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Capillary temperature control during capillary electrophoresis (CE) separations is key for achieving accurate and reproducible results with a broad array of potential methods. However, the difficulty of enabling typical fluid temperature control loops on portable instruments has meant that active capillary temperature control of in situ CE systems has frequently been overlooked. This work describes construction and test of a solid-state device for capillary temperature control that is suitable for inclusion with in situ instruments, including those designed for space missions. Two test articles were built, a thermal mass model (TMM) and a functional model (FM). The TMM demonstrated that temperature gradients could be limited using the proposed control scheme, and that our thermal modeling of the system can be relied on for future adaptations of physical geometries of the system. The FM demonstrated CE analytical performance while under active temperature control and that the device was compatible with the harsh thermal-vacuum environments that might be encountered during space flight., (© 2024 Wiley‐VCH GmbH.)

We report here the first fully automated capillary electrophoresis (CE) system that can be operated underwater. The system performs sample acquisition and analysis by coupling CE to contactless conductivity detection. Using 5 M acetic acid as the background electrolyte (BGE), inorganic cations and amino acids at concentrations as low as 5.2 μM can be separated and identified. This technology could be augmented to include a variety of other detection modes. This system serves as an early prototype for potential future underwater explorers on ocean worlds of the outer solar system such as Europa or Enceladus. This work documents the first step in the development of this general-purpose technology platform.

Capillary electrophoresis (CE) holds great promise as an in situ analytical technique for a variety of applications. However, typical instrumentation operates with open reservoirs (e.g., vials) to accommodate reagents and samples, which is problematic for automated instruments designed for space or underwater applications that may be operated in various orientations. Microgravity conditions add an additional challenge due to the unpredictable position of the headspace (air layer above the liquid) in any two-phase reservoir. One potential solution for these applications is to use a headspace-free, flow-through reservoir design that is sealed and connected to the necessary reagents and samples. Here, we demonstrate a flow-through high-voltage (HV) reservoir for CE that is compatible with automated in situ exploration needs, and which can be electrically isolated from its source fluidics (in order to prevent unwanted leakage current). We also demonstrate how the overall system can be rationally designed based on the operational parameters for CE to prevent electrolysis products generated at the electrode from entering the capillary and interfering with the CE separation. A reservoir was demonstrated with a 19 mm long, 1.8 mm inner diameter channel connecting the separation capillary and the HV electrode. Tests of these reservoirs integrated into a CE system show reproducible CE system operation with a variety of background electrolytes at voltages up to 25 kV. Rotation of the reservoirs, and the system, showed that their performance was independent of the direction of the gravity vector., (© 2023 Wiley-VCH GmbH. California Institute of Technology. Government sponsorship acknowledged. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.)

Sample injection is a critical step in a capillary electrophoresis (CE) analysis. Electrokinetic injection is the simplest approach and is often selected for implementation in portable CE instruments. However, in order to minimize the effect of sample matrix upon the results of a CE analysis, hydrodynamic injection is preferred. Although portable CE instruments with hydrodynamic injection have been reported, injection has always been performed at the grounded end of the capillary. This simplifies fluidic handling but limits coupling with electrochemical detectors and electrospray ionization-mass spectrometry (ESI-MS). We demonstrated previously that injection at the high-voltage (HV) end of the capillary could be performed using an HV-compatible rotary injection valve (fixed-volume injection). However, the mismatch between the bore sizes of the channels on the rotor-stator valve and the separation capillary caused peak tailing and undesired mixing, impairing analytical performance. In this work, we present an HV-compatible hydrodynamic injection approach that overcomes the issues associated with the fixed-volume injection approach reported previously. The performance of the CE instrument was demonstrated by analyzing a mixture of 13 amino acids by CE coupled to laser-induced fluorescence, which showed relative standard deviations for peak area and migration time below 5% and 1%, respectively, for triplicate analysis. Additionally, replicate measurements of a mixture of amino acids, peptides, nucleobases, and nucleosides by CE coupled to electrospray ionization-mass spectrometry (CE-ESI-MS) were performed to evaluate peak tailing, and results were similar to those obtained with a commercial CE-ESI-MS setup., (© 2023 Jet Propulsion Laboratory, California Institute of Technology. Government sponsorship acknowledged.)

