AGREEMIP: The Analytical Greenness Assessment Tool for Molecularly Imprinted Polymers Synthesis.

Molecular imprinting technology is well established in areas where a high selectivity is required, such as catalysis, sensing, and separations/sample preparation. However, according to the Principles of Green Chemistry, it is evident that the various steps required to obtain molecularly imprinted polymers (MIPs) are far from ideal. In this regard, greener alternatives to the synthesis of MIPs have been proposed in recent years. However, although it is intuitively possible to design new green MIPs, it would be desirable to have a quantitative measure of the environmental impact of the changes introduced for their synthesis. In this regard, this work proposes, for the first time, a metric tool and software (termed AGREEMIP) to assess and compare the greenness of MIP synthesis procedures. AGREEMIP is based on 12 assessment criteria that correspond to the greenness of different reaction mixture constituents, energy requirements, and the details of MIP synthesis procedures. The input data of the 12 criteria are transformed into individual scores on a 0-1 scale that in turn produce an overall score through the calculation of the weighted average. The assessment can be performed using user-friendly open-source software, freely downloadable from mostwiedzy.pl/agreemip. The assessment result is an easily interpretable pictogram and visually appealing, showing the performance in each of the criteria, the criteria weights, and overall performance in terms of greenness. The application of AGREEMIP is presented with selected case studies that show good discrimination power in the greenness assessment of MIP synthesis pathways.

Droplet-based luminescent sensor supported onto hydrophobic cellulose substrate for assessing fish freshness following smartphone readout.

In this work, two sensitive droplet-based luminescent assays with smartphone readout for the determination of trimethylamine nitrogen (TMA-N) and total volatile basic nitrogen (TVB-N) are reported. Both assays exploit the luminescence quenching of copper nanoclusters (CuNCs) produced when exposed to volatile nitrogen bases. In addition, hydrophobic-based cellulose substrates demonstrated their suitability as holders for both in-drop volatile enrichment and subsequent smartphone-based digitization of the enriched colloidal solution of CuNCs. Under optimal conditions, enrichment factors of 181 and 153 were obtained with the reported assays for TMA-N and TVB-N, respectively, leading to methodological LODs of 0.11 mg/100 g and 0.27 mg/100 g for TMA-N and TVB-N, respectively. The repeatability, expressed as RSD, was 5.2% and 5.6% for TMA-N and TVB-N, respectively (N = 8). The reported luminescent assays were successfully applied to the analysis of fish samples, showing statistically comparable results to those obtained with the reference methods of analysis.

Detection of gases and organic vapors by cellulose-based sensors.

The growing interest in the development of cost-effective, straightforward, and rapid analytical systems has found cellulose-based materials, including cellulose derivatives, cellulose-based gels, nanocellulosic materials, and the corresponding (nano)cellulose-based composites, to be valuable platforms for sensor development. The present work presents recent advances in the development of cellulose-based sensors for the determination of volatile analytes and derivatives of analytical relevance. In particular, strategies described in the literature for the fabrication and modification of cellulose-based substrates with responsive materials are summarized. In addition, selected contributions reported in the field of paper-based volatile sensors are discussed, with a particular emphasis on quick response (QR) code paper-based platforms, intelligent films for food freshness monitoring, and sensor arrays for volatile discrimination purposes. Furthermore, analytical strategies devised for the determination of ionic species by in situ generation of volatile derivatives in both paper-based analytical devices (PADs) and microfluidic PADs will also be described.

Waterproof Cellulose-Based Substrates for In-Drop Plasmonic Colorimetric Sensing of Volatiles: Application to Acid-Labile Sulfide Determination in Waters.

The present work reports on the assessment of widely available waterproof cellulose-based substrates for the development of sensitive in-drop plasmonic sensing approaches. The applicability of three inexpensive substrates, namely, Whatman 1PS, polyethylene-coated filter paper, and tracing paper, as holders for microvolumes of colloidal solutions was evaluated. Waterproof cellulose-based substrates demonstrated to be highly convenient platforms for analytical purposes, as they enabled in situ generation of volatiles and syringeless drop exposure unlike conventional single-drop microextraction approaches and can behave as sample compartments for smartphone-based colorimetric sensing in an integrated way. Remarkably, large drop volumes (≥20 µL) of colloidal solutions can be employed for enrichment processes when using Whatman 1PS as holder. In addition, the stability and potential applicability of spherical, rod-shaped, and core-shell metallic NPs onto waterproof cellulose-based substrates was evaluated. In particular, Au@AgNPs showed potential for the colorimetric detection of in situ generated H2S, I2, and Br2, whereas AuNRs hold promise for I2, Br2, and Hg0 colorimetric sensing. As a proof of concept, a smartphone-based colorimetric assay for determination of acid-labile sulfide in environmental water samples was developed with the proposed approach taking advantage of the ability of Au@AgNPs for H2S sensing. The assay showed a limit of detection of 0.46 µM and a repeatability of 4.4% (N = 8), yielding satisfactory recoveries (91-107%) when applied to the analysis of environmental waters.

