In-syringe Solid-phase Extraction Research Articles

A porous composite sorbent incorporating a metal organic framework and zinc oxide in cryogel to extract carbamate pesticides

A composite sorbent was designed and fabricated by incorporating the Materials of Institute Lavoisier (MIL-101) and zinc oxide (ZnO) into polyvinyl alcohol (PVA) cryogel. The composite sorbent was produced to extract carbamates (carbofuran, carbaryl, isoprocarb and diethofencarb) by in-syringe solid phase extraction (SPE). MIL-101 and ZnO enhanced the adsorption of the carbamates by creating π-π stacking and hydrogen bonding, while porous PVA cryogel acted as a solid support which helped to reduce backpressure in the system. The extraction of the target carbamates was optimized by varying the amount of MIL-101 and ZnO used in the sorbent fabrication, desorption conditions, sample pH, ionic strength, sample flow rate and sample volume. The extracted target carbamates were quantitatively determined using high performance liquid chromatography technique. The developed method exhibited linearity from 1.0 to 150.0 μgL−1 for all four target carbamate pesticides with a limit of detection 0.3 µg/L. The method identified carbamates in fruit juice and white wine, obtaining recoveries from 78.1 to 108.2 % and the relative standard deviation (RSD) lower than 6.3 %. The developed composite sorbent showed good accuracy, is simple to fabricate, works rapidly and can be used for 17 extraction-regeneration cycles.

Natural kapok fiber as a green and efficient adsorbent for in-syringe solid-phase extraction in the determination of antidepressants in biofluids

Effective antidepressant monitoring is crucial for safe treatment, with liquid chromatography being the primary detection method. Due to the complexity of biofluids, meticulous sample preparation is vital to remove interferences and concentrate analytes. In this study, a novel solid-phase extraction method utilizing unprocessed kapok fiber (KF) as an eco-friendly and efficient sorbent, ingeniously incorporated within an in-syringe device for the extraction of antidepressants from biofluids was introduced. The extraction process displayed several advantages, including simplicity and rapidity (less than 3 min with minimal manual intervention), as well as the potential for automation, which represents significant advancements in sample preparation techniques. The method demonstrated excellent analytical performance when coupled with high-performance liquid chromatography-ultraviolet detection, achieving good linearity (R2 ≥ 0.991), excellent relative recovery (92.6–107.5 %), high precision in intraday and interday analyses (RSDs within 0.8–6.0 % and 1.2–7.9 %, respectively), and good sensitivity with limits of quantification between 5–10 ng/mL. Notably, given the use of a renewable and biodegradable material with KF, and a low-toxicity desorption solvent with ethanol, the developed method stands out for its environmental sustainability, aligning with green analytical chemistry principles. Its application to real biological samples validates its efficacy as a rapid and reliable tool for clinical and forensic monitoring of antidepressants. Moreover, the low cost of this method facilitated by the economical nature of KF and the reusability of syringes further enhances its practicability. This study presents a unique approach by employing natural and renewable KF as adsorbents, thereby eliminating the need for complex material synthesis and making a pioneering contribution to the field of analytical chemistry for drug analysis in complex matrices.

A hierarchically porous PEDOT embedded cryogel for in-syringe solid phase extraction of parabens in beverages

A hierarchically porous adsorbent was fabricated using polyethylene dioxythiophene (PEDOT) embedded in a polyvinyl alcohol cryogel. This adsorbent was designed for use in the in-syringe solid-phase extraction (IS-SPE) of parabens present in beverage samples. The creation of a hierarchical pore system was achieved through a reaction between a hydrochloric acid solution and calcium carbonate, strategically introduced during the cryogel synthesis within a needle hub. The porous structure of the cryogel allowed for efficient entrapment of adsorption materials, significantly increasing the number of available adsorption sites. Additionally, PEDOT was incorporated to enhance paraben adsorption through hydrophobic and π-π interactions. High-performance liquid chromatography was employed to quantify the extracted parabens. Under optimized conditions, the developed method exhibited detection limits ranging from 0.15 to 0.25 µg L–1 and quantification limits ranging from 0.50 to 1.0 µg L–1. The technique was successfully applied to assess parabens in various beverage samples, consistently obtaining extraction recoveries between 88.4% and 98.4%, and relative standard deviations (RSDs) below 6%. We conclude that the in-syringe extraction approach offers a straightforward and efficient method, while the composite adsorbent demonstrates ease of preparation and robust reproducibility, allowing for twelve extraction–desorption cycles.

Biochar/sodium alginate mixed matrix membrane as adsorbent for in-syringe solid-phase extraction towards trace nitroimidazoles in water samples prior to ultra-high-performance liquid chromatography-tandem mass spectrometry analysis.

