Experimental Detection Limit Research Articles

In situ generation of cuprous oxide in metal-organic framework for significantly enhanced room-temperature ammonia sensing: Synergy enabling excellent sensitivity and selectivity

Development of effective strategies to improve the response sensitivity of metal-organic frameworks (MOFs) to target gases is imperative to further enhancing their application potential in gas sensing. In this work, series of CuHHTP/Cu2O (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) composites are successfully constructed by in-situ electrochemical reduction treatment of CuHHTP, and the changing trend of first increasing and then decreasing with increase of CuHHTP electrochemical reduction degree for their sensitivity to NH3 detection is revealed. When the average size of Cu2O nanoparticles generated in CuHHTP is 3.6 nm, the corresponding CuHHTP/Cu2O-A composite exhibits the best NH3 sensing performance compared to pristine CuHHTP, including significantly enhanced response sensitivity, ultralow experimental detection limit of 10 ppb, superior selectivity, good reproducibility, and excellent response stability even after placed for 90 days. More impressively, thanks to integration and synergy of the uniformly-dispersed small-sized Cu2O nanoparticles with significantly enhanced adsorption activity and capacity for NH3, the released large amount of uncoordinated hydroxyl groups that can interact with NH3, as well as the active sites of the CuHHTP substrate itself, the 10 ppb experimental detection limit for the CuHHTP/Cu2O-A-based sensors is not only the lowest one reported in the past 10 years for NH3 sensors based on copper-containing MOF and oxide materials, but also superior to that of 0.1–1 ppm for the existing commercial NH3 sensors. This work opens the avenue for design and development of novel MOF-based sensing materials.

Magnetic solid-phase extraction of amoxicillin and doxycycline from water and urine samples based on cetylpyridinium chloride-modified Fe3O4 nanoparticles followed by spectrophotometric determination.

This research describes an easy, rapid, and inexpensive magnetic solid-phase extraction (MSPE) approach employing Fe3O4 magnetic nanoparticles modified with cetylpyridinium chloride (Fe3O4@CPC/MNPs) for extracting amoxicillin (AMX) and doxycycline (DOX) after derivatization with 4-chloroaniline as a color reagent. The azo-coupling of AMX and DOX with the color reagent in the alkaline medium caused yellow and yellow-orange azo dyes with maximum absorption wavelengths of 435 and 438 nm, respectively. The UV-Vis spectroscopy was utilized to determine the target analyte after the extraction procedure. Good linearities (R2 > 0.99) in the concentration ranges of 0.03-4.50 and 0.05-6.00µg/mL were obtained for AMX and DOX, respectively. The experimental detection limits of AMX and DOX were obtained as 0.01 and 0.02 µg/mL, respectively. The developed approach was effectively applied to pre-concentrate and quantify AMX and DOX in environmental water and urine samples.

High-sensitive and fast-responsive In2O3 thin film sensors for dual detection of NO2 and H2S gases at room temperature

In this work, the room-temperature dual gas sensing characteristics of indium oxide (In2O3) thin films towards NO2 and H2S have been studied. In2O3 thin films were synthesized by the thermal oxidation of indium metal films of various thicknesses in the range of 50–250 nm deposited by thermal evaporation method. Grazing incidence X-ray diffraction (GI-XRD) revealed the change in preferred orientation of In2O3 thin films corresponding to varying thickness, while field-emission electron microscopy studies showcased evolving surface morphologies from individual grains to granular network with respect to the increase in film thickness. Investigations were made on the ability of In2O3 thin films to detect various low concentrations of nitrogen dioxide (NO2) and hydrogen sulfide (H2S) gases at ambient temperature. In2O3 thin films synthesized using 100 nm thick In films exhibited good sensing response of around 58 and 68 % towards NO2 and H2S gases of 5 ppm respectively, at room temperature (27 °C) with the response time of 36 and 18 s. Remarkably, the lower experimental detection limit of these toxic gases could be extended up to 100 ppb. Using X-ray photoelectron spectroscopy, a large presence of surface oxygen is observed on the In2O3 thin film. The sensor has demonstrated remarkable sensing abilities, including strong selectivity, quick sensing response, and good repeatability.