Paper-Based Analytical Devices for Colorimetric and Luminescent Detection of Mercury in Waters: An Overview.

Lab-on-paper technologies, also known as paper-based analytical devices (PADs), have received increasing attention in the last years, and nowadays, their use has spread to virtually every application area, i.e., medical diagnostic, food safety, environmental monitoring, etc. Advantages inherent to on-field detection, which include avoiding sampling, sample preparation and conventional instrumentation in central labs, are undoubtedly driving many developments in this area. Heavy metals represent an important group of environmental pollutants that require strict controls due to the threat they pose to ecosystems and human health. In this overview, the development of PADs for Hg monitoring, which is considered the most toxic metal in the environment, is addressed. The main emphasis is placed on recognition elements (i.e., organic chromophores/fluorophores, plasmonic nanoparticles, inorganic quantum dots, carbon quantum dots, metal nanoclusters, etc.) employed to provide suitable selectivity and sensitivity. The performance of both microfluidic paper-based analytical devices and paper-based sensors using signal readout by colorimetry and luminescence will be discussed.

Assessing citric acid-derived luminescent probes for pH and ammonia sensing: A comprehensive experimental and theoretical study.

The present work reports on the assessment of luminescent probes derived from citric acid (CA) and ß-aminothiols (namely, l-cysteine (Cys) and cysteamine) for instrumental and smartphone-based fluorimetric sensing purposes. Remarkably, the evaluated luminescent probes derived from natural compounds showed pH-dependent dual excitation/dual emission features. Both fluorophores hold promise for the ratiometric fluorimetric sensing of pH, being especially convenient for the smartphone-based sensing of pH via ratiometric analysis by proper selection of B and G color channels. Time dependent density functional theory (TDDFT) calculations allowed to substantiate the pH dependent structure-property relationship and to unveil the critical role of the CA derived carboxyl group, these findings contributing to the fundamental knowledge on these systems for the rational design of new fluorophores and in establishing fluorescence sensing mechanisms of CA-derived systems. Besides, paper-based devices modified with CA-Cys were implemented in a three-phase separation approach for sensitive and selective ammonia sensing, yielding a remarkable enrichment factor of 389 and a limit of detection of 37 µM under optimal conditions. The proposed approach was successfully applied to the determination of ammonia nitrogen and extractable ammonium in water samples and marine sediments, respectively.

Miniaturized analytical methods for determination of environmental contaminants of emerging concern - A review.

The determination of contaminants of emerging concern (CECs) in environmental samples has become a challenging and critical issue. The present work focuses on miniaturized analytical strategies reported in the literature for the determination of CECs. The first part of the review provides brief overview of CECs whose monitoring in environmental samples is of particular significance, namely personal care products, pharmaceuticals, endocrine disruptors, UV-filters, newly registered pesticides, illicit drugs, disinfection by-products, surfactants, high technology rare earth elements, and engineered nanomaterials. Besides, an overview of downsized sample preparation approaches reported in the literature for the determination of CECs in environmental samples is provided. Particularly, analytical methodologies involving microextraction approaches used for the enrichment of CECs are discussed. Both solid phase- and liquid phase-based microextraction techniques are highlighted devoting special attention to recently reported approaches. Special emphasis is placed on newly developed materials used for extraction purposes in microextraction techniques. In addition, recent contributions involving miniaturized analytical flow techniques for the determination of CECs are discussed. Besides, the strengths, weaknesses, opportunities and threats of point of need and portable devices have been identified and critically compared with chromatographic methods coupled to mass chromatography. Finally, challenging aspects regarding miniaturized analytical methods for determination of CECs are critically discussed.

Nanomaterial-Integrated Cellulose Platforms for Optical Sensing of Trace Metals and Anionic Species in the Environment.

