Fused deposition modeling, one of the most common techniques in three-dimensional printing and additive manufacturing, has many practical applications in the fields of chemistry and pharmacy. We ...demonstrate that a thermoplastic elastomer-poly(vinyl alcohol) (PVA) composite material (LAY-FOMM 60), which presents porous properties after PVA removal, is useful for the extraction of small-molecule drug-like compounds from water samples. The usefulness of the proposed approach is demonstrated by the extraction of glimepiride from a water sample, followed by LC-MS analysis. The recovery was 82.24%, with a relative standard deviation of less than 5%. The proposed approach can change the way of thinking about extraction and sample preparation due to a shift to the use of sorbents with customizable size, shape, and chemical properties that do not rely on commercial suppliers.
Techniques of additive manufacturing commonly referred to as 3D-printing (3DP), obviously have taken a permanent place in the analytical chemistry laboratory toolbox. In the recent five years, one ...could observe the rapid spread of 3DP in several areas, especially in the instant design, prototyping, development, and final fabrication of custom analytical systems, which was not possible with the help of previously available laboratory methods. The two most achievable technologies: fused deposition modeling and stereolithography, rely on polymer materials that can be shaped according to the current, custom laboratory needs. Herein, we focus on so-called fourth-level applications in separation science, namely devices recognizable by the surface chemistry of printed objects and utilized because of this chemical activity. Besides obvious benefits, including simplicity and affordability of usage and the possibility to achieve complex geometries and structures, we consider the design of novel materials as the most potent direction of further expansion of 3D printing. This review article is intended to point out recent achievements in the development of functional materials that can be processed by 3DP and applied in separation science. We want to pronounce approaches to design successful new materials, especially composites and chemically modified surfaces. Moreover, several potentially useful approaches derived from the material chemistry field and not yet directly applied in analytical chemistry will be listed as a perspective for further evolution and advancements in separation science.
•Recent advances in the 3D printing of chemically active separation devices.•Fused deposition modeling is the most achievable technology among chemists.•Stereolithography needs novel, innovative resins to expand applicability.•Selective laser sintering is hoped to evolve as a tool to produce porous devices.
Extraction of endogenous compounds and drugs and their corresponding metabolites from complex matrices, such as biofluids and solid tissues, requires adequate analytical approach facilitating ...qualitative and quantitative analysis. To this end, solid‐phase microextraction has been introduced as modern technology that is capable of efficient and high‐throughput extraction of compounds due to its ability to amalgamate sampling, extraction, and pre‐concentration steps, while requiring minimal use of organic solvents. The ability of solid‐phase microextraction to enable analyses on small‐volume biological samples and growing availability of biocompatible solid‐phase microextraction coatings make it a highly useful technology for variety of applications. For example, solid‐phase microextraction is particularly useful for identifying biomarkers in metabolomics studies, and it can be successfully applied in pharmaceutical and toxicological studies requiring the fast and sensitive determination of drug levels, especially those that are present at low levels in biological matrices such as plasma, urine, saliva, and hair. Moreover, solid‐phase microextraction can be directly applied in in vivo studies because this extraction technique is non‐exhaustive and its biocompatible probes offer minimal invasiveness to the analyzed system. In this article, we review recent progress in well‐established solid‐phase microextraction technique for in vitro and in vivo analyses of various metabolites and drugs in clinical, pharmaceutical, and toxicological applications.
Ionic liquids (ILs), also known as “designer solvents,” comprise a large group of compounds that can improve overall sample preparation performance due to their unique physical and chemical ...properties. Some of them have a comparable structure to surfactants, which can be also considered as effective extraction solvents. In this study, nine different ILs and a double-chained surfactant were investigated as potential coating materials for iron oxide-based nanoparticles (NPs) used in the pretreatment of human plasma samples. Various methods of synthesizing and functionalizing NPs were employed in fabricating the magnetic sorbents, with the physicochemical properties of the resultant extraction phases (i.e., naked NPs, NPs coated with silica, and NPs coated with silica and selected IL or surfactant) being characterized via X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TG), and transmission electron microscopy (TEM). The effectiveness of the developed NP-based extraction phases was tested by applying them for the extraction of epirubicin hydrochloride (EPI) from plasma samples, followed by analysis via liquid chromatography with fluorescence detection (LC-FL). The results showed that NPs coated with both silica and IL or silica and surfactant provided significantly higher extraction efficiency compared to naked NPs and NPs coated solely with silica. Additionally, the findings also revealed that the adsorption of analytes depends not only on the coating procedure but also on the type of coating material used to functionalize the NPs. Among the tested structures, didodecyldimethylammonium bromide provided the best performance for the functionalization of NP sorbents previously coated with silica.
