in vegetable and fruit samples.

A covalent organic framework named N-COF was successfully constructed by the aldehyde-amine condensation reaction between 2,4,6-tris (4-formyl phenoxy)-1,3,5-triazine and 1,3-bis(4-aminophenyl) urea for the first time. The prepared N-COF exhibited good stability and high affinity to organochlorine pesticides (OCPs). Thus, the N-COF was served as solid phase microextraction fiber coating for extraction of six OCPs from vegetables and fruits including romaine lettuce, cabbage, Chinese cabbage, apple, pear and peach, followed by quantitation with gas chromatography-electron capture detector (GC-ECD). Under the optimal conditions, good linearities for the OCPs existed in the ranges from 0.1 to 1.0 ng g-1 to 100.0 ng g-1 for the samples. The low limits of detection for analytes were obtained in the range of 0.03-0.3 ng g-1. The present work can offer new alternative for sensitive analysis of trace level of OCPs in vegetables and fruits.

Endogenous NO-releasing Carbon Nanodots for Tumor-specific Gas Therapy.

Carbon nanodots based on L-arginine (L-Arg) were developed for enhanced nitric oxide (NO) gas therapy for cancer. The L-Arg-based carbon nanodots (Arg-dots) produced high levels of NO in the tumor environment rich in endogenous H2O2. In vitro cell experiments revealed that the Arg-dots could kill tumor cells (including human breast cancer cell line MCF-7, female gastric cancer cell line BGC-823, male lung cancer cell line A549, and female leukemic cell line K562) but did not affect the activity of normal cells (human normal lung epithelial cell line BEAS-2B). The Arg-dots produced twice the amount of NO for an equivalent amount of L-Arg. Theoretical calculations showed that the carbonization structure of the Arg-dots promoted significantly more electrons toward the guanidinium groups of L-Arg and boosted the adsorption of H2O2 molecules. In vitro and in vivo investigations confirmed that the Arg-dots reduced the multidrug resistance (MDR) effect of the tumor cells (MCF-7/ADR cells) and produced a combined antitumor efficacy with traditional chemotherapeutic drugs (adriamycin [ADR]). The fluorescence property (quantum yield, 6.88%) allows the Arg-dots to be used as a suitable fluorescent probe for fluorescence imaging of tumor cells. The ultra-small size of the Arg-dots (diameter: ca. 2.5 nm) enables them not only to penetrate deep tumors and provide enhanced antitumor activity but also to be removed through kidney filtration and have a renal clearance property. STATEMENT OF SIGNIFICANCE: Nitric oxide (NO), which serves as a biological messenger, can be used in gas therapy for cancer. The development of a safe and efficient NO cancer therapy is, however, challenging because of the low NO release amount and poor tumor specificity of most NO donors. Many efforts have been made to overcome these drawbacks, but solving both these limitations through a single approach has been seldom achieved. In the present work, carbon nanodots (Arg-dots) from L-arginine were used for gas therapy of cancer. The Arg-dots produced NO in the H2O2-rich tumor environment. Theoretical calculations were consistent with the mechanism of enhanced NO release amount. The Arg-dots also reduced the multidrug resistance effect in cancer chemotherapy. In vivo and in vitro toxicity assessments confirmed that the Arg-dots have excellent biosafety.

Synthesis of hypercrosslinked polymers for efficient solid-phase microextraction of polycyclic aromatic hydrocarbons and their derivatives followed by gas chromatography-mass spectrometry determination.

Three novel hypercrosslinked polymers (HCPs) were synthesized via Friedel-Crafts reaction employing 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene as alkylating agent, and triphenylbenzene, tetraphenylethylene and p-quaterphenyl as the aromatic units, respectively. The prepared HCPs were applied as solid-phase microextraction coatings for direct immersion extraction of polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and nitrated derivatives in environmental water samples. The key factors affecting the extraction efficiency including extraction time, extraction temperature, stirring rate, ionic strength and desorption conditions, were carefully studied. Coupled with gas chromatography mass spectrometry analysis, a new method for determining PAHs and their derivatives was developed. Under the optimized conditions, the limits of detection (S/N=3) and limits of quantitation (the lowest concentration for quantification) of the method were in the range of 2.5-25.0 and 7.5-75.0 ng L-1, respectively. The recoveries of spiked samples were in the range of 73.1-118.3% with relative standard deviations less than 13.0%. The developed method was applied for the simultaneous determination of nine PAHs and their derivatives in environmental water samples, showing good accuracy and reliability.

Dual-responsive mesoporous silica nanoparticles coated with carbon dots and polymers for drug encapsulation and delivery.