The development of disposable sensors that can be easily adapted to every analytical problem is currently a hot topic that is revolutionizing many areas of science and technology. The need for decentralized analytical measurements at real time is increasing for solving problems in areas such as environment pollution, medical diagnostic, food quality assurance, etc., requiring fast action. Despite some current limitations of these devices, such as insufficient detection capability at (ultra)trace level and risk of interferent effects due to matrix, they allow low-cost analysis, portability, low sample consumption, and fast response. In the last years, development of paper-based analytical devices has undergone a dramatic increase for on-site detection of toxic metal ions and other pollutants. Along with the great availability of cellulose substrates, the immobilization of receptors providing enhanced recognition ability, such as a variety of nanomaterials, has driven the design of novel sensing approaches. This review is aimed at describing and discussing the different possibilities arisen with the use of different nanoreceptors (e.g., plasmonic nanoparticles, quantum dots, carbon-based fluorescent nanoparticles, etc.) immobilized onto cellulose-based substrates for trace element detection, their advantages and shortcomings.

AGREE-Analytical GREEnness Metric Approach and Software.

Green analytical chemistry focuses on making analytical procedures more environmentally benign and safer to humans. The amounts and toxicity of reagents, generated waste, energy requirements, the number of procedural steps, miniaturization, and automation are just a few of the multitude of criteria considered when assessing an analytical methodology's greenness. The use of greenness assessment criteria requires dedicated tools. We propose the Analytical GREEnness calculator, a comprehensive, flexible, and straightforward assessment approach that provides an easily interpretable and informative result. The assessment criteria are taken from the 12 principles of green analytical chemistry (SIGNIFICANCE) and are transformed into a unified 0-1 scale. The final score is calculated based on the SIGNIFICANCE principles. The result is a pictogram indicating the final score, performance of the analytical procedure in each criterion, and weights assigned by the user. Freely available software makes the assessment procedure straightforward. It is open-source and downloadable from https://mostwiedzy.pl/AGREE.

Searching for Solvents with an Increased Carbon Dioxide Solubility Using Multivariate Statistics.

Ionic liquids (ILs) are used in various fields of chemistry. One of them is CO2 capture, a process that is quite well described. The solubility of CO2 in ILs can be used as a model to investigate gas absorption processes. The aim is to find the relationships between the solubility of CO2 and other variables-physicochemical properties and parameters related to greenness. In this study, 12 variables are used to describe a dataset consisting of 26 ILs and 16 molecular solvents. We used a cluster analysis, a principal component analysis, and a K-means hierarchical clustering to find the patterns in the dataset and the discriminators between the clusters of compounds. The results showed that ILs and molecular solvents form two well-separated groups, and the variables were well separated into greenness-related and physicochemical properties. Such patterns suggest that the modeling of greenness properties and of the solubility of CO2 on physicochemical properties can be difficult.

A paper-based gas sensor for simultaneous noninstrumental colorimetric detection of nitrite and sulfide in waters.

The use of paper-based devices in combination with noninstrumental detection systems is becoming increasingly important in the analytical field due to its simplicity, rapidity, and low cost. However, their use for determination of volatile analyte derivatives is still relatively scarce. The present work reports on the assessment of a paper-based gas-sensing approach for the simultaneous noninstrumental colorimetric detection of nitrite and sulfide. Colorimetric systems based on the Griess and methylene blue assays, formation of colored metallic sulfides, and interaction/reaction with in situ generated metallic nanoparticles were preliminary evaluated. Then, the effect of experimental variables affecting the analytical performance of the paper-based gas sensor was studied with two digitization systems, namely a scanner and a smartphone. Under optimal conditions, the developed system yielded limits of detection of 0.055 and 0.005 mg/L for nitrite and sulfide, respectively. The repeatability, expressed as relative standard deviation, was found to be 5.9 and 6.7% for nitrite and sulfide, respectively. The proposed method was finally applied to the analysis of water samples, showing recoveries in the range of 95-105%.

A paper-based colorimetric assay with non-instrumental detection for determination of boron in water samples.

The present work reports on the combination of paper-based analytical devices (PADs) and information technology (IT) equipment for non-instrumental determination of boron. PADs prepared with curcumin as a receptor and ethanolic extracts of Curcuma longa L. powder were evaluated for sensing. The colorimetric assay is based on a two step-strategy involving initially the formation of rosocyanin in the PAD under acidic conditions, with subsequent color change (from red to blue-green) at alkaline pH. The color change produced in the PAD is then exploited for determination of boron by digitization and image processing with IT devices (scanner and tablet camera) and an image analysis program, respectively. Under optimal conditions, the proposed assay showed limits of detection in the range 0.2-0.8 mg/L depending on the PADs and IT devices used for colorimetric reaction and digitization, respectively. In addition, the repeatability, expressed as relative standard deviation, was found to be below 5% (5 mg/L, N = 10). PADs prepared with curcumin and ethanolic extracts of Curcuma longa L. powder showed excellent lifetime and successful applicability to the analysis of water samples of different complexity with recoveries in the range 93-105%.