Indicator displacement-based colorimetric assay for dibutyl phthalate in pharmaceutical products with titanium(IV)-pyridylazo resorcinol (PAR)

Taking advantage of the competitive binding affinity towards Ti(IV) between 4-(2-pyridylazo) resorcinol (PAR) and phthalate, a simple indicator displacement (ID)–based colorimetric assay was designed for indirect determination of a well-known phthalic acid ester, dibutyl phthalate (DBP). The indicator PAR and Ti(IV) formed a purplish-red-colored Ti(IV)-PAR complex (λmax = 540 nm) at a 1:1 ratio. In the presence of pre-hydrolyzed DBP, colorless complex formation of phthalate ion (emerging from alkaline hydrolysis of DBP) with Ti(IV) resulted in a hypsochromic shift in absorbance maximum, accompanying a color change from purplish-red to yellowish-orange (λmax = 390 nm) by the release of PAR from Ti(IV)-PAR system. Based on this mechanism, the linear response range of the system for DBP was found to lie between 0.16 and 0.37 mmol L–1 with an experimental detection limit of 11.6 µmol L–1. The recommended Ti(IV)-PAR system was successfully applied to DBP-containing pharmaceutical products (as real sample) after a simple clean-up process for removing possible water-soluble interferents. The analytical results obtained from the recommended method (by applying the standard addition approach) and the reference liquid chromatography-tandem mass spectrometric (LC–MS/MS) method were statistically compared using DBP-extract of the drug samples. Consequently, a simple and selective colorimetric ID strategy was proposed for the analysis of DBP in pharmaceuticals for the first time.

Based on Fe and Ni prepared organic colloidal materials as efficient oxide nanozymes for chemiluminescence detection of GSH and Hg(II) ions

Metal-organic gels (MOGs) are a type of metal-organic colloid material with a large specific surface area, loose porous structure, and open metal active sites. In this work, FeNi-MOGs were synthesized by the simple one-step static method, using Fe(III) and Ni(II) as the central metal ions and terephthalic acid as the organic ligand. The prepared FeNi-MOGs could effectively catalyze the chemiluminescence of luminol without the involvement of H2O2, which exhibited good catalytic activity. Then, the multifunctional detected platform was constructed for the detection of GSH and Hg2+, based on the antioxidant capacity of GSH, and the strong affinity between mercury ion (Hg2+) and GSH which inactivated the antioxidant capacity of GSH. The experimental limits of detection (LOD) for GSH and Hg2+ were 76 nM and 210 nM, and the detection ranges were 2–100 μM and 8–4000 μM, respectively. The as-proposed sensor had good performance in both detection limit and detection range of GSH and Hg2+, which fully met the needs of daily life. Surprisingly, the sensor had low detection limits and an extremely wide detection range for Hg2+, spanning five orders of magnitude. Furthermore, the detection of mercury ions in actual lake water and GSH in human serum showed good results, with recovery rates ranging from 90.10 % to 105.37 %, which proved that the method was accurate and reliable. The as-proposed sensor had great potential as the platform for GSH and Hg2+ detection applications.

Gold nanodendrites enriched with gold nanoclusters on carbon-fiber as flexible acetaminophen sensor for clinical diagnostics

