Seamless integration of Internet of Things, miniaturization, and environmental chemical surveillance.

IoT is a game-changer across all fields, including chemistry. Embracing sustainable practices and green chemistry, the miniaturization and automation of systems, and their integration into IoT is key to achieving these principles, as a rising trend with momentum. Particularly, IoT and analytical chemistry are linked in the rapid exchange of analytical data for environmental, industrial, healthcare, and educational applications. Meanwhile, cooperation with other fields of science is evident, and there is a prompt and subjective analysis of information related to analytical systems and methodologies. This paper will review the concepts, requirements, and architecture of IoT and its role in the miniaturization and automation of analytical tools using electronic modules and sensors. The aim is to explore the standards and perspectives of IoT and its interaction with different aspects of analytical chemistry. Additionally, it aimed to explain the basics and applications of IoT for chemists, and its relevance to different subfields of analytical chemistry, particularly in the field of environmental chemical surveillance. The article also covers updating IoT devices and creating DIY-based degradation devices to enhance the educational aspect of chemistry and reduce barriers to lab facilities and equipment. Lastly, it will explore how IoT is really important and how it's going to significantly impact analytical chemistry.

Application of a portable ion chromatograph for real-time field analysis of nitrite and nitrate in soils and soil pore waters.

Real-time monitoring of nitrite and nitrate is crucial for maintaining soil health and promoting plant growth. In this study, a portable ion-chromatograph (IC, Aquamonitrix) analyser, coupled with a field-applicable ultrasonic-assisted extraction method, was utilised for in-field determination of nitrate and nitrite in soils. This is the first application of this type of analyser to soil nutrients. On-site analysis of soil from a local sports field showed 94.8 ± 4.3 µg g-1 nitrate, with LODs of 32.0 µg g-1 for nitrate and 5.4 µg g-1 for nitrite. The results were in close agreement with those obtained using a conventional lab-based IC. Relative standard deviations (%RSDs) for soil analysis using Aquamonitrix were consistently below 10%. The obtained average recoveries of samples spiked with nitrite were 100% and 104% for the portable IC and conventional IC, respectively. Furthermore, to assess the suitability of portable IC for samples with high organic matter content, various natural organic fertilisers were extracted and analysed. The results showed 16.2 ± 0.7 µg g-1 nitrite and 28.5 ± 5.6 µg g-1 nitrate in sheep manure samples with LODs of 2.0 µg g-1 for nitrite and 12.0 µg g-1 for nitrate. The portable IC system was further demonstrated via real-time on-site analysis of soil pore-water acquired using a portable battery-based ceramic pore-water sampler. A continuous increase in nitrate concentration over time was observed (from 80 to 148 µg mL-1) in the soil pore-water in a vegetable garden four days after heavy rain. Unlike conventionally sampled natural waters, 7-day storage of the studied pore water samples revealed no changes in nitrate concentrations. An average of 558 ± 51 µg mL-1 nitrate was detected in the soil pore-water samples analysed on a spinach farm, immediately after irrigation.

Chemical bonding of cross-linked glutaraldehyde/chitosan on the surface of a titanium wire to prepare a robust biocompatible SPME fiber for analysis of phytohormones in plants.

A robust biocompatible solid-phase microextraction (SPME) fiber, so-called Ti/APTS/GA/CS, was prepared by chemical bonding of cross-linked glutaraldehyde-chitosan to the surface of a titanium wire using APTS. The fiber was applied for sampling of phytohormones in plant tissues, followed by HPLC-UV analysis. The structure and morphology of the fiber coating was investigated by FT-IR, SEM, EDX, XRD, and TGA techniques. A Box-Behnken design was implemented to optimize the experimental variables. The calibration graphs were linear over a wide linear range (0.5-200 µg L-1) with LODs over the range of 0.01-0.06 µg L-1. The intra-day and inter-day precisions were found to be 1.3-6.3% and 4.3-7.3%, respectively. The matrix effect values ranged from 86.5% to 111.7%, indicating that the complex sample matrices had an insignificant effect on the determination of phytohormones. The fiber was successfully employed for the direct-immersion SPME (DI-SPME-HPLC) analysis of the phytohormones in cucumber, tomato, date palm, and calendula samples.

Urinary biomonitoring of fuel ether oxygenates using a needle trap device packed with a novel molecularly imprinted polymer surface modified Zeolite Y.

