•Overview of analytical derivatizations methods.•Pros and cons of analytical derivatization methods in environmental analysis.•Challenges and future directions of derivatization method in ...environmental analysis.
Analytical derivatization is a technique that alters the structure of an analyte and produces a product more suitable for analysis. While this process can be time-consuming and add reagents to the procedure, it can also facilitate the isolation of the analyte(s), enhance analytes’ stability, improve separation and sensitivity, and reduce matrix interferences. Since derivatization is a functional group analysis, it improves selectivity by separating reactive from neutral compounds during sample preparation. This technique introduces detector-orientated tags into analytes that lack suitable physicochemical properties for detection at low concentrations. Notably, many regulatory bodies, especially those in the environmental field, require these characteristics in analytical methods. This review focuses on note-worthy analytical derivatization methods employed in environmental analyses with functional groups, phenol, carboxylic acid, aldehyde, ketone, and thiol in aqueous, soil, and atmospheric sample matrices. Both advantages and disadvantages of analytical derivatization techniques are discussed. In addition, we discuss the future directions of analytical derivatization methods in environmental analysis and the potential challenges.
With a notable rise in the consumption of commercial baby foods in recent years, there is a pressing need for a rapid and efficient method to analyze the levels of nitrate and nitrite in these ...products. In the present study, we have successfully developed, validated, and applied a UPLC-PDA method for the quantification of nitrate and nitrite in various samples. This method involves an extraction procedure, followed by a straightforward derivatization step using sulfanilamide for nitrite determination. After derivatization, nitrate was directly quantified based on its corresponding peak, and nitrite was determined through its derivative response. The validation process demonstrated good linearity and specificity over a range of 25–400 mg/kg, along with satisfactory precision, accuracy, and excellent recoveries. Furthermore, the detection and quantification limits were found to be very satisfactory. The effectiveness of the method was confirmed through the analysis of various matrices, showcasing its rapidity, and reliability.
•Simultaneous nitrate and nitrite determination in baby foods.•Nitrite determination through straightforward sulfanilamide derivatization, omitting the need for a coupling agent.•Nitrate quantified directly, while nitrite via its derivative response.•Validation of a rapid, robust, and precise method with a short analysis time, ideal for routine testing.
A versatile and robust end‐group derivatization approach using oximes has been developed for the detection of oxidative degradation of synthetic polyisoprenes and polybutadiene. This method ...demonstrates broad applicability, effectively monitoring degradation across a wide molecular weight range through ultraviolet (UV)‐detection coupled to gel permeation chromatography. Importantly, it enables the effective monitoring of degradation via derivatization‐induced UV‐maximum shifts, even in the presence of an excess of undegraded polyene, overcoming limitations previously reported with refractive index detectors. Notably, this oxime‐based derivatization methodology is used in enzymatic degradation experiments of synthetic polyisoprenes characterized by a cis: trans ratio with the rubber oxygenase LcpK30. It reveals substantial UV absorption in derivatized enzymatic degradation products of polyisoprene with molecular weights exceeding 1000 g mol−1 ‐ an unprecedented revelation for this enzyme's activity on such synthetic polyisoprenes. This innovative approach holds promise as a valuable tool for advancing research into the degradation of synthetic polyisoprenes and polybutadiene, particularly under conditions of low organocatalytic or enzymatic degradation activity. With its broad applicability and capacity to reveal previously hidden degradation processes, it represents a noteworthy contribution to sustainable polymer chemistry.
An oxime‐based derivatization method, combined with UV‐detection in gel permeation chromatography to detect oxidative degradation in synthetic polyisoprenes and polybutadiene, is described. It reveals UV absorption of derivatized enzymatic degradation products, offering insights into rubber oxygenase degradation in synthetic polyisoprenes. This method represents a novel tool for enzymatic and organocatalytic degradation investigations in polyenes, even at low activity levels.
Thiol compounds (R–SH) have many important biological functions and are principal controls of the speciation of several toxic metals in the environment. However, determining the concentration of ...thiols associated with environmental matrices is challenging due to the compounds’ low abundance and interferences from non-thiol compounds for many available methods. Here a novel method has been developed and validated to quantify the total concentration of thiol functional groups in aqueous samples using derivatization with monobromo(trimethylammonio)bimane (qBBr) and quantification with tandem mass spectrometry. The thiol concentration was determined by titration of the sample with qBBr, which reacts selectively with thiols, and quantification of the residual qBBr. We systematically evaluated potential interferences from various organic compounds, inorganic ions (including sea water matrices), sulfide and mercury (Hg) species, and demonstrate that the method is highly sensitive, selective and robust. The limit of detection (LOD) for total thiols is in the nanomolar concentration range (~6 nM). The method performance was also demonstrated by determination of the total thiol concentration in different natural samples including boreal stream water (1.16 μM), wetland porewater (0.96 μM) and the Suwanee River natural organic matter (NOM) reference material SR101 N (7.9 μmol g−1). The developed method represents a combination of low LOD and high selectivity and robustness that is unsurpassed for total thiol concentration measurements.
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•Highly sensitive, selective and robust method.•Low detection limit of 6 nM for total thiol concentration determinations.•High tolerance to inorganic and organic matrix constituents.•Accurate determination of low thiol concentrations in complex environmental samples.