In this work, we demonstrate a flexible acetaminophen (APAP) microsensor based on gold dendrites decorated with gold nanoclusters on flexible carbon fiber (AuDS-AuNC|FCF) microelectrodes. The AuDS-AuNC|FCF microelectrodes are fabricated with a facile and single-step electrochemical strategy for electrocatalytic oxidation and sensing acetaminophen in a 0.1 M phosphate buffer (PB) (pH ∼7.4) solution. The as-developed AuDS-AuNC|FCF microsensors demonstrate excellent electrocatalytic oxidation of acetaminophen with a low oxidation potential of ∼0.54 V (vs. Ag/AgCl) and high catalytic current of ∼1.33 μA. This is because they have a lot of active sites, a large quantity of electrochemical active surface area (ECSA), and gold nanoclusters that are spread out homogeneously. The AuDS-AuNC|FCF microsensors exhibit fast sensing response time of ∼5.0 s, low experimental detection limit of ∼5.0 nM, high sensitivity of ∼0.375 ± 0.017 mA μM−1 cm−2 with a broad linear range of 5.0 nm–500.0 mM, good reproducibility, and possessed a robust anti-interference ability against sensing acetaminophen in the presence of potential interferences such as ascorbic acid, uric acid, adenine, guanine, glucose, etc. Notably, the present microsensor platform based on AuDS-AuNC|FCF microelectrodes is successfully tested for sensing acetaminophen in practical human serum samples, demonstrating its practicability in clinical diagnostics.

Enhanced selectivity of novel sea urchin-like h-/m-WO3 hetero nanoflowers for highly sensitive detection of ammonia by double filtration method

Real-time monitoring of toxic gases and breath markers can be performed by metal oxide semiconductor-based chemo-resistive gas sensors due to their simple structures, low cost, and faster and better recovery and response. Due to the effective electron-hole separation, tuning the development of phase junctions of the metal oxide is an efficient method for improving their gas sensing properties. In this study, two distinct hydrothermal methods were used to synthesize h-/m-WO3 hetero-nanoflowers. In the first method, L-Cysteine was used to facilitate the formation of phase junctions between h-WO3 and m-WO3 nanostructures, whereas Thiourea was used in the second. Various characterisation approaches validated the hexagonal-monoclinic phase junction development in the nanoflowers. The sensing material fabricated using Thiourea with a concentration of 0.01M performed better than other sensors. At 350°C, the selected sample displayed outstanding ammonia sensing capacity with the experimental detection limit of 1 ppm (response=3.33). The theoretical detection limit is determined to be 27 ppb. The selectivity of the sensor towards NH3 over H2S and acetone is increased by combining the devices with a double filtration setup. The effectiveness of the selected h-/m-WO3 sensor for diagnosing kidney dysfunction was evaluated by analyzing simulated breath samples.

Oxygen Vacancy-Rich Bimetallic Au@Pt Core-Shell Nanosphere-Functionalized Electrospun ZnFe2O4 Nanofibers for Chemiresistive Breath Acetone Detection.

Sensitive and selective acetone detection is of great significance in the fields of environmental protection, industrial production, and individual health monitoring from exhaled breath. To achieve this goal, bimetallic Au@Pt core-shell nanospheres (BNSs) functionalized-electrospun ZnFe2O4 nanofibers (ZFO NFs) are prepared in this work. Compared to pure NFs-650 analogue, the ZFO NFs/BNSs-2 sensor exhibits a stronger mean response (3.32 vs 1.84), quicker response/recovery speeds (33 s/28 s vs 54 s/42 s), and lower operating temperature (188 vs 273 °C) toward 0.5 ppm acetone. Note that an experimental detection limit of 30 ppb is achieved, which ranks among the best cases reported thus far. Besides the demonstrated excellent repeatability, humidity-enhanced response, and long-term stability, the selectivity toward acetone is remarkably improved after BNSs functionalization. Through material characterizations and DFT calculations, all these improvements could be attributed to the boosted oxygen vacancies and abundant Schottky junctions between ZFO NFs and BNSs, and the synergistic catalytic effect of BNSs. This work offers an alternative strategy to realize selective subppm acetone under high-humidity conditions catering for the future requirements of noninvasive breath diabetes diagnosis in the field of individual healthcare.

Surface modification of Co3O4 nanosheets through Cd-doping for enhanced CO sensing performance.