This study introduces an innovative needle trap device (NTD) featuring a molecularly imprinted polymer (MIP) surface-modified Zeolite Y. The developed NTD was integrated with gas chromatography-flame ionization detector (GC-FID) and employed for analysis of fuel ether oxygenates (methyl tert­butyl ether, MTBE, ethyl tert­butyl ether, ETBE, and tert­butyl formate, TBF) in urine samples. To optimize the key experimental variables including extraction temperature, extraction time, salt concentration, and stirring speed, a central composite design-response surface methodology (CCD-RSM) was employed. The optimal values for extraction in the study were found to be 51.2 °C extraction temperature, 46.2 min extraction time, 27 % salt concentration, and 620 rpm stirring speed. Under the optimized conditions, the calibration curves demonstrated excellent linearity within the range of 0.1-100 µg L-1, with correlation coefficients (R2) exceeding 0.99. The limits of detection (LODs) for MTBE, ETBE, and TBF were obtained 0.06, 0.08, and 0.09 µg L-1, respectively. Moreover, the limits of quantification (LOQs) for MTBE, ETBE, and TBF were obtained 0.18, 0.24, and 0.27 µg L-1, respectively. The enrichment factor was also found to be in the range of 98-129.The NTD-GC-FID procedure demonstrated a high extraction efficiency, making it a promising tool for urinary biomonitoring of fuel ether oxygenates with improved sensitivity and selectivity compared to current methods.

Comparative study of molecularly imprinted polymer surface modified magnetic silica aerogel, zeolite Y, and MIL-101(Cr) for dispersive solid phase extraction of fuel ether oxygenates in drinking water.

The study was performed in two phases. First, the polymerization was carried out upon three magnetized surfaces of silica aerogel, zeolite Y, and MIL-101(Cr). Then, optimal molecularly imprinted polymer and optimal extraction conditions were determined by the central composite design-response surface method. Subsequently, the validation parameters of dispersive solid-phase extraction based optimal molecularly imprinted polymer were examined for the extraction of the fuel ether oxygenates. The optimal conditions include the type of adsorbent: Zeolite-magnetic molecularly imprinted polymer, the amount of adsorbent: 40 mg, pH: 7.7, and absorption time: 24.8 min which was selected with desirability equal to 0.996. The calibration graphs were linear between 1 and 100 µg L-1, with good correlation coefficients. The limits of detection were found to be 0.64, 0. 4, and 0.34 µg L-1 for methyl tert-butyl ether, ethyl tert-butyl ether, and tert butyl formate, respectively. The method proved reliable for analyzing fuel ether oxygenates in drinking water.

Exploring the optimal electropolymerization strategy for the preparation of solid-phase microextraction fibers using pyrrole-dopamine copolymers.

In-situ electropolymerization of conductive polymers on the surface of stainless-steel substrates is a well-established but promising procedure for the preparation of solid-phase microextraction (SPME) tools. Herein, different electrochemical methods including constant potential (CP), constant potential pulse (CPP), and cyclic voltammetry (CV) were utilized to fabricate SPME fibers by in-situ electropolymerization of pyrrole-dopamine copolymers (PPY/PDA) on the surface of stainless-steel fibers. The coated fibers were characterized and applied for the direct-immersion SPME (DI-SPME) sampling of ultra-trace amounts of plant hormones including abscisic acid (ABA), gibberellic acid (GA3), and indole acetic acid (IAA) in fruit juices, followed by HPLC-UV determination. The results showed that CV electropolymerization is significantly more efficient than the two other methods. The coatings created by the CV method were satisfactorily uniform, adhesive, and durable and exhibited higher extraction performance compared to the CP and CPP procedures. The important experimental variables of the proposed DI-SPME-HPLC method were evaluated and optimized using response surface methodology with a Box-Behnken design. The developed method showed wide-range linearities, spanning from 0.05 to 20µg mL-1 for GA3, and 0.02 to 20µg mL-1 for ABA and IAA. The limits of detection were obtained 0.01µg mL-1 for GA3, and 0.005µg mL-1 for ABA and IAA. The fiber was successfully employed for the simultaneous DI-SPME-HPLC analysis of plant hormones in fruit juice samples.

A comprehensive theory for vacuum-assisted headspace extraction of solid samples.

