Greener derivatization in analytical chemistry Lavilla, I.; Romero, V.; Costas, I. ...
TrAC, Trends in analytical chemistry (Regular ed.),
October 2014, 2014-10-00, Letnik:
61
Journal Article
Recenzirano
•We review different strategies for achieving greener derivatization procedures.•We emphasize less hazardous reagents and solvents and more efficient energy.•We consider alternative media to ...classical organic solvents.•We discuss alternative forms of energy for activating derivatization processes.
Principle 8 of Green Chemistry recommends eliminating derivatization, yet it is difficult to fulfill in analytical chemistry, so we consider the design of environment-friendly derivatization procedures in this article. We provide an overview on the main strategies for achieving greener derivatization procedures, emphasizing the use of less hazardous reagents and solvents and more efficient forms of energy. We consider using alternative media, such as water, bio-derived solvents, natural deep eutectic solvents, supercritical fluids, ionic liquids and organic solvents instead of classical undesirable solvents. We highlight derivatization with natural compounds and enzymes. We also discuss use in derivatization of different forms of energy, such as microwaves, ultrasound, photochemical or electrochemical. We present numerous examples where the overall green profile of the analytical methodology can be enhanced by focusing on the derivatization steps.
The combination of post-column derivatization (PCD) and liquid chromatography (LC) has become a promising technique for enhancing detection sensitivity and selectivity, while simultaneously ...facilitating rapid and automated analysis. This paper presents a comprehensive review of PCD techniques spanning from 2013 to 2023, focusing on LC-UV-Vis/fluorescence spectrometry and LC-mass spectrometry detection methods. It encompasses an array of PCD methods, including chemical, photochemical, and electrochemical derivatization, as well as post-column complexation. This review delves deeply into key areas, exploring the underlying principles of derivatization, examining the current applications of classical PCD methods, and shedding light on emerging derivatization reactions. The review also provides remarks and insights into future directions, offering a perspective on the evolving landscape of the field. The overarching goal is to equip researchers with innovative ideas and strategies for PCD, thereby enhancing the practical application and utility of this technology in scientific research.
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•LC coupled PCD enhances detection sensitivity/selectivity.•Chemical/photochemical/electrochemical reactions and complexation are the main methods.•Advances in post-column derivatization techniques from 2013 to 2023 are reviewed.•Principles of derivatization reaction and their applications are examined.•Insights on future trends advancing post-column derivatization research are offered.
•A convenient and efficient workflow for absolute quantification of carboxyl submetabolome was established based on the DEABA-labeled polarity-response-homodispersed strategy.•Carboxyl submetabolome ...profiling in the whole course of hepatocellular carcinoma was monitored.•Combined with analysis of variance (ANOVA), orthogonal partial least squares discrimination analysis (OPLS-DA) and Bayesian linear discriminant analysis (BLDA), the biomarkers were screened out and the diagnostic model was established.
Recent studies have shown that dysregulation of carboxyl submetabolome homeostasis is closely related to the occurrence and development of hepatocellular carcinoma (HCC). However, it is still a challenge to quantify carboxyl metabolites with high efficiency by conventional methods due to their species diversity and nature differences. Moreover, there are few studies on carboxyl submetabolome profiling during the whole progression of HCC. In this study, a convenient and efficient workflow for absolute quantification of carboxyl submetabolome was established based on the 4-(diethylamino)-butylamine (DEABA)-labeled polarity-response-homodispersed strategy. After optimizing derivation conditions with response surface methodology (RSM), the reaction only needed 1 min at room temperature, which radically simplified the labeling process. Compared with nonderivatization, the gaps of polarities and responses of the analytes were narrowed by DEABA labeling, realizing the polarity-response-homodispersion. Then resolution and sensitivity in HPLC-MS/MS were improved significantly. Ultimately, the workflow was applied to monitor carboxyl metabolic profile in human plasma of the whole progressive course of hepatocellular carcinoma. Combined with analysis of variance (ANOVA), orthogonal partial least squares discrimination analysis (OPLS-DA), Bayesian linear discriminant analysis (BLDA) and other data mining methods, the biomarkers of “health-hepatitis-cirrhosis-HCC” were screened out, and the diagnostic model was established. Furthermore, the relevancy between carboxyl submetabolome disorders and the pathogenesis of HCC was investigated. The developed method has the characteristics of high sensitivity, high coverage and high practicability, which is suitable for the study of biomarkers of carboxyl submetabolome in the whole progression of HCC.
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•Review of HPLC-PCD applied to food analysis.•Coverage of twenty years of research in the field.•Various classes of compounds/analytes are included.•Legislation issues are also discussed.•Sample ...preparation for each class of compounds is included.
High performance liquid chromatography coupled with post–column derivatization is used for increasing the sensitivity and selectivity of the desirable analytes after the chromatographic separation. The transformation of the analytes can be conducted through the addition of a suitable reagent in the eluted stream or the ultraviolet irradiation of the eluted analytes, forming detectable derivatives for ultraviolet or fluorescence detectors. This review focuses on the developed methods using high performance liquid chromatography coupled with post-column derivatization for the determination of substances in food samples during the last two decades. The significance of the determination of each analyte in foods and the existing guidelines in each case are discussed. Preparation of the samples and the analytical methods are commented. For each analyte, official methods and commercially available systems and reagents are mentioned, as well.
