Critical Reviews in Analytical Chemistry

Natural carotenoids are secondary metabolites that exhibit antioxidant, anti-inflammatory, and anti-cancer properties. These types of compounds are highly demanded by pharmaceutical, cosmetic, nutraceutical, and food industries, leading to the search for new natural sources of carotenoids. In recent years, the production of carotenoids from bacteria has become of great interest for industrial applications. In addition to carotenoids with C40-skeletons, some bacteria have the ability to synthesize characteristic carotenoids with C30-skeletons. In this regard, a great variety of methodologies for the extraction and identification of bacterial carotenoids has been reported and this is the first review that condenses most of this information. To understand the diversity of carotenoids from bacteria, we present their biosynthetic origin in order to focus on the methodologies employed in their extraction and characterization. Special emphasis has been made on high-performance liquid chromatography-mass spectrometry (HPLC-MS) for the analysis and identification of bacterial carotenoids. We end up this review showing their potential commercial use. This review is proposed as a guide for the identification of these metabolites, which are frequently reported in new bacteria strains.

Saliva is one of the most critical human body fluids that can reflect the state of the human body. The detection of saliva is of great significance for disease diagnosis and health monitoring. Microfluidics, characterized by microscale size and high integration, is an ideal platform for the development of rapid and low-cost disease diagnostic techniques and devices. Microfluidic-based saliva testing methods have aroused considerable interest due to the increasing need for noninvasive testing and frequent or long-term testing. This review briefly described the significance of saliva analysis and generally classified the targets in saliva detection into pathogenic microorganisms, inorganic substances, and organic substances. By using this classification as a benchmark, the state-of-the-art research results on microfluidic detection of various substances in saliva were summarized. This work also put forward the challenges and future development directions of microfluidic detection methods for saliva.

Peptides and proteins having D-amino acids in their sequences are now believed to be widespread among different living organisms. Their significance is attributed to the diverse functions of these molecules, such as having a certain pathological implication or enhancing biological activity. Indeed, some peptide molecules with D-amino acids in their structure have already found their way to clinical use such as the antibacterial gramicidin and the antidiabetic nateglinide. Ion mobility mass spectrometry (IM-MS) added an additional dimension of separation as it depends on ions mobility in the space, which is dependent on their shapes, and the shape depends on the orientation of atoms. Thus, D-amino acids containing peptides (DAACPs) will have different mobility and collision cross-section values than those with L-amino acids. Eventually, this will lead to baseline separation of the two peptides. Additionally, ion mobility can precisely locate the position of D-amino acids by analyzing the difference in the arrival times of the fragment ions. The importance of DAACPs, as well as the difficulties in discovering them, were addressed in this review. Similarly, we emphasized how recent developments in IM-MS have improved their detection and analysis. Consequently, the LC-IM-MS/MS platform appears to be promising in isomeric mixture analysis.

Chronological sequencing of ink strokes has been a challenge for the Forensic Document Examiners (FDE). Document forgery is a common practice and the ability to determine the order in which the primary and the subsequent strokes have been made is crucial for establishing the authenticity of a document. Lately, the prime thrust of establishing the sequence of intersection of ink lines has shifted from an optical to an analytical approach. Several studies have been reported to explore the use of spectroscopic techniques in determining the sequence of ink strokes made using gel pen inks, ball pen inks, fountain inks, printed ink, stamp inks, etc. The present study aims to study the existing trends in examining the sequence of ink strokes or crossing of lines using vibrational spectroscopic techniques viz. Infrared and Raman Spectroscopy. Several interesting inferences have been drawn, such as factors like paper type and time gap between the application of two intersecting strokes does not influence the determination of the sequence of inter-crossing strokes. A trend of using two analytical techniques viz. VSC, AFM, HPTLC, TOF-SIMS, and SEM/EDX with vibrational spectroscopic techniques have been found to provide reliable results. The study also suggests future research directions in the field, aiming to address challenges faced by the FDEs and provide accurate and reliable solutions for document examination.