Vacuum-assisted headspace extraction (VA-HSE) has proven to be an efficient solution for the rapid and effective extraction of volatile and semi-volatile species. The research has been mainly focused on liquid samples by considering differences in Henry's constants, while the accelerating effect of vacuum is more significant and practically more important in solid samples with complex matrices. Nevertheless, the lack of a comprehensive theory for VA-HSE in solid samples, based on the adsorption/desorption phenomena, is quite evident. This research was done with the aim of modeling VA-HSE of solid samples from a thermodynamic point of view. To understand the impact and mechanism of reduced pressure, the sampling space was divided into three separate areas including the solid matrix (the surface and cavities of the solid sample), the headspace of the sample, and the extraction phase (the surface and cavities of the adsorbent). The effects of vacuum on the movement of analyte molecules in all three areas were investigated and included in a comprehensive equation. According to the theoretical model, when a solid sample is subjected to vacuum conditions, the enthalpy of the analytes in their free state decreases. As a result, the analytes become more volatile. Additionally, vacuum reduces the thickness of the boundary layer in solid samples. This facilitates the diffusion of analyte molecules into the cavities within the solid material and eventually into the headspace of the sample. A similar effect is observed on the extractive phase side when vacuum is applied. The reduction in boundary layer thickness promotes the adsorption of analytes onto the extractive phase, thereby facilitating a quicker equilibrium of analyte concentration in the extraction phase. The proposed model was validated by correlating it with the experimental data found in the literature. The results of this analysis have shown a robust correlation between the theoretical model and the experimental data, bolstering the reliability of the model, and highlighting its practical relevance.

Recent advances in miniaturization of portable liquid chromatography with emphasis on detection.

Liquid chromatography is a prominent analytical technique in separation science and chemical analysis, applied across numerous fields of research and within industrial applications. Over the past few decades, there has been a growing interest in the miniaturization of this technique, which has been particularly enabled through new miniature and portable detection technologies for in-field, at-site, and point-of-need (collectively 'out-of-lab') analyses. Accordingly, significant advances have been made in recent years in the development of miniaturized liquid chromatography with photometric, electrochemical, and mass spectrometric detection, enabling the development of field-deployable and portable instruments for various applications. Herein, recent developments in the miniaturization of detection systems for inclusion within, and/or coupling with, portable liquid chromatographic systems, are reviewed in detail together with critical comments and expected future trends in this area.

Dynamic in situ growth of bonded-phase silica nanospheres on silica capillary inner walls for open-tubular liquid chromatography.

Silica nanospheres (SNS) were grown on the inner walls of silica capillaries through a dynamic in situ nucleation process to prepare a highly porous and large accessible surface area substrate. The SNS were then functionalized with octadecyl (C18), 3-aminopropyltriethoxysilane (APTES), beta-cyclodextrin (ß-CD), and amino groups to develop robust and efficient chromatographic stationary phases. The modified silica capillaries were exploited for open-tubular liquid chromatography (OT-LC) and open-tubular capillary electrochromatography (OT-CEC) applications. The prepared stationary phases were compared to conventional capillaries in terms of separation performance. The synthesis process was optimized, and the bonded-phase stationary phases were characterized by the electron microscopy technique. The effects of different solvents, additives, and functional groups on the geometry and chromatographic resolving power of the SNS were envisaged. The capillaries modified with octadecyl groups were evaluated for the separation of non-steroidal anti-inflammatory drugs, phenones, alkenylbenzenes, and enantiomers of chlorophenoxy herbicides. As an application instance, an SNS-C18-coated capillary was utilized for the separation of alkenylbenzenes from clove extract and protein digest medium, through OT-LC and OT-CEC techniques, respectively. The ß-CD functionalized capillary was applied for the OT-CEC separation of a dichlorprop racemic mixture.

Cholestasis-Associated Pulmonary Inflammation, Oxidative Stress, and Tissue Fibrosis: The Protective Role of the Biogenic Amine Agmatine.