How green are ionic liquids? - A multicriteria decision analysis approach.

Due to various desirable physicochemical properties, ionic liquids (ILs) are still gaining in popularity. ILs have been recurrently considered green solvents. However, environmental, health and safety assessments of ILs have raised certain doubts about their benignness, and their greenness status is currently unclear. To clarify the situation on their greenness, we perform a comprehensive assessment of more than 300 commercially available ILs. We apply multicriteria decision analysis, the tool that allows ranking many alternatives according to relevant criteria. They are toxicity towards various organisms, biodegradability, hazard statements and precautionary measures during their handling. We incorporated organic solvents to rankings, as their greenness is better described, so they serve as greenness reference points. The ranking results obtained considering the whole set of criteria show that ILs are placed between recommended polar solvents and problematic/undesirable non polar organic solvents in terms of greenness. However, the exclusion of toxicity data due to unavailability of endpoints results in assessment of ILs as greener than most of organic solvents.

Speciation of gold nanoparticles and total gold in natural waters: A novel approach based on naked magnetite nanoparticles in combination with ascorbic acid.

A novel method for AuNPs/total Au speciation based on the combination of magnetic solid phase extraction and graphite furnace atomic absorption spectrometry (GFAAS) is described. Ascorbic acid enabled the quantitative extraction of both AuNPs and Au(III) by naked Fe3O4NPs, whereas a selective extraction of AuNPs was achieved in the presence of sodium thiosulfate. Experimental parameters influencing the extraction of both AuNPs and total Au, namely Fe3O4NPs mass, L-ascorbic acid concentration, pH, extraction time, sample volume, Na2S2O3 concentration and re-dispersion volume of magnetic solid phase prior to introduction in the graphite tube, were evaluated. Under optimal conditions, the proposed method yielded detection limits of 19.5 and 19.7 ng L-1 for AuNPs and Au(III), respectively. Intraday repeatability and inter-day reproducibility were lower than 5.3% (N = 6) and 7.6% (N = 4) for both species, respectively. Enrichment factors over 196, corresponding to extraction efficiencies higher than 98%, were obtained for both species. Remarkably, non-significant differences in the extraction of AuNPs over a wide range of AuNPs sizes and morphologies with different capping agents were observed. The reported method was applied to the analysis of superficial waters, groundwater, seawater and artificial wastewater with good recoveries. The method represents a suitable alternative to other reported methodologies for AuNPs quantification in environmental waters at (ultra)trace levels.

Expectation-Maximization Model for Substitution of Missing Values Characterizing Greenness of Organic Solvents.

Organic solvents are ubiquitous in chemical laboratories and the Green Chemistry trend forces their detailed assessments in terms of greenness. Unfortunately, some of them are not fully characterized, especially in terms of toxicological endpoints that are time consuming and expensive to be determined. Missing values in the datasets are serious obstacles, as they prevent the full greenness characterization of chemicals. A featured method to deal with this problem is the application of Expectation-Maximization algorithm. In this study, the dataset consists of 155 solvents that are characterized by 13 variables is treated with Expectation-Maximization algorithm to predict missing data for toxicological endpoints, bioavailability, and biodegradability data. The approach may be particularly useful for substitution of missing values of environmental, health, and safety parameters of new solvents. The presented approach has high potential to deal with missing values, while assessing environmental, health, and safety parameters of other chemicals.

Gold nanorods for in-drop colorimetric determination of thiomersal after photochemical decomposition.

This work reports on the implementation of gold nanorods (AuNRs) in headspace solvent microextraction for colorimetric determination of volatile analyte derivatives in a single drop. The exposure of AuNRs to both H2Se and elemental mercury (Hg0) results in a shift of the longitudinal plasmonic band, unlike a number of volatiles. Accordingly, a method is reported for the determination of Hg0 with potential applicability to the determination of thiomersal (sodium ethylmercurithiosalicylate). It is based on the photochemical decomposition of thiomersal into Hg(II) and subsequent exposure of AuNRs-containing microdrop to in situ generated Hg0. Colorimetric analysis of the enriched drop was carried out without dilution by means of a cuvetteless microvolume UV-vis spectrometer. Under optimal conditions, the limit of detection was 0.5 ng mL-1 (as Hg). The repeatability, expressed as relative standard deviation, was 8.4% (for n = 10). AuNRs exposed to increasing concentrations of the analyte were characterized by means of transmission electron microscopy and UV-vis spectrophotometry to ascertain the mechanism of detection. The method was finally applied to the determination of thiomersal in various pharmaceutical samples and showed quantitative recoveries. Graphical abstract Schematic illustration of a miniaturized colorimetric method based on the use of a microdrop of gold nanorods (AuNRs) for thiomersal determination in pharmaceuticals. It is based on the photochemical decomposition of thiomersal and subsequent Hg0 generation with in-drop amalgamation.