Capillary electrophoresis (CE) systems have undergone extensive development for spaceflight applications. A flight-compatible high voltage power supply and the necessary voltage isolation for other energized components can be large contributors to both the volume and mass of a CE system, especially if typical high voltage levels of 25-30 kV are used. Here, we took advantage of our custom CE hardware to perform a trade study for simultaneous optimization of capillary length, high voltage level, and separation time, without sacrificing method performance. A capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C 4 D) method recently developed by our group to target inorganic cations and amino acids relevant to astrobiology was used as a test case. The results indicate that a 50 cm long capillary with 15 kV applied voltage (half of that used in the original method) can be used to achieve measurement goals while minimizing instrument size., (© 2022 Wiley-VCH GmbH. California Institute of Technology. Government sponsorship acknowledged.)

Screen-printed electrodes (SPEs) coupled with flow systems have been reported in recent decades for an ever-growing number of applications in modern electroanalysis, aiming for portable methodologies. The information acquired through this combination can be attractive for future users with basic knowledge, especially due to the increased measurement throughput, reduction in reagent consumption and minimal waste generation. The trends and possibilities of this set rely on the synergistic behavior that maximizes both SPE and flow analyses characteristics, allowing mass production and automation. This overview addresses an in-depth update about the scope of samples, target analytes, and analytical throughput (injections per hour, limits of detection, linear range, etc.) obtained by coupling injection techniques (FIA, SIA, and BIA) with SPE-based electrochemical detection.

In situ missions of exploration require analytical methods that are capable of detecting a wide range of molecular targets in complex matrices without a priori assumptions of sample composition. Furthermore, these methods should minimize the number of reagents needed and any sample preparation steps. We have developed a method for the detection of metabolically relevant inorganic and organic anions that is suitable for implementation on in situ spaceflight missions. Using 55 mM acetic acid, 50 mM triethylamine, and 5% glycerol, more than 21 relevant anions are separated in less than 20 min. The method is robust to sample ionic strength, tolerating high concentrations of background salts (up to 900 mM NaCl and 300 mM MgSO 4 ). This is an important feature for future missions to ocean worlds. The method was validated using a culture of Escherichia coli and with high salinity natural samples collected from Mono Lake, California., (© 2021 Wiley-VCH GmbH.)

The in situ search for chemical signatures of life on extraterrestrial worlds requires automated hardware capable of performing detailed compositional analysis during robotic missions of exploration. The use of electrophoretic separations in this search is particularly powerful, enabling analysis of a wide range of soluble organic compounds potentially indicative of life, as well as inorganic compounds that can serve as indicators of habitability. However, to detect this broad range of compounds with a single electrophoresis instrument, a combination of different detection modes is required. For detection of any ionizable species, including organic compounds that do not participate in terrestrial biology (i.e., "unknown unknowns"), mass spectrometry (MS) is essential. Inorganic ions, or any dissolved charged species present, can be analyzed using capacitively coupled contactless conductivity detection (C 4 D). Additionally, for the trace analysis of compounds of key interest to astrobiology (particularly, amino acids), laser-induced fluorescence (LIF) detection holds unique promise, due to the fact that it has the highest demonstrated sensitivity of any form of detection. Here, we demonstrate a fully automated, portable capillary electrophoresis analyzer that is capable of all these modes of detection. The prototype system developed here addresses the three most significant challenges for doing electrophoretic separations: precise sample injection, HV isolation, and automation of all operational steps. These key challenges were successfully addressed with the use of custom-designed rotor-stator valves with optimized operational sequences incorporating gas purging steps, rinses, and HV application.