INTRODUCTION: Cholestasis is the stoppage of bile flow, leading to the accumulation of potentially cytotoxic bile components in the liver. These cytotoxic molecules affect many organs. Cholestasis-induced lung injury is a severe complication that could lead to tissue fibrosis and respiratory distress. Substantial evidence indicates the role of oxidative stress and inflammatory response in the pathogenesis of cholestasis-associated pulmonary damage. Agmatine (AGM; 1-amino-4-guanidinobutane) is a biogenic amine endogenously synthesized in the human body. This amine provides potent anti-inflammatory and antioxidant properties. METHODS: In the current study, a series (six C57BL/6J male mice/group) of bile duct-ligated (BDL) animals were monitored at scheduled intervals (7, 14, and 28 days after the BDL operation) to ensure inflammatory response in their lung tissue (by analyzing their bronchoalveolar lavage fluid [BALF]). It was found that the level of inflammatory cells, pro-inflammatory cytokines, and IgG in the BALF reached their maximum level on day 28 after the BDL surgery. Therefore, other research groups were selected as follows: 1) Sham-operated (2.5 mL/kg normal saline, i.p., for 28 consecutive days), 2) BDL, 3) BDL + AGM (1 mg/kg/day, i.p., for 28 consecutive days), and 4) BDL + AGM (10 mg/kg/day, i.p., for 28 consecutive days). Then, the BALF was monitored at scheduled time intervals (7, 14, and 28 days post-BDL). RESULTS: It was found that pro-inflammatory cytokines (TNF-α, IL-6, and IL-1ß), bile acids, bilirubin, and inflammatory cells (monocytes, neutrophils, and lymphocytes) were significantly increased in the BALF of BDL mice. Moreover, biomarkers of oxidative stress were significantly increased in the pulmonary tissue of cholestatic animals. Lung tissue histopathological changes, tissue collagen deposition, and increased TGF-ß were also detected. It was found that AGM significantly ameliorated cholestasis-induced lung injury. CONCLUSION: The effects of AGM on inflammatory indicators, oxidative stress biomarkers, and tissue fibrosis seem to play a pivotal role in its protective properties.

A simple and cost-effective synthesis route using itaconic acid to prepare a magnetic ion-imprinted polymer for preconcentration of Pb (II) from aqueous media.

A new Pb (II) magnetic ion-imprinted polymer (Pb-MIIP) was successfully investigated for the selective extraction of Pb (II) from an aqueous solution. MIIP nanostructures were developed using itaconic acid-coated iron oxide nanoparticles (Fe3O4@ITA) as a novel magnetic core, ITA as a functional monomer and chelating agent, ethylene glycol dimethacrylate (EGDMA) as a cross-linker, and 2,2-azobisisobutyronitrile (AIBN) as an initiator. The triple application of ITA in the synthesis and reduction of the number of compounds in the preparation of the MIIP, in addition to being economical, reduces the possibility of side reactions. The synthesized products were followed and confirmed in each step by instrumental and microscopic methods. The limit of detection of the Pb (II)-MIIP method was 0.21 µg L-1. Under the optimal conditions, the recovery (R%) was >90% with a relative standard deviation (RSD%) of <4.9%. The synthesized MIIP was reusable and successfully used to extract Pb (II) from tap water samples.

Pulmonary inflammation, oxidative stress, and fibrosis in a mouse model of cholestasis: the potential protective properties of the dipeptide carnosine.

Cholestasis is a clinical complication that primarily influences the liver. However, it is well known that many other organs could be affected by cholestasis. Lung tissue is a major organ influenced during cholestasis. Cholestasis-induced lung injury could induce severe complications such as respiratory distress, serious pulmonary infections, and tissue fibrosis. Unfortunately, there is no specific pharmacological intervention against this complication. Several studies revealed that oxidative stress and inflammatory response play a role in cholestasis-induced lung injury. Carnosine (CARN) is a dipeptide found at high concentrations in different tissues of humans. CARN's antioxidant and antiinflammatory properties are repeatedly mentioned in various experimental models. This study aimed to assess the role of CARN on cholestasis-induced lung injury. Rats underwent bile duct ligation (BDL) to induce cholestasis. Broncho-alveolar lavage fluid (BALF) levels of inflammatory cells, pro-inflammatory cytokines, and immunoglobulin were monitored at scheduled intervals (7, 14, and 28 days after BDL). Moreover, lung tissue histopathological alterations and biomarkers of oxidative stress were evaluated. A significant increase in BALF inflammatory cells, TNF-α, IL-1ß, IL-6, and immunoglobulin-G (IgG) was detected in the BALF of BDL rats. Moreover, lung tissue histopathological changes, collagen deposition, increased TGF-ß, and elevated levels of oxidative stress biomarkers were evident in cholestatic animals. It was found that CARN (100 and 500 mg/kg, i.p.) significantly alleviated lung oxidative stress biomarkers, inflammatory response, tissue fibrosis, and histopathological alterations. These data indicate the potential protective properties of CARN in the management of cholestasis-induced pulmonary damage. The effects of CARN on inflammatory response and oxidative stress biomarkers seems to play a crucial role in its protective properties in the lung of cholestatic animals.