Aim: Smart mesoporous silica nanoparticles (MSNs) coated with carbon dots (CDs) and poly(N-vinylcaprolactam) (PNVCL) as a mixed shell (CDs/PNVCL polymer grafted MSNs) were prepared for pH-trigged anticancer drug release and real-time monitoring. Materials & methods: The amino-terminated PNVCL and amino-rich CDs were grafted onto the surface of aldehyde group functionalized MSNs through Schiff base reaction. Doxorubicin (DOX) was loaded into the prepared nanoparticles. Results: DOX could be quickly released in the tumor environment, leading to cell apoptosis. The linear fit between the percentage of released DOX and the fluorescence intensity of CDs indicated that the change in fluorescence intensity could be used to monitor drug release in real time. Conclusion: The as-prepared CDs/PNVCL polymer grafted MSNs are promising candidates for integrating controllable release and real-time monitoring in cancer treatment.

Graphene intercalated with carbon nanosphere: a novel solid-phase extraction sorbent for five carbamate pesticides.

Graphene-carbon nanosphere composite (G@CNS) was prepared via a simple hydrothermal method. The G@CNS nanocomposite was characterized by X-ray diffraction, scanning electron microscope, surface area, and porosity analysis. The G@CNS was applied as a new sorbent for solid-phase extraction of five carbamate pesticides (tsumacide, carbaryl, isoprocarb, bassa, diethofencarb) prior to quantitative determination by high-performance liquid chromatography with ultraviolet detection at 208 nm. Some experimental parameters including desorption conditions, sample pH, sample volume, and loading rate were studied carefully. Under the optimized condition, the method provided good linearity ranging from 0.3 to 100.0 ng mL-1 with low limits of detection of 0.10-0.20 ng mL-1 for grape juice, 0.10-0.30 ng mL-1 for blend fruit juice, and 0.10-0.20 ng mL-1 for water sample. Good method recoveries (80.2-110%) with relative standard deviations less than 7.2% and high enrichment factors (167-293) were achieved. Results demonstrated that this novel G@CNS can serve as a promising alternative sorbent for more applications. In this work, a graphene-carbon nanosphere (G@CNS) composite was synthesized via a simple hydrothermal method. Then, the G@CNS was served as a novel sorbent for solid-phase extraction of five carbamate pesticides (tsumacide, carbaryl, isoprocarb, bassa, diethofencarb) in juice and environmental water samples, followed by their quantitative analysis with high-performance liquid chromatography-ultraviolet detection.

Fluorescent carbon nanodots-based artificial tongue for determining and discriminating cigarettes.

Smoking can cause cigarette-related diseases and pose serious threat to human health. Its dangers can be effectively controlled by discriminating cigarettes and monitoring cigarette quality. Herein, a kind of artificial tongue technique based on the indicator displacement assay (IDA) was developed and applied to determine and discriminate cigarettes and their main ingredients (saccharides, organic acids and nicotine). This method was constructed using carbon nanodots (CDs) as a fluorescent indicator and various concentrations of silver ion (Ag+) as a fluorescent regulator. A cigarette extracting solution was prepared to interact with an artificial tongue and produce fluorescence fingerprints. Twenty-nine kinds of cigarettes can be well discriminated in terms of category (flue-cured cigarette, blended cigarette and cigar), brand, origin (domestic or foreign cigarettes) after processing and visualizing the response fingerprints. The artificial tongue fluorescent sensor array can sensitively detect nine kinds of tobacco-based chemical ingredients and discriminate them between different concentrations. The as-prepared fluorescent artificial tongue is a promising platform for monitoring cigarette quality and controlling the harmful effects of smoking because of its cheap material requirements, simple operation, and good performance.

Sensor array based on single carbon quantum dot for fluorometric differentiation of all natural amino acids.

A sensor array is described that consists of a carbon quantum dot (CQD) and metal ions, including Hg2+, Cu2+, Fe3+, Ag+, Cd2+, and Pb2+. The CQDs display blue fluorescence with excitation/emission maxima at 370/440 nm. It is shown that the array can be applied to the determination of all natural amino acids (NAAs). Metal ions can quench the fluorescence of the CQDs, while NAAs can take metal ions away or co-bind to the CQD@metal-ion complex, which enhances or depresses the fluorescence of the CQDs. Based on the differential fluorescence variation, the CQD@metal-ion@NAA array exhibits a unique pattern for NAAs. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were carried out to generate visualized datagrams for NAA discrimination. The design and construction of the sensor array is convenient and economical. The sensor array can distinguish NAAs at a concentration of as low as 30 µM, and can distinguish NAAs into acidic, neutral and basic NAAs. Semi-quantitative assay of alanine and threonine was also realized. Based on the low limit of detection and multi-NAA detection capability, the array can differentiate healthy cases from acute leukemia, chronic leukemia and lymphoma by analyzing the NAA status of serum samples. Graphical abstractSchematic representation of a fluorometric (FL) sensor array based on single CQD (carbon quantum dot) interacting with metal ions for differentiating all NAAs (natural amino acids) into acidic, neutral and basic NAAs (ANs, NNs and BNs) through PCA (principle component analysis).