In the present work, the herb (Poria cocos (Schw.) Wolf) residue, as an environmentally friendly and renewable biomass source, was converted into novel biochar. Biochar/sodium alginate mixed matrix membrane was fabricated. On this basis, a biochar/sodium alginate mixed matrix membrane-based in-syringe solid-phase extraction was developed combined with ultra-high performance liquid chromatography-tandem mass spectrometry to determine nitroimidazoles in water samples. The factors including times of exaction, type, and volume of elution solvent, and sample solution pH were thoroughly optimized. Then the correlation coefficient was 0.9995-0.9997. The limit of detection of four analytes was between 0.006 and 0.014ng/mL, and the recovery was between 79.02% and 99.1%. Consequently, the established method would provide a new perspective on monitoring nitroimidazoles in water samples.

Qualitative and quantitative determination of phenols and their metabolites in urine by in-syringe solid-phase extraction and LC–MS/MS analysis for evaluation of virgin olive oil metabolism

To know the bioavailability of virgin olive oil (VOO) phenols and its impact on health, it is necessary to determine the levels of phenols excreted in urine. We present here a novel strategy for in-syringe solid-phase extraction and analysis of the extract by liquid chromatography–tandem mass spectrometry (LC–MS/MS), using ammonium fluoride as ionization agent to enhance sensitivity. This approach allows avoiding additional steps such as solvent evaporation or analytes derivatization. The method can be used with a previous acid hydrolysis for quantitative determination of tyrosol and hydroxytyrosol to estimate metabolized phenols. We tested this application by analysis of a cohort of volunteers (n = 20) after a standardized intake of VOO. Additionally, the method can be used as such for metabolite profiling of phenolic derivatives in urine using LC–MS/MS in high-resolution data-independent acquisition (DIA). Information about the phenolic profile of the consumed VOO and the human metabolism is thus obtained. The proposed approach represents a simple and versatile tool for qualitative and quantitative characterization of VOO phenolic metabolism.

One-step fabrication of COF-coated melamine sponge for in-syringe solid-phase extraction of active ingredients from traditional Chinese medicine in serum samples.

In this study, a covalent organic framework (COF)-TpBD-supported melamine sponge (MS) was fabricated through a one-step hydrothermal method. The obtained monolithic column was then applied in in-syringe solid-phase extraction (IS-SPE) for the separation of three volatile ingredients from serum samples. Given credit for the superior adsorption capacity of the COF and the homogeneous microporous property of MS, the developed column exhibited satisfactory separation of the targets. And the dominating adsorption mechanism was the hydrophobic interaction forces between TpBD and targets and the high mass transfer efficiency provided by the large pore structure of MS. The results of dynamic adsorption showed that the MS@TpBD column displayed much better adsorption performance than blank MS and TpBD. And it has featured great reusability up to 5 cycles and obtained satisfied recovery values (87.9 ~ 110.3%) in serum samples. As a result of sample clean-up, this column offers low limit of detections (LODs) down to 0.014, 0.010, and 0.020μg/mL, respectively. In summary, we believe that this convenient separation column has prominent application promise in the fields of separating activity ingredients in biological samples.

Ferric iron loaded porphyrinic zirconium MOFs on corncob for the enhancement of diuretics extraction.

Herein, corncob waste was used as a scaffold for the fabrication of effective adsorbents. Porphyrinic zirconium metal-organic frameworks (MOFs) PCN-223 and PCN-224 constructed by different numbers of Zr6 cluster nodes were grown on the surface of the corncob. Fe (Ш) ions were implanted in the porphyrin ring by post-synthesis modification. The results showed that the extraction capacity of diuretics on PCN-224@corncob containing suitable pore size was larger than that of PCN-223@corncob. The adsorption of diuretics was further enhanced because of the electrostatic effect caused by implantation of Fe (Ш) ions. PCN-224-Fe@corncob was recyclable and selective for the extraction of furosemide (Fur) and bumetanide (Bum). Coupled in-syringe solid phase extraction (IS-SPE) with ultra-performance liquid chromatography (UPLC), an efficient, sensitive, and stable method was established. With a sensitivity between 0.6 and 1.0μg/L and a recovery between 83.2% and 119.2%, it is used for the analysis of trace amounts of Fur and Bum in weight loss products and environmental water. The functionalized corncob has potential application for the adsorption of diuretics, and the metal ions implantation in MOFs provides a promising strategy for enhancing extraction capacity.