The main difficulties when analyzing pharmaceutically active compounds (PhACs) in solid environmental samples is the complexity of the samples and the low concentration levels of such pollutants. Most efforts are focused in achieving good analytical performance parameters such as high recoveries or low detection limits without considering if the methods are environmentally friendly. In this work, the main tools proposed for assessing the greenness of analytical methodologies (Analytical Eco-scale, Green Analytical Procedure Index (GAPI), and Analytical GREEnness metric (AGREE)) have been applied to nine analytical procedures that include recent important analytical tendencies. The three metrics identified the paper spray ionization method as the greenest procedure since it used untreated samples for direct mass spectrometry analysis. Using Analytical Eco-scale, most of the evaluated procedures were rated as "acceptable green". However, the use of internal standards resulted key in the environmental impact of the method which provided contradictory results versus other metrics. GAPI found greenness similarities between most of selected methods, hindering a greenness classification. AGREE allowed the weighting of each evaluation criterion providing a greenness ranking. The application of each metric detecting their weaknesses and strengths was discussed. The incorporation of validation analytical features in greenness metrics was a gap revealed.

Sensitive and rapid determination of foodborne pathogenic bacteria is of practical importance for the control and prevention of foodborne illnesses. Nowadays, with the prosperous development of fluorescence assays, fluorescence resonance energy transfer (FRET)-derived diagnostic strategies are extensively employed in quantitative analysis of different pathogenic bacteria in food-related matrices, which displays a rapid, simple, stable, reliable, cost-effective, selective, sensitive, and real-time way. Considering the extensive efforts that have been made in this field so far, we here discuss the up-to-date developments of FRET-based diagnostic approaches for the determination of key foodborne pathogens like Staphylococcus aureus, Escherichia coli, Vibrio parahaemolyticus, Salmonella spp., Campylobacter spp., and Bacillus cereus in complex food-related matrices. Moreover, the principle of this technology, the choosing standards of acceptor-donor pairs, and the fluorescence properties are also profiled. Finally, the current prospects and challenges in this field are also put forward.

Mass spectrometry (MS) has become an attractive analytical method in clinical analysis due to its comprehensive advantages of high sensitivity, high specificity and high throughput. Separation techniques coupled MS detection (e.g., LC-MS/MS) have shown unique advantages over immunoassay and have developed as golden criterion for many clinical applications. This review summarizes the characteristics and applications of MS, and emphasizes the high efficiency of MS in clinical research. In addition, this review also put forward further prospects for the future of mass spectrometry technology, including the introduction of miniature MS instruments, point-of-care detection and high-throughput analysis, to achieve better development of MS technology in various fields of clinical application. Moreover, as ambient ionization mass spectrometry (AIMS) requires little or no sample pretreatment and improves the flux of MS, this review also summarizes its potential applications in clinic.

Flavonoids are plant-derived compounds that have several health benefits, including antioxidative, anti-inflammatory, anti-mutagenic, and anti-carcinogenic effects. Quercetin is a flavonoid that is widely present in various fruits, vegetables, and drinks. Accurate determination of quercetin in different samples is of great importance for its potential health benefits. This review, is an overview of sample preparation and determination methods for quercetin in diverse matrices. Previous research on sample preparation and determination methods for quercetin are summarized, highlighting the advantages and disadvantages of each method and providing insights into recent developments in quercetin sample treatment. Various analytical techniques are discussed including spectroscopic, chromatographic, electrophoretic, and electrochemical methods for the determination of quercetin and its derivatives in different samples. UV-Vis (Ultraviolet-visible) spectrophotometry is simple and inexpensive but lacks selectivity. Chromatographic techniques (HPLC, GC) offer selectivity and sensitivity, while electrophoretic and electrochemical methods provide high resolution and low detection limits, respectively. The aim of this review is to comprehensively explore the determination methods for quercetin and quercetin glycosides in diverse matrices, with emphasis on pharmaceutical and biological samples. The review also provides a theoretical basis for method development and application for the analysis of quercetin and quercetin glycosides in real samples.