DLLME is widely used as a sample preparation technique due to its unique advantages of fast extraction, low solvent consumption, high enrichment factors, and low cost. DLLME extracts are generally ...analyzed by gas or liquid chromatography coupled with different detection systems. However, GC or LC cannot analyze/separate many analytes due to their structural properties. Similarly, some of the analytes are not sensitive to commonly used detectors. In such cases, a derivatization process (chemical conversion) is often applied to improve the structural features of the analytes to make them compatible with separation and/or detection system. The coupling of derivatization with DLLME is a simple way to accomplish the job using minimum volumes of the derivatizing reagents and reducing their impact on workers and the environment. This review explains the different modes of DLLME coupled derivatizations, their applications, and green aspects in a systematic way.
•Sample preparation methods describing DLLME coupled with derivatization are discussed.•Different modes of DLLME coupled derivatizations and their objectives are discussed.•Applications of different modes of DLLME coupled derivatizations are presented with examples.•The green features of DLLME coupled derivatizations are critically appraised.
Gas chromatography is a widely used analytical technique found in many laboratories around the world. However, not all analytes of interest can be directly analysed by gas chromatography, e.g., low ...volatility, asymmetric peaks, or thermolabile nature. In such situations, analytical derivatization, despite being a time-consuming and cumbersome extra step in sample preparation, is required to make analytes more suitable for gas chromatographic analysis by improving their volatility, thermal stability, and detectability. Injector port derivatization takes place in a heated gas chromatography injection port; the technique has broad applications in food, biomedical, and environmental analysis. It is easy to apply in analytical development processes, has a high efficiency of derivatization, and requires fewer hazardous chemical reagents in less quantity. This review aims to cover recent applications of injector port derivatization techniques published within the last ten years to facilitate injector port derivatization in analytical method development applications.
•An up-to-date review on injector port derivatization presented.•Recent injector port derivatization applications discussed.•Injector port derivatization compared with other derivatization approaches.•Limitations and advantages of the injection port derivatization are presented.•Compatible extraction methods for injection port derivatization were discussed.
Because of great diversity of chemical and physical properties and wide ranges of concentrations of different metabolites in metabolome samples, metabolome analysis is a challenging task. Compromises ...in coverage, quantification accuracy and sample throughput are often used to provide a sufficient amount of metabolomic information for a biological or clinical application. Chemical derivatization of metabolites offers an opportunity to improve the overall analytical performance of liquid chromatography mass spectrometry (LC-MS)-based metabolomics. This review highlights recent progresses (since 2016) in the field of chemical derivatization LC-MS for both targeted and untargeted metabolome analysis. Due to increased recognition of the benefits of derivatization in LC-MS metabolome analysis, many research groups have been involved in advancing this active research field. Due to space limitation, we selected a few examples of recently reported derivatization methods and applications to showcase the advantages of chemical derivatization, compared to conventional label-free methods.
•Metabolome analysis is not easy due to chemical/physical diversity of metabolites.•Derivatization can improve metabolite separation, detection and identification.•Labeling reagents targeting different chemical groups have been reported.•Performance of reagents for targeted and untargeted metabolomics varies greatly.•Improved performance often outweighs the inconvenience of doing derivatization.
The step‐economical late‐stage diversification of tryptophan‐containing peptides was accomplished through chemo‐ and site‐selective palladium‐catalyzed CH arylation under exceedingly mild reaction ...conditions. Thus, the CH functionalization occurred efficiently at 23 °C with a catalyst loading as low as 0.5 mol %, and/or in H2O.
CH arylation of oligopeptides was achieved in aqueous media under exceedingly mild reaction conditions. The chemo‐ and site‐selective nature of the late‐stage diversification protocol illustrates the potential of our strategy for peptide ligation and fluorescence labeling (see scheme).
•Overview of solid-phase analytical derivatization in environmental analysis.•Pros and cons of solid-phase analytical derivatization methods.•Challenges and future directions of solid-phase ...analytical derivatization.
The increased accumulation of organic pollutants in various ecological systems in recent decades is a growing concern since these pollutants have detrimental effects on humans, animals, and plants. Two major contributing factors are pharmaceuticals and industrial waste chemicals from anthropogenic sources. To better understand the hazards environmental pollutants, represent to living beings, it is essential to develop sensitive, rapid, and reliable analytical methods. A subset of functional group analysis termed "analytical derivatization" modifies an analyte's structure to make it better suited for chromatographic analysis. Despite being an extra time-consuming step in sample preparation, analytical derivatization improves sensitivity, chromatographic separation, and selectivity in analytical method development. Solid-phase analytical derivatization, which combines extraction and derivatization steps, satisfies many requirements for an efficient sample preparation technique, which include reduced organic solvent usage, low cost, simplicity in automation with gas and liquid chromatographic systems, and applicability in a wide range of complex sample matrices. The focus of this review is on solid-phase analytical derivatization methodologies applied to analytical method development in environmental analysis, such as monitoring air pollution, water quality, and soil matrices. This review discusses the benefits and drawbacks of the solid-phase analytical derivatization approach in environmental analysis, the challenges ahead, and potential applications.
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A convenient and effective protocol for the ruthenium‐catalyzed C–H selenylations of benzamide was achieved under mild reaction conditions. The robust ruthenium catalyst tolerated a wide range of ...functional groups and set the stage for the preparation for diversely decorated benzamides. The amide directing group could be transferred to carboxylic acid, aldehyde and tetrazoles. Preliminary mechanistic study indicated a base‐assisted electrophilic‐type substitution C–H activation event.
The easily transformable amide directing groups assisted ortho‐C–H selenylations of arenes with 1,2‐diphenyldiselane by robust ruthenium catalyst were achieved with ample scope under mild reaction conditions. This general approach offered a straightforward access to various functional group substituted diarylselenide containing compounds. The plausible mechanism was proposed after the detailed mechanistic studies.