Test for arsenic speciation in waters based on a paper-based analytical device with scanometric detection.

A rapid, simple and affordable method for arsenic speciation analysis is described in this work. The proposed methodology involves in situ arsine generation, transfer of the volatile to the headspace and its reaction with silver nitrate at the detection zone of a paper-based analytical device (PAD). Thus, silver nitrate acts as a recognition element for arsine in the paper-based sensor. The chemical reaction between the recognition element and the analyte derivative results in the formation of a colored product which can be detected by scanning the detection zone and data treatment with an image processing and analysis program. Detection and injection zones were defined in the paper substrate by formation of hydrophobic barriers, thus enabling the formation of the volatile derivative without affecting the chemical stability of the recognition element present in the PAD. Experimental parameters influencing the analytical performance of the methodology, namely color mode detection, composition of the paper-based sensor and hydride generation and mass transfer conditions, were evaluated. Under optimal conditions, the proposed method showed limits of detection and quantification of 1.1 and 3.6 ng mL-1, respectively. Remarkably, the limit of detection of the method reported herein was much lower than the maximum contaminant levels set by both the World Health Organization and the US Environmental Protection Agency for arsenic in drinking water, unlike several commercially available arsenic test kits. The repeatability, expressed as relative standard deviation, was found to be 7.1% (n = 8). The method was validated against the European Reference Material ERM®-CA615 groundwater and successfully applied to the determination of As(III), As(V) and total inorganic As in different water samples. Furthermore, the method can be used for the screening analysis of total arsenic in waters when a cut-off level of 7 ng mL-1 is used.

Pre-selection and assessment of green organic solvents by clustering chemometric tools.

The study presents the result of the application of chemometric tools for selection of physicochemical parameters of solvents for predicting missing variables - bioconcentration factors, water-octanol and octanol-air partitioning constants. EPI Suite software was successfully applied to predict missing values for solvents commonly considered as "green". Values for logBCF, logKOW and logKOA were modelled for 43 rather nonpolar solvents and 69 polar ones. Application of multivariate statistics was also proved to be useful in the assessment of the obtained modelling results. The presented approach can be one of the first steps and support tools in the assessment of chemicals in terms of their greenness.

Headspace single-drop microextraction coupled with microvolume fluorospectrometry for highly sensitive determination of bromide.

This work reports on the development of a novel methodology for bromide determination by combining headspace single-drop microextraction with microvolume fluorospectrometry. The method lies in the in situ generation of bromine, transfer of the volatile to the headspace and trapping/reaction onto a fluorescein-containing aqueous drop exposed to the gas phase. The decrease in the fluorescence intensity enabled the determination of bromide without dilution of the enriched microdrop. Experimental parameters influencing the performance of the method, namely, fluorescence parameters, extractant phase composition, bromine generation conditions and microextraction time, were evaluated and controlled. Under optimal conditions, an enrichment factor of 243 was attained. The limits of detection and quantification achieved under optimal conditions for bromide were found to be 1.4 and 4.4µgL-1, respectively. The intra-day repeatability, expressed as relative standard deviation, was 4.4% (n=6). Besides, the inter-day reproducibility, performed at four different days, was 7.1%. Finally, the developed method was successfully applied to the determination of bromide in different water samples, showing recovery values in the range of 95-110%, and validated against certified reference material BCR-611 (ground water, Br- low level). The proposed method represents a highly convenient approach for monitoring of bromide at very low concentrations.

Liquid-phase microextraction combined with graphite furnace atomic absorption spectrometry: A review.

An overview of the combination of liquid-phase microextraction (LPME) techniques with graphite furnace atomic absorption spectrometry (GFAAS) is reported herein. The high sensitivity of GFAAS is significantly enhanced by its association with a variety of miniaturized solvent extraction approaches. LPME-GFAAS thus represents a powerful combination for determination of metals, metalloids and organometallic compounds at (ultra)trace level. Different LPME modes used with GFAAS are briefly described, and the experimental parameters that show an impact in those microextraction processes are discussed. Special attention is paid to those parameters affecting GFAAS analysis. Main issues found when coupling LPME and GFAAS, as well as those strategies reported in the literature to solve them, are summarized. Relevant applications published on the topic so far are included.