Effective extraction of fluoroquinolones from water using facile modified plant fibers

In this study, ecofriendly and economic carboxy-terminated plant fibers (PFs) were used as adsorbents for the effective in-syringe solid phase extraction (IS-SPE) of fluoroquinolone (FQ) residues from water. Based on the thermal esterification and etherification reaction of cellulose hydroxy with citric acid (CA) and sodium chloroacetate in aqueous solutions, carboxy groups grafted onto cotton, cattail, and corncob fibers were fabricated. Compared with carboxy-terminated corncob and cotton, CA-modified cattail with more carboxy groups showed excellent adsorption capacity for FQs. The modified cattail fibers were reproducible and reusable with relative standard deviations of 3.2%–4.2% within 10 cycles of adsorption-desorption. A good extraction efficiency of 71.3%–80.9% was achieved after optimizing the extraction condition. Based on carboxylated cattail, IS-SPE coupled with ultra-performance liquid chromatography with a photodiode array detector was conducted to analyze FQs in environmental water samples. High sensitivity with limit of detections of 0.08–0.25 μg/L and good accuracy with recoveries of 83.8%–111.7% were obtained. Overall, the simple and environment-friendly modified waste PFs have potential applications in the effective extraction and detection of FQs in natural waters.

In-syringe solid phase extraction and in-syringe vortex-assisted solidified floating organic drop microextraction of Sb(III) and Sb(V) in rice wines with determination by graphite furnace atomic absorption spectrometry

ABSTRACT The current non-chromatographic speciation methods generally involve the conversion of different species by oxidation/reduction reactions, which may cause inherent problems such as contamination risk, time consumption and complex operations. In this work, in-syringe solid phase extraction (IS-SPE) was combined with in-syringe vortex-assisted solidified floating organic drop microextraction (IS-VA-SFODME) for the detection of Sb(V) and Sb(III) in rice wines by graphite furnace atomic absorption spectrometry. Firstly, IS-SPE involved the use of ZnFe2O4 nanotubes as the sorbent for the isolation and enrichment of Sb(V) and removal of the matrix components such as ethanol, pigment, sugars and carbohydrates. Then, IS-VA-SFODME was used for enriching Sb(III) in the original sample solution after IS-SPE. This technique exhibited good anti-interference ability and high enrichment efficiency without tedious pre-oxidation/pre-reduction and centrifugation/filtration operations, which may cause the contamination of samples. Under the selected conditions, the detection limits were 4.5 ng L−1 and 3.2 ng L−1 for Sb(III) and Sb(V) with relative standard deviations of 7.3% and 5.1%, respectively. This procedure was used with satisfactory results for the detection of Sb(III) and Sb(V) in rice wine samples and a certified reference material of water sample. Recoveries of spiked experiments ranged from 91.0 to 107%.

Growth of MOF@COF on corncob as effective adsorbent for enhancing adsorption of sulfonamides and its mechanism

MOF@COF composite was fabricated for greater adsorption capacity through the utilization of corncob, which is a natural, sustainable, and cellulose-rich resource. An in-situ growth strategy was implemented to graft UiO-66-NH2 on carboxyl-terminal corncob induced by the thermal esterification of critic acid. Subsequently, corncob@UiO-66-NH2@TpBD was constructed through the Schiff base reaction between 2,4,6-triformylphloroglucinol (Tp) and UiO-66-NH2 as well as benzidine (BD). The ratio of UiO-66-NH2 and TpBD was optimized to be 5:3 for enhancing adsorption capacity. Based on the π-π, hydrogen bonding, and -SO2-Zr-O- coordination effect, sulphonamides (SAs) were chosen to investigate the adsorption capacity of adsorbent using an in-syringe solid phase extraction (IS-SPE) method. The binding energy calculated using density functional theory (DFT) reached −37.45 Kcal/mol, which indicated the strong interactions between SAs and corncob@UiO-66-NH2@TpBD. Combined with ultra-performance liquid chromatography (UPLC), a high sensitivity was obtained with low detection of 0.10 μg/L. The prepared corncob@UiO-66-NH2@TpBD exhibited good reproducibility within relative standard deviations (RSDs) 3.1%-3.4% in intra-batch and 4.3%-8.4% in inter-batch. Moreover, the extraction capacity of adsorbent was not decreased in 20 recycles adsorption–desorption within RSDs 3.8%-8.5%. With features of permanent porosity, multiple active sites, and good renewability, corncob@UiO-66-NH2@TpBD shows great potential towards industrial applications in the field of adsorption.

Self-assembling covalent organic framework functionalized poly (styrene-divinyl benzene-glycidylmethacrylate) composite for the rapid extraction of non-steroidal anti-inflammatory drugs in wastewater