Microextraction and Determination of Poly- and Perfluoroalkyl Substances, Challenges, and Future Trends.

Per- and polyfluoroalkyl substances (PFAS) are fluorocarbon compounds in which hydrogen atoms have been partly or entirely replaced by fluorine. They have a very wide range of applications, while they are persistent in the environment and exhibit bioaccumulative and toxic properties. Neither chemical nor biological mechanisms can decompose PFAS due to their strong C-F bonds. PFAS have shown adverse effects on various organisms, even at trace levels. Accordingly, highly sensitive and selective analytical methods are required for their tracing in biological and environmental matrices. The physicochemical properties of PFAS like surfactant characteristics and high-water solubility are unique and different from other known pollutants. Accordingly, the number of articles on the analysis of PFAS is less than the other well-known contaminants. The routine PFAS sample preparation methods (like solvent extraction) coupled with chromatographic systems, face challenges such as high limits of detection, need for laborious derivatization, limited selectivity, and expensive instrumentation. Recent efforts to address these limitations have aroused considerable attention to the development of microextraction techniques, which are consistent with the principles of green chemistry and can be made easily portable and automated. Moreover, these methods have shown enough sensitivity and selectivity for the analysis of different analytes (including PFAS) in a wide range of samples with different matrices. This research aims to review the microextraction methods and detection techniques, applied for the sample pretreatment of PFAS in various matrices, along with a critical discussion of the challenges and potential future trends.

In-Situ Intercalating of Silica Nanospheres into Polypyrrole During Its Electropolymerization to Prepare a Sorbent for Headspace Microextraction of Aldehydes in Edible Oils.

The quality of edible oils is significantly affected by autoxidation of lipids, which alters their flavor and nutritional quality through production of toxic materials like aldehydes (an important class of oil deterioration markers). Herein, an amino-silica nanospheres/polypyrrole (ASNS/PPy) nanocomposite sorbent was synthesized and used as the fiber coating for headspace solid-phase microextraction (HS-SPME) of aldehydes in edible oils, followed by gas chromatography (GC) separation and determination. Amino-silica nanoparticles were prepared by an amended Stöber method and composited with polypyrrole during its electropolymerization on the surface of a platinized stainless-steel fiber. The synergy between in-situ electropolymerization and rough surface of the platinized metal substrate created a durable fiber coating with unique uniformity, cohesiveness, and adsorption properties. The synthesized nanocomposite was characterized using Fourier transform infrared spectroscopy and scanning electron microscopy techniques. The performance of the prepared fiber was optimized by investigating the affecting variables including extraction temperature and time, stirring rate, and desorption conditions. The obtained limits of detection for hexanal and heptanal in sunflower oil were 0.005-0.009 µg mL-1. The prepared fiber exhibited excellent repeatability and reproducibility with the intra-fiber and inter-fiber relative standard deviations in the ranges of 3.9-8.8% and 7.3-15.1%, respectively. The proposed HS-SPME-GC strategy was successfully applied for the analysis of aldehydes in commercial edible oil samples.

Nanomaterial-assisted thread-based isotachophoresis with on-thread solute trapping.

This research describes a nanomaterial-assisted thread-based isotachophoresis (TB-ITP) setup for the clean-up, preconcentration, and trapping of alkaloids (coptisine, berberine, and palmatine) in biological fluids, followed by their on-thread desorption electrospray ionization mass spectrometry (DESI-MS) determination. The reusable TB-ITP setup and a DESI compatible thread holder were 3D printed. A single nylon thread was employed as the ITP substrate for solute isolation and enrichment, and a short piece of graphene oxide (GO) functionalized nylon thread was tied around the main 'separation' thread as the 'trap' for the trapping of ITP focused alkaloids. Compared to the direct DESI-MS sample analysis, the sensitivity of the proposed method for the model solutes was increased up to 10-fold, benefiting from the TB-ITP focusing and enrichment strategy. This proof-of-concept use of nanomaterial-modified threads in electrofluidic separation and concentration procedures opens up a promising avenue to explore, particularly with regard to the sensitivity and selectivity of thread-based electrofluidic separation coupled with ambient ionization MS.