Cocaine (COC) is one of the most widely consumed illegal drugs around the world. Street COC is commonly adulterated with pharmaceutical compounds that mimic or intensify the COC's sensory effect. Adulteration is performed to increase the profit of criminal organizations and each one has their own way of doing it. Therefore, determining the composition of seized COC samples (chemical profile) provides evidence for the police to track criminal organization networks and their activity patterns. Using filter paper as a substrate, we developed a multiple detection paper-based analytical device (PAD) that combines colorimetric and electrochemical measurements to discriminate COC samples according to adulterant's content. A regular graphite lead modified with a gold film made from Au leaf (graphite/Au) to improve electron transfer was used as a working electrode. Silver and Ag/AgCl were used as auxiliary and reference electrodes, respectively. The colorimetric device was patterned using a laser cutter and coupled to the electrochemical device using a double-sided tape, allowing simultaneous analysis to gather more analytical information about COC samples. Graphite/Au was characterized by scanning and transmission electron microscopies and electrochemical assays. The simultaneous colorimetric and electrochemical analyses combined to principal component analysis improved the analytical characterization of COC trial samples and provided a fast discrimination based on the assembled database., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Silver ions (Ag+) have been proposed as a biocide to treat the water in NASA's next generation of human space exploration vehicles/habitats. One advantage of Ag+ is that it is effective as a biocide in a range (200 to 500 ppb) safe for human consumption. So, monitoring Ag+ is essential to ensure the safety and health of the crew. Here we present two analytical methods based on capillary electrophoresis and capacitively coupled contactless conductivity detection (CE-C4D) to address the need to monitor Ag+ levels in water. Using 5 M acetic acid as a background electrolyte (BGE), 100 ppb of Ag+ could be detected in a simulant of the International Space Station (ISS) water. In addition to Ag+, other inorganic cations (K+, Ca2+, Na+, Mg2+, Ni2+, and Zn2+) frequently found in the ISS potable water can be detected simultaneously using this BGE in less than 4.5 min. By using a BGE composed of 0.5 M acetic acid, levels of Ag+ as low as 25 ppb could be detected in the ISS water simulant in less than 2.5 min. Although in this condition none of the other cations interfered with the detection of Ag+, some of them co-migrated, which could prevent obtaining additional information about the sample composition.

The determination of ethanol is one of the most important parameters in the fermentation industry, influencing not only the production yield and the quality of the product, but also its commercial value. In addition to the traditional approach based on distillation/density, procedure that is considered laborious and time-consuming, methods based on chromatography are widely used. Alternatives using electrochemical, spectroscopic and colorimetric techniques have been also proposed for alcohol analysis. In general, these methods not only offer limited throughput, but also require harsh reaction conditions and/or complex instrumentation. Aiming to address these shortcomings, we propose a fast, simple and clean analytical approach for the determination of primary alcohols based on the photochemical oxidation under UV-LED irradiation in the presence of H 2 O 2 . The proposed method was successfully applied to the analysis of 12 different types of alcoholic beverages with an alcohol content ranging from 5% v/v (beer) to 53% v/v (whiskey)., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

1-propanol is a primary alcohol extensively used in the pharmaceutical, chemical, and food industries. It has been also found as a contaminant in the atmosphere and is considered a model compound to mimic the behavior and fate of aliphatic alcohols exposed to environmental conditions. In order to understand that role of relevant variables, this paper presents results obtained with a simple experimental set-up to investigate the reactivity of 1-propanol under mild oxidizing conditions. Coupling this system with CE-C 4 D allowed the quantification of the carboxylic acids formed. For the described experiments, aqueous solutions of 1-propanol were placed inside a photoreactor and oxidized upon the addition of TiO 2 and/or H 2 O 2 . According to the described results, the addition of H 2 O 2 (0.1% w/w) was the most significant variable, roughly tripled the amount of carboxylic acids generated and led to the conversion of up to 70% of the initially available 1-propanol (1 mmol/L). More importantly, the reaction yielded the formation (within 10 min) of propionate (50 µmol/L), acetate (400 µmol/L), formate (50 µmol/L), and malonate (200 µmol/L). The latter is critically important because it represents the first example of the photochemical oxidation of both terminal carbons of the C 3 -chain of 1-propanol under mild conditions, and opens new avenues for the production of this important chemical building block., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