Digital recombinase polymerase amplification (dRPA) aims to quantify the initial amount of nucleic acid by dividing nucleic acid and all reagents required for the RPA reaction evenly into numerous individual reaction units, such as chambers or droplets. dRPA turns out to be a prominent technique for quantifying the absolute quantity of target nucleic acid because of its advantages including low equipment requirements, short time consumption, as well as high sensitivity and specificity. dRPA combined with microfluidics are recognized as simple, various, and high-throughput nucleic acid quantization systems. This paper classifies the microfluidic dRPA systems over the last decade. We analyze and summarize the vital technologies of various microfluidic dRPA systems (e.g., chip preparation process, segmentation principle, microfluidic control, and statistical analysis methods), and major efforts to address limitations (e.g., prevention of evaporation and contamination, accurate initiation, and reduction of manual operation). In addition, this paper summarizes key factors and potential constraints to the success of the microfluidic dRPA to help more researchers, and possible strategies to overcome the mentioned challenges. Lastly, actual suggestions and strategies are proposed for the subsequent development of microfluidic dRPA.

Interculturally, corrosion has been counted as one of the most expensive factors toward the retrogression of concrete and metallic structures resulting in huge monetary losses and unanticipated loss of life. To a large extent, corrosion-related catastrophes can be avoided by having the ability to monitor corrosion before structural integrity is jeopardized. This paper critically reviews the various accustomed electrochemical techniques utilized for corrosion monitoring in terms of their definition, timeline, experimental set-up, advantages, and shortcomings. Additionally, literature exploiting these techniques as their corrosion detection technique has been focused on here. Furthermore, a comparison between recently reported methods has been made to provide better insights into the research progress in this arena.

Replacing conventional solvents with deep eutectic solvents (DES) has shown promising effects on the extraction yield of (poly)phenols. DES can be combined with ultrasound-assisted extraction (UAE) to further increase the extraction efficiency of (poly)phenols from natural resources compared to conventional methods. This review discusses the factors associated with DES (composition, solvent-to-sample ratio, extraction duration, and temperature) and UAE (ultrasound frequency, power, intensity, and duty cycle) methods that influence the extraction of (poly)phenols and informs future improvements required in the optimization of the extraction process. For the optimum (poly)phenol extraction from natural resources, the following parameters shall be considered: ultrasound frequency should be in the range of 20–50 kHz, ultrasound intensity in the range of 60–120 W/cm2, ultrasound duty cycle in the range of 40–80%, ultrasound duration for 10–30 minutes, and ultrasound temperature for 25–50 °C. Among the reported DES systems, choline chloride with glycerol or lactic acid, with a solvent-to-sample mass ratio of 10–30:1 shown to be effective. The solvent composition and solvent-to-sample mass ratio should be selected according to the target compound and the source material. However, the high viscosity of DES is among the major limitations. Optimizing these factors can help to increase the yield of extracted (poly)phenols and their applications.

Multimodal imaging (MMI) has emerged as a powerful tool in clinical research, combining different imaging modes to acquire comprehensive information and enabling scientists and surgeons to study tissue identification, localization, metabolic activity, and molecular discovery, thus aiding in disease progression analysis. While multimodal instruments are gaining popularity, challenges such as non-standardized characteristics, custom software, inadequate commercial support, and integration issues with other instruments need to be addressed. The field of multimodal imaging or multiplexed imaging allows for simultaneous signal reproduction from multiple imaging strategies. Intraoperatively, MMI can be integrated into frameless stereotactic surgery. Recent developments in medical imaging modalities such as magnetic resonance imaging (MRI), and Positron Emission Topography (PET) have brought new perspectives to multimodal imaging, enabling early cancer detection, molecular tracking, and real-time progression monitoring. Despite the evidence supporting the role of MMI in surgical decision-making, there is a need for comprehensive studies to validate and perform integration at the intersection of multiple imaging technologies. They were integrating mass spectrometry-based technologies (e.g., imaging mass spectrometry (IMS), imaging mass cytometry (IMC), and Ion mobility mass spectrometry ((IM-IM) with medical imaging modalities, offering promising avenues for molecular discovery and clinical applications. This review emphasizes the potential of multi-omics approaches in tissue mapping using MMI integrated into desorption electrospray ionization (DESI) and matrix-assisted laser desorption ionization (MALDI), allowing for sequential analyses of the same section. By addressing existing knowledge gaps, this review encourages future research endeavors toward multi-omics approaches, providing a roadmap for future research and enhancing the value of MMI in molecular pathology for diagnosis.