The detection of hazardous CO gas is an important research content in the domain of the Internet of Things (IoT). Herein, we introduced a facile metal-organic frameworks (MOFs)-templated strategy to synthesize Cd-doped Co3O4 nanosheets (Cd-Co3O4 NSs) aimed at boosting the CO-sensing performance. The synthesized Cd-Co3O4 NSs feature a multihole nanomeshes structure and a large specific surface area (106.579 m2·g-1), which endows the sensing materials with favorable gas diffusion and interaction ability. Furthermore, compared with unadulterated Co3O4, the 2 mol % Cd-doped Co3O4 (2% Cd-Co3O4) sensor exhibits enhanced sensitivity (244%) to 100 ppm CO at 200°C and a comparatively low experimental limit of detection (0.5 ppm/experimental value). The2% Cd-Co3O4 NSs show good selectivity, reproducibility, and long-term stability. The improved CO sensitivity signal is probably owing to the stable nanomeshes construction, high surface area, and rich oxygen vacancies caused by cadmium doping. This study presents a facile avenue to promote the sensing performance of p-type metal oxide semiconductors by enhancing the surface activity of Co3O4 combined with morphology control and component regulation.

Clinical Evaluation of Xpert Xpress CoV-2/Flu/RSV plus and Alinity m Resp-4-Plex Assay.

The performance of the Xpert Xpress CoV-2/Flu/RSV plus and Alinity m Resp-4-Plex Assays were evaluated using 167 specimens, including 158 human respiratory specimens and 9 external quality assessment program (EQAP) samples. For respiratory specimens, CoV-2/Flu/RSV plus exhibited perfect agreement with the standard-of-care (SOC) methods (Cohen's κ: 1, 100% agreement). The overall positive and negative percent agreement (PPA and NPA) were 100%, with 95% confidence intervals of 96.50 to 100% and 85.70 to 100%, respectively. On the other hand, Resp-4-Plex revealed an almost perfect agreement with the SOC methods (Cohen's κ: 0.92, 97.71% agreement). The overall PPA and NPA were 100% (95.76 to 100%) and 88.46% (70.20 to 96.82%), respectively. For EQAP samples, the results of CoV-2/Flu/RSV plus (9/9) and Resp-4-Plex (4/4) were concordant with the expected results. The experimental limit of detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) was the lowest (25 copies/mL for both methods), and that of the respiratory syncytial virus was the highest (400 copies/mL for CoV-2/Flu/RSV plus and 100 copies/mL for Resp-4-Plex). Threshold cycle (Ct) value correlation showed a large positive linear association between CoV-2/Flu/RSV plus and Resp-4-Plex, with R-squared values of 0.92-0.97, and on average, the Ct values of CoV-2/Flu/RSV plus were higher than that of Resp-4-Plex by 1.86-2.78, except for Flu A1 target (-0.66). To conclude, the performance of both assay was comparable to the SOC methods for both upper and lower respiratory specimens. Implementation of these rapid assay may reinforce the diagnostic capacity for the post-pandemic co-circulation of SARS-CoV-2 and other respiratory viruses.

High‐Index and Low‐Loss Topological Insulators for Mid‐Infrared Nanophotonics: Bismuth and Antimony Chalcogenides

AbstractTopological insulators generally have dielectric bulk and conductive surface states. Consequently, some of these materials are shown to support polaritonic modes at visible and THz frequencies. At the same time, the optical properties of topological insulators in the mid‐infrared (mid‐IR) remain poorly investigated. Here, near‐field imaging is employed to probe the mid‐IR response from the exfoliated flakes of bismuth (Bi)/selenide (Se)/telluride (Te)/antimony (Sb) crystals with varying stoichiometry – Bi2Se3, Bi2Te2Se, and Bi1.5Sb0.5Te1.7Se1.3 – in pristine form as well as covered by thin flakes of hexagonal boron nitride (hBN) is employed. Contrary to theoretical expectations, all three materials exhibit a dielectric response with a high refractive index and with a loss below the experimental detection limit. Particularly, the near‐field mapping of propagating phonon‐polaritons in hBN demonstrates that all three van der Waals crystals with different stoichiometry act as a practically lossless dielectric substrate with an ultra‐high refractive index of up to 7.5 in Bi2Te2Se. Such a unique dielectric crystal will be of great advantage for numerous nanophotonic applications in the mid‐IR.