The growing use of non-steroidal anti-inflammatory drugs (NSAIDs) has seriously affected human health and ecosystems, as a result, the World Health Organization (WHO) has regarded them as emerging contaminants. NSAID’s polar nature and trace amount present in wastewater make their extraction and determination challenging in modern analytical science. Therefore, regarding the need, we herein report a rapid, sensitive and selective in-syringe solid-phase extraction (SPE) method coupled with ultrahigh performance liquid chromatography and UV detector for the determination of seven NSAIDs in environmental water samples. Specifically, the NSAIDs in water samples were directly extracted by using synthesized porous covalent organic framework functionalized poly (styrene-divinyl benzene-glycidylmethacrylate) composite (COF@PS-GMA) without further cleanup procedures. The adsorption of NSAIDs on COF@PS-GMA sorbent was investigated by using adsorption isotherms and kinetic studies. Various parameters, including amount of sorbent, pH of the samples, the volume of desorption solvent, and desorption time that were involved in in-syringe SPE were optimized. Under the optimized conditions, good linearity was observed at 0.005–5.0 μg mL−1 with method quantification limits (LOQs) estimated between 0.54–2.74 μg L−1. The recoveries of the seven NSAIDs at the level of 0.5, 5.0 and 20.0 μg L−1 were ranging from 84.3% to 99.6%.

Selective, fast and semi-automatic enrichment of nucleosides by using a phenylboronic acid modified hybrid material composed of graphene oxide and melamine sponge.

A hybrid material was prepared from graphene oxide and melamine sponge, and modified with phenylboronic acid to obtain a sorbent for the enrichment of the nucleosides cytidine, uridine, inosine, guanosine and adenosine. The loading capacity typically is around 27.8mgg-1 which is comparable to other sorbents, and highly selectivity for cis-diols is observed even if the concentration of potential interferents is 1500-fold higher. The sorbent was placed in an injector, and the process was operated semiautomatically by using a peristaltic pump. The sorbent is stable and can be re-used six times without decrease in efficiency. It was applied to the selective extraction of the cis-diols (cytidine, uridine, inosine, guanosine, adenosine) from HepG2 cells. It presents good linear between 3 to 5000μgL-1 and the limits of detection (in HPLC analysis with UV detection) are 1-4μgL-1. Good recoveries of 85-101% were obtained with spiked HepG2 cells samples, with relative standard deviation of ≤9.9%. Graphical abstract Schematic for the preparation of boronic acid modified graphene oxide/melamine sponge composite for in-syringe solid-phase extraction of nucleosides.

Metal-organic framework based in-syringe solid-phase extraction for the on-site sampling of polycyclic aromatic hydrocarbons from environmental water samples.

In-syringe solid-phase extraction is a promising sample pretreatment method for the on-site sampling of water samples because of its outstanding advantages of portability, simple operation, short extraction time, and low cost. In this work, a novel in-syringe solid-phase extraction device using metal-organic frameworks as the adsorbent was fabricated for the on-site sampling of polycyclic aromatic hydrocarbons from environmental waters. Trace polycyclic aromatic hydrocarbons were effectively extracted through the self-made device followed by gas chromatography with mass spectrometry analysis. Owing to the excellent adsorption performance of metal-organic frameworks, the analytes could be completely adsorbed during one adsorption cycle, thus effectively shortening the extraction time. Moreover, the adsorbed analytes could remain stable on the device for at least 7 days, revealing the potential of the self-made device for on-site sampling of degradable compounds in remote regions. The limit of detection ranged from 0.20 to 1.9ng/L under the optimum conditions. Satisfactory recoveries varying from 84.4 to 104.5% and relative standard deviations below 9.7% were obtained in real samples analysis. The results of this study promote the application of metal-organic frameworks in sample preparation and demonstrate the great potential of in-syringe solid-phase extraction for the on-site sampling of trace contaminants in environmental waters.

In-syringe solid-phase extraction for on-site sampling of pyrethroids in environmental water samples

On-site sampling is an analytical approach that can ensure the accuracy of monitoring data and enhance the effectiveness of environmental protection measures. In the present work, an in-syringe solid-phase extraction (SPE) device was designed for on-site sampling of trace contaminants in environmental water samples followed by gas chromatography-mass spectrometry (GC-MS) analysis. Template assisted freeze casting followed by hydrazine vapor reduction approach was used to synthesize a hierarchical porous graphene aerogel (HPGA), which was used as the sorbent in the in-syringe SPE device. Environmental degradable pyrethroids were selected as the model analytes. Owing to the large specific surface area and hydrophobicity of HPGA, the target molecules could be completely extracted during one aspirating/dispensing cycle. The analytes were stable on the sorbent for at least 72 h when the device was stored under airtight and light-free conditions, and were not affected by the pH value of sample solution. All results demonstrated that the device could meet the requirements of on-site sampling. For practical application, the limits of detection were found to be in the range of 0.012–0.11 ng mL−1 under the optimized conditions, and satisfactory recoveries in the range of 65.7–105.9% were obtained for the analysis of real samples. The results of this study demonstrate the immense potential of HPGA for the enrichment of trace environmental pollutants, and meanwhile promote the application of the in-syringe SPE technique as a promising candidate for on-site sampling.

In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers

Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni–Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15–0.35μgL−1. The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD’s, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6–11.2%. Enrichment factors of 15–21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7–95.3%.