In this study, a large volume sample stacking (LVSS) with polarity switching (PS) and cyclodextrin electrokinetic chromatography (CDEKC) method has been developed for the simultaneous separation and ...determination of 8 preservatives: methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), isobutylparaben (IBP), sorbic acid (SA), benzoic acid (BA), p-hydroxybenzoic acid (PHBA) in pharmaceuticals. The effects of some typical parameters such as sample volume, applied voltage, composition and pH of the running buffer and organic modifier concentration were examined and optimized. Moreover, the impact of type and concentration of cyclodextrin as electrolyte modifiers was also investigated. The detection limits of analytes for the elaborated LVSS-PS-CDEKC method were found to be in 0.8–5 ng mL−1 range, which were around 500 times lower than normal CDEKC without preconcentration technique. All analytes were completely resolved in less than 11 min in an uncoated fused-silica capillary of 75 μm internal diameter (I.D) x 50 cm length. The electrophoretic separation was performed in a 2 mM α-cyclodextrin and 25 mM tetraborate system (pH = 9.3) with an applied voltage of 25 kV. The established method was validated and confirmed to be applicable for the determination of the preservatives in a quality control of pharmaceuticals.
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•For the first time the impact of highly-sulfated cyclodextrins on the separation of common preservatives was examined.•The LVSS with polarity switching was first described in a combination with CDEKC for the separation of the preservatives.•The detection limits of the developed LVSS-PS-CDEKC method was about 500 times lower than standard HDI method.•For three acidic analytes (BA, SA, and PHBA), an additional stacking effect was observed in the form of dynamic pH-junction.
With metabolism being one of the main routes of drug elimination from the body (accounting for removal of around 75% of known drugs), it is crucial to understand and study metabolic stability of drug ...candidates. Metabolically unstable compounds are uncomfortable to administer (requiring repetitive dosage during therapy), while overly stable drugs increase risk of adverse drug reactions. Additionally, biotransformation reactions can lead to formation of toxic or pharmacologically active metabolites (either less‐active than parent drug, or even with different action). There were numerous approaches in estimating metabolic stability, including in vitro, in vivo, in silico, and high‐throughput screening to name a few. This review aims at describing separation techniques used in in vitro metabolic stability estimation, as well as chemometric techniques allowing for creation of predictive models which enable high‐throughput screening approach for estimation of metabolic stability. With a very low rate of drug approval, it is important to understand in silico methods that aim at supporting classical in vitro approach. Predictive models that allow assessment of certain biological properties of drug candidates allow for cutting not only cost, but also time required to synthesize compounds predicted to be unstable or inactive by in silico models.
In this work, performance of five nature-inspired optimization algorithms, genetic algorithm (GA), particle swarm optimization (PSO), artificial bee colony (ABC), firefly algorithm (FA), and flower ...pollination algorithm (FPA), was compared in molecular descriptor selection for development of quantitative structure–retention relationship (QSRR) models for 83 peptides that originate from eight model proteins. The matrix with 423 descriptors was used as input, and QSRR models based on selected descriptors were built using partial least squares (PLS), whereas root mean square error of prediction (RMSEP) was used as a fitness function for their selection. Three performance criteria, prediction accuracy, computational cost, and the number of selected descriptors, were used to evaluate the developed QSRR models. The results show that all five variable selection methods outperform interval PLS (iPLS), sparse PLS (sPLS), and the full PLS model, whereas GA is superior because of its lowest computational cost and higher accuracy (RMSEP of 5.534%) with a smaller number of variables (nine descriptors). The GA-QSRR model was validated initially through Y-randomization. In addition, it was successfully validated with an external testing set out of 102 peptides originating from Bacillus subtilis proteomes (RMSEP of 22.030%). Its applicability domain was defined, from which it was evident that the developed GA-QSRR exhibited strong robustness. All the sources of the model’s error were identified, thus allowing for further application of the developed methodology in proteomics.
