Uncovering the green frontier: harnessing deep eutectic solvents for sustainable bioanalysis (original) (raw)
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future science group Experimental Chemicals & reagents Analytical standards for the model compounds (Table 1) were obtained from Sigma-Aldrich (St. Louis, MO, USA). Ammonium acetate and DMSO were obtained from Fluka (Milwaukee, WI, USA). HPLC-grade methanol (MeOH) and acetonitrile (ACN) were obtained from JT Baker (Phillipsburg, NJ, USA). Deionized water was prepared in-house by a Barnstead Nanopure water purification system (Dubuque, IA, USA). Sprague-Dawley rat plasma (K 2-EDTA) was obtained from Bioreclamation Inc. (Hicksville, NY, USA). Stock solution of each compound was prepared at 1.0 mg/ml in DMSO. A working solution containing a mixture of all compounds was prepared at 10 µg/ml in ACN.
Analytical and Bioanalytical Chemistry
Over the past six decades, acetonitrile (ACN) has been the most employed organic modifier in reversed-phase high-performance liquid chromatography (RP-HPLC), followed by methanol (MeOH). However, from the growing environmental awareness that leads to the emergence of Bgreen analytical chemistry,^new research has emerged that includes finding replacements to problematic ACN because of its low sustainability. Deep eutectic solvents (DES) can be produced from an almost infinite possible combinations of compounds, while being a Bgreener^alternative to organic solvents in HPLC, especially those prepared from natural compounds called natural DES (NADES). In this work, the use of three NADES as the main organic component in RP-HPLC, rather than simply an additive, was explored and compared to the common organic solvents ACN and MeOH but additionally to the greener ethanol for separating two different mixtures of compounds, one demonstrating the elution of compounds with increasing hydrophobicity and the other comparing molecules of different functionality and molar mass. To utilize NADES as an organic modifier and overcome their high viscosity monolithic columns, temperatures at 50°C and 5% ethanol in the mobile phase were used. NADES are shown to give chromatographic performances in between those observed for ACN and MeOH when eluotropic strength, resolution, and peak capacity were taken into consideration, while being less environmentally impactful as shown by the HPLC-Environmental Assessment Tool (HPLC-EAT) metric. With the development of proper technologies, DES could open a new class of mobile phases increasing the possibilities of new separation selectivities while reducing the environmental impact of HPLC analyses. Keywords Green analytical chemistry. NADES. Low transition temperature mixtures. Green solvents. Natural designer solvents. Green chromatography
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Journal of the American Society for Mass Spectrometry, 2006
A dry sample preparation strategy was previously established as a new method for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS), so-called solvent-free MALDI-MS. In this contribution, we examine systems that have been shown problematic with conventional solvent-based MALDI approaches. Problems frequently encountered are solubility, miscibility, and segregation effects during crystallization as a result of unfavorable analyte and matrix polarities. In all cases studied, solvent-free MALDI-MS simplified the measurement and improved the analysis. Solvent-free MALDI-MS enables more reliable results in well-known problematic systems such as polydimethylsiloxane with its segregation effects. However, even in highly compatible analyte/matrix systems such as polystyrene and dithranol, there were undesirable suppression effects when employing THF as solvent. Generally, the solvent-free method allows for more homogeneous analyte/matrix mixtures as well as higher shot-to-shot and sample-to-sample reproducibility. As a result, less laser power has to be applied, which yields milder MALDI conditions, reduced background signals, and provides better resolution of the analyte signals. Solvent-free MALDI-MS proved valuable for the characterization of nanosized material, e.g., fullereno-based structures, which indicated having an increased fragmentation-susceptibility. New analyte/matrix combinations (e.g., polyvinylpyrrolidone/dithranol) are accessible independent of solubility and compatibility in common solvents. An improved quantitation potential is recognized (e.g., insoluble polycyclic aromatic hydrocarbon against soluble dendrite precursor). The rapid and easy measurement of industrial products demonstrates the solvent-free method capable for improved throughput analysis of a variety of compounds (e.g., poly(butylmethacrylate) diol) in routine industrial analysis. Hence, this new MALDI method leads to qualitative and quantitative improvements, making it a powerful tool for analytical purposes, which may also prove to be valuable in future automation attempts.
