There are a variety of complementary observations that could be used in the search for life in extraterrestrial settings. At the molecular scale, patterns in the distribution of organics could provide powerful evidence of a biotic component. In order to observe these molecular biosignatures during spaceflight missions, it is necessary to perform separation science in situ. Microchip electrophoresis (ME) is ideally suited for this task. Although this technique is readily miniaturized and numerous instruments have been developed over the last 3 decades, to date, all lack the automation capabilities needed for future missions of exploration. We have developed a portable, automated, batterypowered, and remotely operated ME instrument coupled to laserinduced fluorescence detection. This system contains all the necessary hardware and software interfaces for end-to-end functionality. Here, we report the first application of the system for amino acid analysis coupled to an extraction unit in order to demonstrate automated sample-to-data operation. The system was remotely operated aboard a rover during a simulated Mars mission in the Atacama Desert, Chile. This is the first demonstration of a fully automated ME analysis of soil samples relevant to planetary exploration. This validation is a critical milestone in the advancement of this technology for future implementation on a spaceflight mission.

Understanding basic concepts of electronics and computer programming allows researchers to get the most out of the equipment found in their laboratories. Although a number of platforms have been specifically designed for the general public and are supported by a vast array of on-line tutorials, this subject is not normally included in university chemistry curricula. Aiming to provide the basic concepts of hardware and software, this article is focused on the design and use of a simple module to control a series of PDMS-based valves. The module is based on a low-cost microprocessor (Teensy) and open-source software (Arduino). The microvalves were fabricated using thin sheets of PDMS and patterned using CO2 laser engraving, providing a simple and efficient way to fabricate devices without the traditional photolithographic process or facilities. Synchronization of valve control enabled the development of two simple devices to perform injection (1.6 ± 0.4 μL/stroke) and mixing of different solutions. Furthermore, a practical demonstration of the utility of this system for microscale chemical sample handling and analysis was achieved performing an on-chip acid-base titration, followed by conductivity detection with an open-source low-cost detection system. Overall, the system provided a very reproducible (98%) platform to perform fluid delivery at the microfluidic scale.

This paper describes a long-range remotely controlled CE system built on an all-terrain vehicle. A four-stroke engine and a set of 12-V batteries were used to provide power to a series of subsystems that include drivers, communication, computers, and a capillary electrophoresis module. This dedicated instrument allows air sampling using a polypropylene porous tube, coupled to a flow system that transports the sample to the inlet of a fused-silica capillary. A hybrid approach was used for the construction of the analytical subsystem combining a conventional fused-silica capillary (used for separation) and a laser machined microfluidic block, made of PMMA. A solid-state cooling approach was also integrated in the CE module to enable controlling the temperature and therefore increasing the useful range of the robot. Although ultimately intended for detection of chemical warfare agents, the proposed system was used to analyze a series of volatile organic acids. As such, the system allowed the separation and detection of formic, acetic, and propionic acids with signal-to-noise ratios of 414, 150, and 115, respectively, after sampling by only 30 s and performing an electrokinetic injection during 2.0 s at 1.0 kV.

Although H + and OH À are the most common ions in aqueous media, they are not usually observable in capillary electrophoresis (CE) experiments, because of the extensive use of buffer solutions as the background electrolyte. In the present work, we introduce CE equipment designed to allow the determination of such ions in a similar fashion as any other ion. Basically, it consists of a fourcompartment piece of equipment for electrolysis-separated experiments (D. P. de Jesus et al., Anal. Chem., 2005, 77, 607). In such a system, the ends of the capillary are placed in two reservoirs, which are connected to two other reservoirs through electrolyte-filled tubes. The electrodes of the high-voltage power source are positioned in these reservoirs. Thus, the electrolysis products are kept away from the inputs of the capillary. The detection was provided by two capacitively coupled contactless conductivity detectors (C 4 D), each one positioned about 11 cm from the end of the capillary. Two applications were demonstrated: titration-like procedures for nanolitre samples and mobility measurements. Strong and weak acids (pK a < 5), pure or mixtures, could be titrated. The analytical curve is linear from 50 mM up to 10 mM of total dissociable hydrogen (r ¼ 0.99899 for n ¼ 10) in 10-nL samples. By including D 2 O in the running electrolyte, we could demonstrate how to measure the mixed proton/deuteron mobility. When H 2 O/D 2 O (9 : 1 v/v) was used as the solvent, the mobility was 289.6 AE 0.5 Â 10 À5 cm 2 V À1 s À1 . Due to the fast conversion of the species, this value is related to the overall behaviour of all isotopologues and isotopomers of the Zundel and Eigen structures, as well as the Stokesian mobility of proton and deuteron. The effect of neutral (o-phenanthroline) and negatively charged (chloroacetate) bases and aprotic solvent (DMSO) over the H + mobility was also demonstrated.