Hydrazine, as a crucial raw material in the fine chemical industry, plays an indispensable role in fuel, catalyst, pesticide and drug synthesis. Due to its good water solubility and high toxicity, hydrazine can cause irreparable damage to water and soil in the environment, and it can also be released by taking certain drugs, which brings potential risks to human health. Therefore, it is vital to develop a method that can specifically detect hydrazine in the environment and in vivo. As an effective analysis and detection tool, fluorescence probe has attracted extensive attention in recent years. In this review, we summarized and classified hydrazine fluorescence probes based on various reaction mechanisms, and discussed their structures and applications in the past ten years. At least, we briefly outline the challenges and prospects in this field.

Phospholipids (PhLs) are essential components of cell membranes, characterized by a hydrophobic tail and a hydrophilic headgroup. They play several roles in biological systems, including energy storage, protection, and antioxidant properties. PhLs are found naturally in foods such as egg yolks, milk, or vegetable oils. The composition and concentration of PhLs observed in these foods vary according to the analytical methodology applied, mainly in the extraction and sample treatment process. Analytical targeted approaches for characterized PhLs involve liquid chromatography and mass spectrometry techniques. These methods provide insights into the composition and content of PhLs in food matrices. However, there is limited research on using PhL profiles for food quality evaluation and authentication purposes. Untargeted approaches, such as fingerprinting, have the potential to assess the authenticity of food products by capturing analytical signals linked to the PhL fraction. This review focusses on recent analytical strategies used in characterizing PhLs in distinctive foodstuffs (eggs, milk, and vegetable oils). It discusses sample preparation, analytical separation, and detection techniques. The review also highlights the potential of multivariate approaches to incorporate information on PhL composition to assess the authenticity of food products, an area that has been largely overlooked in previous studies.

Recently, organic sensors for the detection of Ag+ and other metal ions have experienced significant advancements. This is because there is a growing demand for reliable and sensitive tools to monitor various environmental pollutants. Organic sensors have O-, S-, and N-donor atoms, which can act as a ligand and coordinate with different metal ions, hence stabilizing them in a variety of oxidation states. This interaction gives colorimetric and fluorescence changes, which are used to monitor Ag+ and other metal ions. This comprehensive review highlights the latest developments in organic sensors for the recognition of Ag+. We present an in-depth analysis of the underlying principles and mechanisms governing Ag+ ion recognition. Various organic sensing platforms, such as fluorescent and colorimetric sensors, are discussed, shedding light on their unique advantages and limitations. Special attention is given to the diverse range of organic ligands, receptors, and functional materials used to achieve high sensitivity, selectivity, and quantification accuracy. Additionally, we delve into real-world applications of organic sensors for Ag+ ion detection, examining their performance in complex matrices such as biological, environmental, industrial and agricultural matrices.

Lipids, as one of the most important organic compounds in organisms, are important components of cells and participate in energy storage and signal transduction of living organisms. As a rapidly rising field, lipidomics research involves the identification and quantification of multiple classes of lipid molecules, as well as the structure, function, dynamics, and interactions of lipids in living organisms. Due to its inherent high selectivity and high sensitivity, mass spectrometry (MS) is the "gold standard" analysis technique for small molecules in biological samples. The combination chemical derivatization with MS detection is a unique strategy that could improve MS ionization efficiency, facilitate structure identification and quantitative analysis. Herein, this review discusses derivatization-based MS strategies for lipidomic analysis over the past decade and focuses on all the reported lipid categories, including fatty acids and modified fatty acids, glycerolipids, glycerophospholipids, sterols and saccharolipids. The functional groups of lipids mainly involved in chemical derivatization include the C=C group, carboxyl group, hydroxyl group, amino group, carbonyl group. Furthermore, representative applications of these derivatization-based lipid profiling methods were summarized. Finally, challenges and countermeasures of lipid derivatization are mentioned and highlighted to guide future studies of derivatization-based MS strategy in lipidomics.