Interfacially Confined Dynamic Reaction Resulted to Fluorescent Nanofilms Depicting High-Performance Ammonia Sensing.

Sensing materials innovation plays a crucial role in the development of high-performance film-based fluorescent sensors (FFSs). In our current study, we present the innovative fabrication of four fluorescent nanofilms via interfacially confined dynamic reaction of a specially designed fluorescent building block, a new boron-coordinated compound (NI-CHO), with a chosen one, benzene-1,3,5-tricarbohydrazide (BTH). The nanofilms as prepared are robust, uniform, flexible, and thickness tunable, at least from 40 to 1500 nm. The fabricated FFSs based on Film 3, one of the four nanofilms, shows highly selective and fully reversible response to NH3 vapor with an experimental detection limit of <0.1 ppm and a response time of 0.2 s. The unprecedented high performance of the nanofilm is ascribed to the specific quenching of its fluorescence emission owing to formation of an excited-state complex between the sensing unit and the analyte molecule. Efficient mass transfer also contributes to the high performance owing to the porous adlayer structure of the nanofilm. This work provides an example to show how to develop a high-performance sensing film via controlling the film's structure, especially the thickness.

Machine learning assisted dual-functional nanophotonic sensor for organic pollutant detection and degradation in water

This study presents a dual-functional thin film, known as Ag nanoparticles decorated, ZnO nanorods coated silica nanofibers (AgNP-ZnONR-SNF), which demonstrates remarkable capabilities in both water purification and organic pollutants sensing. The 3D fibrous structure of ZnONR-SNF provides a large surface-area-to-volume ratio for piezo- and photo-catalytic degradation of organic pollutants under UV irradiation, achieving over 98% efficiency. Ag nanoparticles decorated on ZnONR-SNF form “hot-spot” that significantly enhance the surface-enhanced Raman spectroscopy (SERS) signal, resulting in an enhancement factor of 1056 and an experimental detection limit of 1 pg mL−1. Furthermore, a machine learning algorithm is developed for the qualitative and quantitative detection of multiple contaminants, achieving high accuracy (92.3%) and specificity (89.3%) without the need for preliminary processing of Raman spectra. This work provides a promising nanoengineering solution for water purification and sensing with improved detection accuracy, purification efficiency, and cost-effectiveness.

Self-assembled monolayer of poly(o-phenylenediamine)/silver core-shell hybrid-based enzyme-free impedimetric glucose sensor for blood samples.

A core-shell hybrid of poly(o-phenylenediamine)/silver was prepared by a simple single-step process and self-assembled on a glassy carbon electrode to design an enzyme-free electrochemical glucose sensor. The working electrode was fabricated by self-assembling a dimethyl sulfoxide (DMSO) solution of the prepared hybrid on a glassy carbon electrode. The electrochemical properties of the fabricated electrode were analyzed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in an aqueous potassium chloride electrolyte containing the [Fe(CN)6]3-/4- redox couple. The electrochemical sensing responses towards varying concentrations of glucose were studied by CV and EIS in the same redox electrolyte medium. The poly(o-phenylenediamine)/silver core-shell hybrid-based sensor was found to show a reliable response in the EIS experiment over the CV experiment. By analyzing the EIS sensing responses, the experimental limit of detection was determined to be 10 μL of ∼80 mg per dL glucose solution in 25 mL of 1 (M) KCl electrolyte containing the 10-3 M [Fe(CN)6]3-/4- redox couple with a sensitivity of 298 Ω mg-1 dL cm-2. Excellent selectivity towards glucose was confirmed over various bioactive interfering biomolecules like ascorbic acid, dopamine, uric acid, lactose, fructose and sucrose. The glucose content in the human blood sample was verified by the designed sensor with almost 100% recovery.

Fabrication of a graphite-paraffin carbon paste electrode and demonstration of its use in electrochemical detection strategies.