Preparation of nickel-doped nanoporous carbon microspheres from metal-organic framework as a recyclable magnetic adsorbent for phthalate esters.

In this work, magnetic Ni doped nanoporous carbon (Ni-C) microspheres were prepared by directly calcinating Ni based metal-organic framework at 400 °C in nitrogen. The morphology and surface area of Ni-C microspheres were characterized by electron microscopy and N2 adsorption-desorption isotherms. The results demonstrated that Ni nanoparticles were wrapped by the carbon matrix, resulting in the Ni-C microspheres with a strong magnetic response. The Ni-C microspheres also showed high surface area and micro/meso-porous structure, which make them efficient and recyclable magnetic adsorbent. The Ni-C microspheres were employed for magnetic solid phase extraction of phthalate esters from juice and water samples before high performance liquid chromatographic analysis. The limits of detection (S/N = 3) of the method were 0.2-0.3 ng mL-1 for juice sample and 0.02-0.03 ng mL-1 for water sample. The recoveries of all analytes were between 90.0%-100.6%. The Ni-C microspheres showed a great deal of potential to be an adsorbent for enrichment of other organic pollutants in different samples.

Solid phase extraction of carbamate pesticides with porous organic polymer as adsorbent followed by high performance liquid chromatography-diode array detection.

A solid phase extraction (SPE) method with a porous organic polymer as adsorbent was established for the extraction of five carbamate pesticides (metolcarb, carbaryl, isoprocarb, bassa and diethofencarb) from milk, white wine and juice samples prior to high performance liquid chromatography-diode array detection. The main factors affecting the SPE were optimized, including sample volume, sample loading rate, sample solution pH, desorption conditions and cartridge reusability. Under the optimal conditions, a good linearity existed in the range from 1.0 to 320.0 ng mL-1 for milk and white wine samples and from 0.5 to 160.0 ng mL-1 for juice sample with the correlation coefficients between 0.9956 and 0.9998. The method recoveries of the carbamates were 82.0%-110.0%. The limits of detection were 0.12-0.40 ng mL-1 for milk and white wine samples, and 0.06-0.20 ng mL-1 for juice sample. The adsorption mechanism of the adsorbent was investigated by the extraction of different types of organic compounds (carbamates, benzoylurea insecticides, endocrine disrupting chemicals and polycyclic aromatic hydrocarbons) with the adsorbent. The results showed that the existence of the hydrogen-bonding between the adsorbent and the analytes is favorable for the adsorption and strong hydrophobicity seems to have an adverse effect.

Covalent Organic Framework as Fiber Coating for Solid-Phase Microextraction of Chlorophenols Followed by Quantification with Gas Chromatography-Mass Spectrometry.

Headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry was adopted for the simultaneous determination of seven chlorophenols (CPs) from honey and canned-yellow-peach samples. A covalent organic framework made of 1,3,5-triformylphloroglucinol (Tp) and benzidine (BD) was used as the SPME fiber coating to preconcentrate the acetylation derivatives of the CPs. The main experimental parameters including derivatization conditions, extraction temperature and time, headspace volume, salt concentration, and desorption temperature were investigated. The fiber showed a high extraction capability for the CPs. The limits of detection (LODs) for the analytes were 0.3-0.7 µg kg-1 for honey and 0.8-1.8 µg kg-1 for canned-yellow-peach samples, suggesting good sensitivity for the method. The response linearity was 2.4-250 µg kg-1 for 2-CP and 3,4-CP and 1.0-150 µg kg-1 for the other remaining analytes in the honey samples. For the canned-yellow-peach samples, the response linearity was 6.0-300 µg kg-1 for 2-CP and 3,4-CP and 3.0-200 µg kg-1 for the others. The correlation coefficients were higher than 0.9919. Good repeatability (RSD < 11.9%) for the method and high recoveries (70.2-113%) of the analytes were observed under the optimal conditions. The established method was satisfactorily applied for the analysis of honey and canned-yellow-peach samples.