Catecholamines (CAs), including adrenaline, noradrenaline, and dopamine, are neurotransmitters and hormones that play a critical role in regulating the cardiovascular system, metabolism, and stress response in the human body. As promising methods for real-time monitoring of catecholamine neurotransmitters, LC-MS detectors have gained widespread acceptance and shown significant progress over the past few years. Other detection methods such as fluorescence detection, colorimetric assays, surface-enhanced Raman spectroscopy, and surface plasmon resonance spectroscopy have also been developed to varying degrees. In addition, efficient pretreatment technology for CAs is flourishing due to the increasing development of many highly selective and recoverable materials. There are a few articles that provide an overview of electrochemical detection and efficient enrichment, but a comprehensive summary focusing on analytical detection technology is lacking. Thus, this review provides a comprehensive summary of recent analytical detection technology research on CAs published between 2017 and 2022. The advantages and limitations of relevant methods including efficient pretreatment technologies for biological matrices and analytical methods used in combination with pretreatment technology have been discussed. Overall, this review article provides a better understanding of the importance of accurate CAs measurement and offers perspectives on the development of novel methods for disease diagnosis and research in this field.

Pesticides have an important role in rising the overall productivity and yield of agricultural foods by eliminating and controlling insects, pests, fungi, and various plant-related illnesses. However, the overuse of pesticides has caused pesticide pollution of water bodies and food products, along with disruption of environmental and ecological systems. In this regard, developing low-cost, simple, and rapid-detecting approaches for the accurate, rapid, efficient, and on-site screening of pesticide residues is an ongoing challenge. Electrochemiluminescence (ECL) possesses the benefits of great sensitivity, the capability to resolve several analytes using different emission wavelengths or redox potentials, and excellent control over the light radiation in time and space, making it a powerful strategy for sensing various pesticides. Cost-effective and simple ECL systems allow sensitive, selective, and accurate quantification of pesticides in agricultural fields. Particularly, the development and progress of nanomaterials, aptamer/antibody recognition, electric/photo-sensing, and their integration with electrochemiluminescence sensing technology has presented the hopeful potential in reporting the residual amounts of pesticides. Current trends in the application of nanoparticles are debated, with an emphasis on sensor substrates using aptamer, antibodies, enzymes, and molecularly imprinted polymers (MIPs). Different strategies are enclosed in labeled and label-free sensing along with luminescence determination approaches (signal-off, signal-on, and signal-switch modes). Finally, the recent challenges and upcoming prospects in this ground are also put forward.

Pesticides are applied widely to increase agricultural output and quality, however, this practice results in residual issues that not only harm the environment but also put people and animals' lives and health at risk. As a result, it is critical to find pesticide residues in a variety of sources, including crops, water supplies, and soil. Aptamers are more flexible in their synthesis and modification, have a high level of specificity, are inexpensive, and have good stability compared to conventional detection methods. They have therefore attracted a lot of interest in the industry. This study reviews the most recent aptasensor advancements in the detection of pesticide residues. Firstly, aptamers specifically binding to many pesticides are summarized. Secondly, the combination of aptasensors with colorimetric, fluorescent, surface enhanced Raman spectroscopy (SERS), resonance Light Scattering (RLS), chemiluminescence (CL), electrochemical, and electrochemiluminescence (ECL) technologies are systematically introduced, and their advantages and disadvantages are expounded. Importantly, the aptasensors for the detection of various pesticides (organochlorine, organophosphorus, neonicotinoids, carbamates, and pyrethroids) that have been developed so far are systematically analyzed and discussed. Finally, the furture prospects and challenges of the aptasensors are highlighted. It is expected to offer suggestions for the later creation of novel, highly effective and sensitive aptasensors for the detection of pesticide residues.