Electrochemical detection methods hold many advantages over their optical counterparts, such as operation in complex sample matrices, low-cost and high volume manufacture and possible equipment miniaturisation. Despite these advantages, the use of electrochemical detection is currently limited in the clinical setting. There is a wide range of potential electrode materials, selected for optimal signal-to-noise ratios and reproducibility when detecting target analytes. The use of carbon paste electrodes (CPEs) for electrochemical detection can be limited by their analytical performance, however they remain very attractive due to their low cost and biocompatibility. This paper presents the fabrication of an easy-to-make and use graphite powder/paraffin wax paste combined with a substrate produced via additive manufacturing and confirms its functionality for both direct and indirect electrochemical measurements. The produced CPEs enable the direct voltammetric detection of hexaammineruthenium(III) chloride and dopamine at an experimental limit of detection (ELoD) of 62.5 μM. The key inflammatory biomarker Interleukin-6 through an enzyme-linked immunosorbant assay (ELISA) was also quantified, yielding a clinically-relevant ELoD of 150 pg ml-1 in 10% human serum. The performance of low-cost and easy-to-use CPEs obtained in 0.5 hours is showcased in this study, demonstrating the platform's potential uses for point-of-need electroanalytical applications.

Fiber optic cadmium ion sensors based on functionalization of a magnetic ion-imprinted polymer.

Cadmium poisoning is a chronic accumulation process, and long-term drinking of even low cadmium content water will cause kidney damage, so an ultra-low detection limit is particularly important. However, at the present stage, the traditional detection method cannot reach a sufficiently low detection limit, the response time is too long, and the cost of detection is very high, so that real-time measurement cannot be realized. Therefore, the traditional cadmium ion detection method has a slow response and an insufficient detection limit. This paper presents a fiber optic cadmium ion sensor functionalized based on an Fe3O4@SiO2@CS magnetic ion imprinting polymer (M-IIP). The sensor is based on the coupling characteristics of the optical microfiber coupler (OMC) cone region to achieve a highly sensitive response to the change in the cadmium ion concentration. M-IIP materials were prepared by surface imprinting polymerization to achieve low cross-sensitivity and thus improve the detection limit of the sensor. The results show that the developed fiber sensor has high specificity and a rapid response to cadmium ions. The experimental limit of detection (LOD) reached 0.051 nM within 0-1 μM with a response time of less than 50 s. Moreover, the proposed fiber cadmium ion sensor exhibits excellent performance in terms of sensitivity, stability, repeatability and biocompatibility.

Enhanced biosensing of tumor necrosis factor-alpha based on aptamer-functionalized surface plasmon resonance substrate and Goos-Hänchen shift.

Tumor necrosis factor-alpha (TNF-α) serves as a crucial biomarker in various diseases, necessitating sensitive detection methodologies. This study introduces an innovative approach utilizing an aptamer-functionalized surface plasmon resonance (SPR) substrate together with an ultrasensitive measure, the Goos-Hänchen (GH) shift, to achieve sensitive detection of TNF-α. The developed GH-aptasensing platform has shown a commendable figure-of-merit of 1.5 × 104 μm per RIU, showcasing a maximum detectable lateral position shift of 184.7 ± 1.2 μm, as characterized by the glycerol measurement. Employing aptamers as the recognition unit, the system exhibits remarkable biomolecule detection capabilities, including the experimentally obtained detection limit of 1 aM for the model protein bovine serum albumin (BSA), spanning wide dynamic ranges. Furthermore, the system successfully detects TNF-α, a small cytokine, with an experimental detection limit of 1 fM, comparable to conventional SPR immunoassays. This achievement represents one of the lowest experimentally derived detection limits for cytokines in aptamer-based SPR sensing. Additionally, the application of the GH shift marks a ground breaking advancement in aptamer-based biosensing, holding significant promise for pushing detection limits further, especially for small cytokine targets.