7-dehydrocholesterol (7-DHC) and cholesterol (CHOL) are biomarkers of Smith-Lemli-Opitz Syndrome (SLOS), a congenital autosomal recessive disorder characterized by elevated 7-DHC level in patients. ...Hair samples have been shown to have great diagnostic and research value, which has long been neglected in the SLOS field. In this study, we sought to investigate the feasibility of using hair for SLOS diagnosis. In the presence of antioxidants (2,6-ditert-butyl-4-methylphenol and triphenylphosphine), hair samples were completely pulverized and extracted by micro-pulverized extraction in alkaline solution or in n-hexane. After microwave-assisted derivatization with N,O-Bis(trimethylsilyl)trifluoroacetamide, the analytes were measured by GC-MS. We found that the limits of determination for 7-DHC and CHOL were 10 ng/mg and 8 ng/mg, respectively. In addition, good linearity was obtained in the range of 50–4000 ng/mg and 30–6000 ng/mg for 7-DHC and CHOL, respectively, which fully meets the requirement for SLOS diagnosis and related research. Finally, by applying the proposed method to real hair samples collected from 14 healthy infants and two suspected SLOS patients, we confirmed the feasibility of hair analysis as a diagnostic tool for SLOS. In conclusion, we present an optimized and validated analytical method for the simultaneous determination of two SLOS biomarkers using human hair.
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Accurate and specific analysis of target molecules in complex biological matrices remains a significant challenge, especially when ultra‐trace detection limits are required. Liquid chromatography ...with mass spectrometry is often the method of choice for bioanalysis. Conventional sample preparation and clean‐up methods prior to the analysis of biological fluids such as liquid–liquid extraction, solid‐phase extraction, or protein precipitation are time‐consuming, tedious, and can negatively affect target recovery and detection sensitivity. An alternative or complementary strategy is the use of an off‐line or on‐line in situ derivatization technique. In situ derivatization can be incorporated to directly derivatize target analytes in their native biological matrices, without any prior sample clean‐up methods, to substitute or even enhance the extraction and preconcentration efficiency of these traditional sample preparation methods. Designed appropriately, it can reduce the number of sample preparation steps necessary prior to analysis. Moreover, in situ derivatization can be used to enhance the performance of the developed liquid chromatography with mass spectrometry‐based bioanalysis methods regarding stability, chromatographic separation, selectivity, and ionization efficiency. This review presents an overview of the commonly used in situ derivatization techniques coupled to liquid chromatography with mass spectrometry‐based bioanalysis to guide and to stimulate future research.
The rapidly growing, competitive biopharmaceutical market requires tight bioprocess monitoring. An integrated, automated platform for the routine online/at‐line monitoring of key factors in the cell ...culture medium could greatly improve process monitoring. Mono‐ and disaccharides, as the main energy and carbon source, are one of these key factors. A CE‐LIF method was developed for the analysis of several mono‐ and disaccharides, considering requirements and restrictions for analysis in an integrated, automated monitoring platform, such as the possibility for miniaturization to microchip electrophoresis. Analysis was performed after fluorescent derivatization with 8‐aminopyrene‐1,3,6‐trisulfonic acid. The derivatisation reaction and the separation BGE were optimized using design of experiments. The developed method is applicable to the complex matrix of cell culture medium and proved transferable to microchip electrophoresis.
Estrogens and their analogues can cause harm to human health through the food chain. Ten estrogens in different milk samples were directly extracted by amphiphilic ...divinylbenzene/N-vinyl-2-pyrrolidone (DVB/NVP)-Fe3O4@SiO2-based magnetic solid-phase extraction (MSPE) followed by pre-column derivatization and ultra-high performance liquid chromatography tandem mass-spectrometry (UHPLC-MS/MS) detection. Under the optimal conditions, the limits of detection for ten analytes were in the range of 0.05–0.38 ng mL−1 in whole liquid milk matrix and 0.04–3.00 ng g−1 in milk powder matrix. The intra-/inter-day accuracy ranged in 83.4–113.8%, with RSDs in 2.5–15.0%. A total of 15 brands of liquid milk and milk powder samples were analyzed, and only estradiol was detected in three brands of boxed liquid milk within safe range. The proposed sample pretreatment eliminated the common protein precipitation process, improved the sample throughput, and has the potential for routine testing of estrogens and their analogues in market-sale milk samples.
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•Amphiphilic DVB/NVP-Fe3O4@SiO2 adsorbent was synthesized.•The MSPE was directly used for the extraction of analytes from milk samples.•The proposed sample pretreatment eliminates the common protein precipitation process.•Ten estrogens in 15 brands of liquid milk and milk powder samples were analyzed.
•LC/ESI–MS/MS has been widely used for the quantification of endogenous steroids.•However, the ESI efficiency and fragmentation behavior of some steroids are poor.•Chemical derivatization is ...effective for enhancing detectability of steroids.•This article reviews chemical derivatization for LC/ESI–MS/MS of steroids.•Stable isotope-coded derivatization for the steroid analysis is also described.
Sensitive and specific methods for the detection, characterization and quantification of endogenous steroids in body fluids or tissues are necessary for the diagnosis, pathological analysis and treatment of many diseases. Recently, liquid chromatography/electrospray ionization–tandem mass spectrometry (LC/ESI–MS/MS) has been widely used for these purposes due to its specificity and versatility. However, the ESI efficiency and fragmentation behavior of some steroids are poor, which lead to a low sensitivity. Chemical derivatization is one of the most effective methods to improve the detection characteristics of steroids in ESI–MS/MS. Based on this background, this article reviews the recent advances in chemical derivatization for the trace quantification of steroids in biological samples by LC/ESI–MS/MS. The derivatization in ESI–MS/MS is based on tagging a proton-affinitive or permanently charged moiety on the target steroid. Introduction/formation of a fragmentable moiety suitable for the selected reaction monitoring by the derivatization also enhances the sensitivity. The stable isotope-coded derivatization procedures for the steroid analysis are also described.
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