Solid-phase microextraction (SPME) has gained attention as a simple, fast, and non-exhaustive extraction technique, as its unique features enable its use for the extraction of many classes of drugs ...from biological matrices. This sample-preparation approach consolidates sampling and sample preparation into a single step, in addition to providing analyte preconcentration and sample clean-up. These features have helped SPME become an integral part of several analytical protocols for monitoring drug concentrations in human matrices in clinical, toxicological, and forensic medicine studies. Over the years, researchers have continued to develop the SPME technique, resulting in the introduction of novel sorbents and geometries, which have resulted in improved extraction efficiencies. This review summarizes developments and applications of SPME published between 2016 and 2022, specifically in relation to the analysis of central nervous system drugs, drugs used to treat cardiovascular disorders and bacterial infections, and drugs used in immunosuppressive and anticancer therapies.
Modern bioanalysis, which involves the quantitative and qualitative determination of small-molecule endogenous and exogenous substances in biological samples, is a powerful and useful tool that can ...generate valuable information related to many areas connected with human health and quality of life. Although LC-MS and GC-MS are widely viewed as the gold standards for many bioanalytical tasks, the scientific community has not abandoned its search for newer, more efficient, and more inexpensive methods of performing extraction as a sample preparation step before final analysis. Recent research showing the immense potential of 3D printing compelled our group to explore how this technology could be applied to techniques used in analytical chemistry. In particular, 3D printing offers three promising advantages: availability, low cost of materials and equipment, and the ability to fabricate objects of nearly any shape to suit the needs of a given application. Previously, we demonstrated that a commercial 3D material (LAY-FOMM) can function as a chemically active object that enables the reversible sorption of the antidiabetic drug, glimepiride, and endogenous steroids. In this report, we use a 3D printer to fabricate sorbents with a scabbard-like shape for use with a 96-blade system, which, along with the use of a 96-well plate, allows multiple extractions to be performed simultaneously. In order to assess the relative benefits of this 3D printed approach, we compare the performance of the proposed LAY-FOMM-based sorbent to that of the widely used C18 sorbent. Although the LAY-FOMM sorbent showed lower extraction recovery rates than the C18 sorbent, all of the other validation parameters suggest that it is suitable for use in high-throughput analysis of steroids in human plasma.
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•Thermoplastic fabricated via 3D printing is capable of acting as a sorbent.•3D printing enables to fabricate chemically active objects of desired shape.•3D printing-based extraction protocol enabling high-throughput analysis.•The protocol can be applied in biomedical analyses.
•3D- printing technique enables in-lab fabrication of extraction sorbent.•The proposed sample preparation technique is cost effective, efficient, and repeatable.•A novel procedure for extracting ...endogenous steroids from plasma was developed and optimized.
In recent years, there has been an increasing worldwide interest in the use of alternative sample preparation methods that are proceeded by separation techniques. Fused deposition modeling (FDM) is a 3D printing technique that is based the consecutive layering of softened/melted thermoplastic materials.
In this study, a group of natural steroids and sexual hormones – namely, aldosterone, cortisol, β-estradiol, testosterone, dihydrotestosterone, and synthetic methyltestosterone and betamethasone – were separated and determined using an optimized high-performance liquid chromatography coupled to mass spectrometry (LC–MS) method in positive ionization mode. 3D-printed sorbents were selected as the pre-concentration technique because they are generally low cost, fast, and simple to make and automate. Furthermore, the use of 3D-printed sorbents helps to minimize potential errors due to their repeatability and reproducibility, and their ability to eliminate carry over by using one printed sorbent for a single extraction of steroids from biological matrices.
The extraction procedure was optimized and the parameters influencing 3D-printed Layfomm 60® based sorbent and LC–MS were studied, including the type of extraction solvent used, sorption and desorption times, temperature, and the salting-out effect. To demonstrate this method’s applicability for biological sample analysis, the SPME-LC–MS method was validated for its ability to simultaneously quantify endogenous steroids. This evaluation confirmed good linearity and an R2 that was between 0.9970 and 0.9990. The recovery rates for human plasma samples were 86.34–93.6% for the studied steroids with intra- and inter-day RSDs of 1.44–7.42% and 1.44–9.46%, respectively. To our knowledge, this study is the first time that 3D-printed sorbents have been used to extract trace amounts of endogenous low-molecular-weight compounds, such as steroids, from biological samples, such as plasma.
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