With growing interest in exploring ocean worlds, such as Europa and Enceladus, there is a fundamental need to develop liquid-based analytical techniques capable of handling high salinity samples while performing both bulk and trace species measurements. In this context, CE with capacitively coupled contactless conductivity detection (CE-C 4 D) has tremendous potential. One of its advantages is that this combination allows the detection of a wide number of charged species (both organic and inorganic) without the need of derivatization. Amino acids are an example of organic targets that are powerful biosignatures in the search for life beyond Earth. Simultaneous information on the inorganic cations in a sample helps with assessing the habitability of an extraterrestrial environment, as well as providing sample context for any measurements of trace amino acids. In this work, we present a series of flight-compatible methods capable of simultaneously measuring inorganic cations and amino acids in samples of varying salinity by CE-C 4 D. Regardless of the sample total salinity, 5.0 M acetic acid was selected as the optimum BGE. The methods were evaluated by analyzing natural samples of low and high salinity from Hot Creek Gorge, Mono Lake, and Santa Monica beach. Prospects for mission implementation are also discussed., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The importance of microorganisms and biotechnology in space exploration and future planets colonization has been discussed in the literature. Meteorites are interesting samples to study microbe-mineral interaction focused on space exploration. The chemolithotropic bacterium Acidithiobacillus ferrooxidans has been used as model to understand the iron and sulfur oxidation. In this work, capillary electrophoresis with capacitively coupled contactless conductivity detection and UV detection was used to monitor bacterial growth in a meteorite simulant by measuring the conversion of Fe 2+ into Fe +3 . The effect of Co 2+ and Ni 2+ (metals also found in meteorites) on the bacterial growth was also evaluated. The presented method allowed the analyses of all metals in a single run (less than 8 min). The background electrolyte was composted of 10 mmol/L α-hydroxyisobutyric acid/Histidine. For comparison purpose, the samples were also analyzed by UV-Vis spectrophotometry. The Fe 2+ conversion into Fe 3+ by A. ferrooxidans was observed up to 36 h with the growth rate constant of 0.19/h and 0.21/h in Tuovinen and Kelly (T&K) and in meteorite simulant media, respectively. The developed method presents favorable prospect to monitor the growth of other chemolithotropic microorganisms for biotechnology applications., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An EC-CE-C 4 D flow system was applied to the investigation of electrocatalytic processes by monitoring carboxylic acids formed during the electro-oxidation at various potentials of primary alcohols (mixture of 1 mmol/L of ethanol, n-propanol, n-butanol and n-pentanol) in acidic, neutral and alkaline media. The electro-oxidation was carried out on gold and platinum disk electrodes (3 mm of diameter) in a thin-layer electrochemical flow cell. Products were sampled 50 μm apart from the electrode directly into the capillary. All the generated carboxylates were determined in near real time (less than 2 min) by CE-C 4 D in counter-flow mode, with Tris/HCl buffer solution (pH 8.6) as BGE. Long sequences of 5-min experiments were run automatically, exploring the applied potential, electrolysis time and solution composition. Electro-oxidation at 1.5 V (versus Ag/AgCl quasi-reference) during 50 s in acidic medium was found appropriate for both Pt and Au electrodes when the determination of alcohols after derivatization is intended. A noteworthy selectivity effect was observed on the Au electrode. The signal corresponding to pentanoate is similar on both electrodes while the signal of ethanoate (acetate) is four times larger on gold than on platinum. The carboxylate signals were lower in alkaline medium (below the determination limit on Pt) than in acidic and neutral media. On gold, the formation of carboxylates was anticipated (0.85 V in alkaline medium versus 1.40 V in neutral medium). The automatic online monitoring of electrochemical processes by EC-CE-C 4 D holds great potential to investigate ionic/ionizable intermediates/products of new electrocatalysts and/or alternative fuels., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)