Mimic Nature Using Chemotaxis of Ionic Liquid Microdroplets for Drug Delivery Purposes.

Due to the growing prevalence of incurable diseases, such as cancer, worldwide, nowadays, the development of smart drug delivery systems is an inevitable necessity. Chemotaxis-driven movement of ionic liquid microdroplets containing therapeutic compounds is a well-known example of a smart drug delivery system. This review aims to classify, summarize, and compare ionic liquid-based chemotaxis systems in an easily understandable article. Chemotaxis is the basis of the movement of cells and microorganisms in biological environments, which is the cause of many vital biochemical and biological processes. This review attempts to summarize the available literature on single-component biomimetic and self-propelling microdroplet systems based on ionic liquids, which exhibit chemotaxis and spontaneously move in a determined direction by an external gradient, particularly a chemical change. It also aims to review artificial ionic liquid-based chemotaxis systems that can be used as drug carriers for medical purposes. The various ionic liquids used for this purpose are discussed, and different forms of chemical gradients and mechanisms that cause movement in microfluidic channels will be reviewed.

Thread-based isotachophoresis coupled with desorption electrospray ionization mass spectrometry for clean-up, preconcentration, and determination of alkaloids in biological fluids.

A thread-based isotachophoresis method coupled with desorption electrospray ionization mass spectrometry (TB-ITP-DESI-MS) was developed and applied for clean-up, preconcentration, and determination of alkaloids in biological fluids. This simple approach enables the focusing and rapid analysis of analytes of interest in complex matrices that are otherwise challenging using direct ambient mass spectrometry. The TB-ITP platform components were rapidly and reproducibly fabricated at low-cost using 3D printing. A single string of nylon 6 thread was used as the electrophoresis substrate and a cotton knot, tied to the nylon thread, was used as the trapping zone of the ITP focused model analytes (coptisine, berberine and palmatine). The trapping efficiency was evaluated upon different commercially available threads with different chemical properties and cotton was selected as the best material due to its highest trapping efficiency and subsequent DESI-MS ionization efficiency. Up to 11.6-fold increase in signal to noise ratio (S/N) was obtained using the proposed method compared to direct DESI-MS detection, due to the reduced matrix interference and focusing. The results demonstrated that the TB-ITP-DESI-MS approach is a viable solution for the analysis of complicated biological fluid samples.

Small-Footprint, Field-Deployable LC/MS System for On-Site Analysis of Per- and Polyfluoroalkyl Substances in Soil.

Per- and polyfluoroalkyl substances (PFASs) are emerging environmental pollutants of global concern. For rapid field site evaluation, there are very few sensitive, field-deployable analytical techniques. In this work, a portable lightweight capillary liquid chromatography (capLC) system was coupled with a small footprint portable mass spectrometer and configured for field-based applications. Further, an at-site ultrasound-assisted extraction (pUAE) methodology was developed and applied with a portable capLC/mass spectrometry (MS) system for on-site analysis of PFASs in real soil samples. The influential variables on the integration of capLC with MS and on the resolution and signal intensity of the capLC/MS setup were investigated. The important parameters affecting the efficiency of the pUAE method were also studied and optimized using the response surface methodology based on a central composite design. The mean recovery for 11 PFASs ranged between 70 and 110%, with relative standard deviations ranging from 3 to 12%. In-field method sensitivity for 12 PFASs ranged from 0.6 to 0.1 ng/g, with wide dynamic ranges (1-600 ng/g) and excellent linearities (R2 > 0.991). The in-field portable system was benchmarked against a commercial lab-based LC-tandem MS (MS/MS) system for the analysis of PFASs in real soil samples, with the results showing good agreement. When deployed to a field site, 12 PFASs were detected and identified in real soil samples at concentrations ranging from 8.1 ng/g (for perfluorooctanesulfonic acid) to 2935.0 ng/g (perfluorohexanesulfonic acid).