Indirect detection of acid phosphatase at the macroscopic electrified liquid-liquid interface

Acid phosphatase (AcidP) is a biomarker of prostate cancer (PC) when found in blood and urine at elevated levels. Moreover, AcidP could also be used as a target biomarker in presumptive test for the presence of semen in case of sexual assault. Therefore, this preliminary work proposes an alternative approach for the electrochemical (cyclic voltammetry) detection of AcidP having specific activity ≥0.4 unit·mg−1 over electrified liquid-liquid interface (eLLI). Proposed idea is simple and based on the reaction catalyzed by AcidP, this is hydrolysis of phosphocholine ester (PCE) resulting in the production of choline that generate electrochemical signal upon potential difference controlled transfer across the eLLI. Mechanisms, interfacial behavior, physicochemical parameters pertaining to choline, PCE and AcidP have been studied using cyclic voltammetry. Observed optimal parameters were employed for the indirect detection of the AcidP in the presence of PCE. We have found that when the mixture of AcidP and PCE were incubated for 24 h at 37 ˚C in 10 mM Britton-Robinson-Buffer (pH 4.8) the clear signals attributed to choline transfer started appearing within the available potential window. Even with very low specific activity of AcidP (only 0.4 unit·mg−1), eLLI based enzyme biosensor demonstrated a linear detection range from 0.4 to 2.0 mg·mL−1 with experimental detection limit of 0.4 mg·mL−1. Moreover, sensitivity of the proposed biosensor was found 5.15 µA·L·g−1. Results obtained in this study can be considered as the proof of concept with high potential for the detection of AcidP in real clinical and forensic samples.

Room-temperature synthesis of ionic liquid@covalent organic frameworks for the solid phase extraction and analysis of six herbicides from water samples

Waters contaminated with pesticides poses a potential hazard to ecosystems and human health, so sensitive and efficient analytical methods are essential for water monitoring. Herein, in order to efficiently extract six commonly used herbicides, a novel ionic liquid covalent organic framework (IL@COF) was prepared using a simple room-temperature synthesis in this study. As an adsorbent for solid phase extraction (SPE), the mesoporous material exhibits rapid adsorption performance for six typical herbicides from water samples. Under the optimal experimental conditions, wide linearities (500 ∼ 20,000 μg L–1) and low limits of detection (prometryn: 17.9 μg L–1; metribuzin: 36.7 μg L–1; bentazon: 14.5 μg L–1; isoproturon: 18.0 μg L–1; acetochlor: 19.6 μg L–1; butachlor: 37.1 μg L–1) for six analytes were obtained via high performance liquid chromatography (HPLC). The adsorbent has stable physical and chemical properties and can be reused for 10 times after effective elution. The applicability of this method is further evaluated by analyzing ten kinds of real water sample. The recoveries of six kinds of herbicides ranged from 85.3 % to 122.9 %. The mechanism of adsorption is the interaction between hydrogen bond acceptor and donor. These results indicate that HPLC after SPE with a new type of IL@COF as the SPE adsorbent is a promising technique for the simultaneous detection of six pesticides in environmental water samples.

Just laser irradiation of silver benzoate water solution — A direct way of Ag nanofibers synthesis for broadband SERS detection

Highly efficient, homogeneous and reproducible substrates for surface enhanced Raman spectroscopy (SERS) are in high demand for practical broadband sensing and the detection of various analytes. The most promising SERS structures in terms of morphology are nanofibers, forming homogeneous coatings with broadband electric field enhancement. However, existing synthesis methods for the formation of nanofibers are multistage, requiring the preliminary synthesis of templates, using additional components, such as surfactants and capping agents, species extraction from the reaction mixture, washing and sedimentation onto a substrate. Here, we present a simple and scalable synthesis approach allowing the fabrication of long winding silver nanofibers directly on a substrate surface, without any additional stages. The process proposed is ecologically friendly and based on laser irradiation of a substrate–solution interface using a low intensity continuous wave unfocused laser beam with a wavelength of 448 nm. As the liquid phase, a silver benzoate water solution without any additional chemicals was used. The deposited nanofibers formed a continuous coating with an area corresponding to the laser beam, ca. 3 mm2, and were characterized by an enhancement factor as high as 107 in the broad spectral region, a low experimental detection limit of 10−11 M and high reproducibility of the SERS signal with a variation of ∼10%.