Hydrogen peroxide (H2O2) has an important role in living organisms, and its detection is of great importance in medical, chemical, and food safety applications. This review provides a comparison of different types of Surface-enhanced Raman scattering (SERS) sensors for H2O2 and related substances with respect to their detection limits, which are of interest due to high sensitivity compared to conventional sensors. According to the latest research report, this review focuses on the sensing mechanism of different sensors and summarizes the linear range, detection limits, and cellular applications of new SERS sensors, and discusses the limitations in vivo and future prospects of SERS technology for the detection of H2O2.

Retention prediction through Artificial intelligence (AI)-based techniques has gained exponential growth due to their abilities to process complex sets of data and ease the crucial task of identification and separation of compounds in most employed chromatographic techniques. Numerous approaches were reported for retention prediction in different chromatographic techniques, and consistent results demonstrated that the accuracy and effectiveness of deep learning models outclassed the linear machine learning models, mainly in liquid and gas chromatography, as ML algorithms use fewer complex data to train and predict information. Support Vector machine-based neural networks were found to be most utilized for the prediction of retention factors of different compounds in thin-layer chromatography. Cheminformatics, chemometrics, and hybrid approaches were also employed for the modeling and were more reliable in retention prediction over conventional models. Quantitative Structure Retention Relationship (QSRR) was also a potential method for predicting retention in different chromatographic techniques and determining the separation method for analytes. These techniques demonstrated the aids of incorporating QSRR with AI-driven techniques acquiring more precise retention predictions. This review aims at recent exploration of different AI-driven approaches employed for retention prediction in different chromatographic techniques, and due to the lack of summarized literature, it also aims at providing a comprehensive literature that will be highly useful for the society of scientists exploring the field of AI in analytical chemistry.

Soil is one type of Earth material demonstrating a wide range of physical, chemical, and biological properties. As the compositional profile of soil is a product of interaction between numerous abiotic and biotic components, it tends to be unique by its geographic origin. Hence, soil is paramount for predicting source or origin in forensic provenance and intelligence, food provenance, biosecurity, and archaeology. In the context of forensic investigation, source tracing of soil could be executed by a comparison or provenance analysis. Soil compositional fingerprints acquired using analytical methods must be carefully interpreted via suitable mathematical and statistical tools since multiple sources can contribute to the variability of soil other than its provenance. This article reviews recent trends in soil sampling and data interpretation strategies proposed for source tracing of soil evidence. Performances of soil provenance indicators are also described. Then, perspectives on possible research directions guiding forensic soil provenance are proposed. This timely critical review reveals the essential idea and gap in forensic soil provenance for stimulating the development of more efficient and effective provenance strategies.

The need for consistency in analytical method development reinforces the dependence of pharmaceutical product development and manufacturing on robust analytical data. The Analytical Quality by Design (AQbD), akin to the product Quality by Design (QbD) endows a high degree of confidence to the method quality developed. AQbD involves the definition of the analytical target profile as starting point, followed by the identification of critical method variables and critical analytical attributes, supported on risk assessment and design of experiment tools for the establishment of a method operable design region and control strategy of the method. This systematic approach moves away from reactive troubleshooting to proactive failure reduction. The objective of this review is to highlight the elements of the AQbD framework and provide an overview of their implementation status in various analytical methods used in the pharmaceutical field. These methodologies include but are not limited to, high-performance liquid chromatography, UV-Vis spectrophotometry, capillary electrophoresis, supercritical fluid chromatography, and high-performance thin-layer chromatography. Finally, a critical appraisal is provided to highlight how regulators have encouraged AQbD principles application to boost the prevention of method failures and a better understanding of the method operable design region (MODR) and control strategy, ultimately resulting in cost-effectiveness and regulatory flexibility.