Concurrently with ethanol, many other compounds can be formed during the fermentation of grains and fruits. Among those, methanol is particularly important (because of its toxicity) and is typically formed at concentrations much lower than ethanol, presenting a particular challenge that demands the implementation of separation techniques. Aiming to provide an alternative to traditional chromatographic approaches, a hybrid electrophoresis device with electrochemical preprocessing and contactless conductivity detection (hybrid EC-CE-CD) is herein described. The device was applied to perform the electro-oxidation of primary alcohols, followed by the separation and detection of the respective carboxylates. According to the presented results, the optimum conditions were obtained when the sample was diluted with 2 mmol L HNO and then electro-oxidized by applying a potential of 1.4 V for 60 s. The oxidation products were then electrokinetically injected by applying a potential of 3 kV for 4 s and separated using a potential of 3 kV and a background running electrolyte (BGE) consisting of 10 mmol L N-cyclohexyl-2-aminoethanesulfonic acid (CHES) and 5 mmol L sodium hydroxide (NaOH). n-Propanol was used as an internal standard and the three carboxylate peaks were resolved with baseline separation within <3 min, defining linear calibration curves in the range of 0.10-5.0 mmol L. Limits of detection (LODs) of 20, 40, and 50 μmol L were obtained for ethanol, n-propanol, and methanol, respectively. To demonstrate the applicability of the proposed strategy, a laboratory-made sample (moonshine) was used. Aliquots collected along the beginning of the fractional distillation presented a decreasing methanol ratio (from 4% to <0.5%) and a growing ethanol ratio (from 80% to 100%) in the collected volume.

The formation and properties of carbonate adducts of some organic hydroxy compounds in aqueous medium were investigated. Fatty alcohols and sugars were chosen as representative classes of biological interest, and the medium was carbonated aqueous solution with pH ranging from 3.0 to 8.3. Capillary electrophoresis with two capacitively coupled contactless conductivity detectors (C⁴ Ds) was used for quantitation and to obtain the mobility of the monoalkyl carbonates (MACs), which were used to determine the equilibrium and kinetic constants of the reaction as well as the diffusion coefficients. For increasing chain length of the alcohols, the equilibrium constant tends to the unit, which suggests that fatty alcohols can form the corresponding MACs. The formation of MACs for cyclohexanol and cyclopentanol also suggest the existence of similar species for sterols. Carbonate adducts of fructose, glucose, and sucrose were also detected, which suggests that these counterparts of the well-known phosphates can also occur in the cytosol. Our calculations suggest that one in 1000 to one in 10,000 molecules of these hydroxy compounds would be available as the corresponding MAC in such a medium. Experiments carried out at pH values less than 3.0 showed that there is a catalytic effect of hydronium on the interconversion of bicarbonate and a MAC. Taking into account the great number of hydroxy compounds similar to the ones investigated and that bicarbonate is ubiquitous in living cells, one can anticipate the existence of a whole new class of carbonate adducts of these metabolites.

A top-level NASA exploration goal is the search for signs of life beyond Earth. Molecular biosignatures can be sought via in situ organic chemical analyses of samples collected from planetary bodies. Current spaceflight-ready technologies lack the required sensitivity to perform these analyses on key polar organic species primarily due to the low efficiency of transferring these molecules from natural samples into chemical instrumentation. One promising approach to improve the liberation of these molecules from sample matrices prior to analysis is through the use of liquid extraction, in which organic molecules are dissolved in heated, pressurized water. This process has never been performed on a spaceflight mission. As part of instrument maturation efforts, we describe the development of the first spaceflight prototype of a fully automated subcritical water extractor designed to provide this essential functionality on a potential future planetary mission. The prototype extractor was mounted on a Mars test rover platform and successfully operated remotely in the Atacama Desert, Chile. Samples acquired by the rover's drill and sample acquisition/delivery system were remotely transferred to the extractor inlet funnel, and all subsequent extractor operations were performed automatically. To validate the instrument and demonstrate its suitability as a front-end unit for an organic analyzer, we tested low-bioload Atacama Desert soil extracts for amino acid content using capillary electrophoresis coupled to laser-induced fluorescence. We show that hot extraction under subcritical conditions is required to liberate amino acids from the sample, as no amino acids were found in the extract produced at room temperature. Plain Language SummaryThe search for signs of life beyond Earth is one of NASA's highest priorities. One powerful way to look for extraterrestrial life is to perform chemical analyses on planetary samples in order to characterize any organic molecules present. Past and current spaceflight instruments analyze various components in gases collected or gases produced from solid samples; however, the instruments either lack the sensitivity to detect organic molecules or the instruments destroy many of the organic molecules during the preparation required to perform a gas-phase-based measurement. This work presents an automated pressurized hot water extractor that can be used to release organic molecules from a solid sample. Pressurized hot water is a powerful and easy-to-handle solvent for a wide range of different compounds. The extractor acts as a front-end instrument and prepares the sample for highly sensitive, liquid-based analysis. This automated and remotely controlled prototype has been successfully tested on a simulated Mars rover mission in the Atacama Desert in Chile. Extracts of the Atacama soil samples were then analyzed by capillary electrophoresis coupled to laser-induced fluorescence to determine the extracts' amino acid content, as amino acids are an auspicious class of molecules in the search fo...

Glass is one of the most convenient materials for the development of microfluidic devices. However, most fabrication protocols require long processing times and expensive facilities. As a convenient alternative, polymeric materials have been extensively used due their lower cost and versatility. Although CO2 laser ablation has been used for fast prototyping on polymeric materials, it cannot be applied to glass devices because the local heating causes thermal stress and results in extensive cracking. A few papers have shown the ablation of channels or thin holes (used as reservoirs) on glass but the process is still far away from yielding functional glass microfluidic devices. To address these shortcomings, this communication describes a simple method to engrave glass-based capillary electrophoresis devices using standard (1 mm-thick) microscope glass slides. The process uses a sacrificial layer of wax as heat sink and enables the development of both channels (with semicircular shape) and pass-through reservoirs. Although microscope images showed some small cracks around the channels (that became irrelevant after sealing the engraved glass layer to PDMS) the proposed strategy is a leap forward in the application of the technology to glass. In order to demonstrate the capabilities of the approach, the separation of dopamine, catechol and uric acid was accomplished in less than 100 s.