The review, as can be deduced from the title, focuses on both theoretical and practical aspects of the use of mass spectrometry as a third, added dimension to a comprehensive LC (LC Â LC) system, generating the most powerful analytical tool today for non-volatile analytes. The first part deals with the technical requirements for linkage of an LC Â LC system to an MS one, including the choice of the mobile phase (buffer and salts), flow rate (splitting), type of ionization (interface); advantages and disadvantages of off-line and on-line methods are discussed, as well. A discussion of the various aspects of instrumentation is provided, both from a chromatographic and mass spectrometry standpoint, with particular emphasis directed to the choice of column sets, spatial resolution, mass resolving power, mass accuracy, and tandem-MS capabilities. The extent to which mass spectrometry may be of aid in unraveling column-outlet multi-compound bands is highlighted, along with its effectiveness as a chromatographic detector of excellent sensitivity, universality yet with potential in terms of selectivity and amenability to quantitative analysis over a wide dynamic range. The following section of the review contains significant applications of comprehensive two-dimensional LC coupled to MS in different areas of research, with details on interfaces, column stationary phases, modulation and MS parameters. It is not the intention of the authors to provide a comprehensive description of the techniques , but merely to discuss only those aspects which are essential for successful applications of the LC–MS combination. The reader will be acquainted with the enormous potential of this hyphenated technique, and the factors and instrumental developments that have concurred to make it emerge to a central role in specialized fields, such as proteomics.
10years of MS instrumental developments – Impact on LC–MS/MS in clinical chemistry
Journal of Chromatography B, 2012
The combination of liquid chromatography and mass spectrometry (LC-MS) is a powerful and indispensable analytical tool that is widely applied in many areas of chemistry, medicine, pharmaceutics and biochemistry. In this review recent MS instrumental developments are presented as part of a special issue covering various aspects of liquid chromatography tandem mass spectrometry (LC-MS/MS) in clinical chemistry. Improvements, new inventions as well as new combinations in ion source technology are described focusing on dual or multimode sources and atmospheric pressure photoionization (APPI). Increasing demands regarding sensitivity, accuracy, resolution and both quantitation and identification guarantee ongoing improvements in mass analyzer technology. This paper discusses new hybrid MS instruments that can perform novel scan modes as well as high-resolution mass spectrometers (HRMS) that finally seem to be able to overcome, or at least significantly reduce, their weaknesses in quantitative applications. Ion mobility-mass spectrometry (IMMS) itself is not an invention of the last 10 years, but a lot of progress was made within the last decade that reveals the potential benefits of this combination. This is clearly reflected by the increased number of commercially available instruments and the various designs of IMMS are covered in detail in this review. Selected applications for all these instrumental developments are given focusing on the perspective of clinical chemistry.
Multisample preparation methods for the solvent-free MALDI-MS analysis of synthetic polymers
Journal of the American Society for Mass Spectrometry, 2007
A limitation of any current approach using solvent-free MALDI mass spectrometry is that only one sample at a time can be prepared and transferred to the MALDI-plate. For this reason, multiple-sample preparation approaches for solvent-free MALDI MS analysis of synthetic polymers were developed that are simple and practical. One approach multiplexed sample preparation by simultaneously preparing multiple samples. With this approach, as many as 384 samples could be prepared by addition of analyte, matrix, salt, and 1-mm metal beads to each well of a 384-well disposable bacti plate, capping the plate with the lid and homogenizing all samples simultaneously using a common laboratory vortex device. Besides the time savings achieved by a single vortex step for multiple samples, an additional advantage of this method relative to previously reported solvent-free preparation methods is that the mixing volume per sample is reduced, which allows a reduction in the amount of analyte required. This method, however, still requires the transfer of each homogenized sample to the MALDI plate for subsequent analysis. Here we report a novel approach that combines multiple simultaneous solvent-free sample preparation with automatic sample transfer to the MALDI target plate. This approach reduces the possibility of cross-contamination, the amount of sample and matrix consumed for an analysis, and the time required for preparation of multiple samples. These methods were shown to provide high-quality mass spectra for various synthetic polymer standards with M n values to 10 kDa. The methods are efficient in that small sample amounts are required, the sample/salt/matrix ratio is not critical, and the time necessary to achieve sufficient homogenization of multiple samples is less than 5 min. (J Am Soc Mass Spectrom 2007, 18, 377-381)