EXPRESS: Landmark Publications in Analytical Atomic Spectrometry: Fundamentals and Instrumentation Development.

The almost-two-centuries history of spectrochemical analysis has generated a body of literature so vast that it has become nearly intractable for experts, much less for those wishing to enter the field. Authoritative, focused reviews help to address this problem but become so granular that the overall directions of the field are lost. This broader perspective can be provided partially by general overviews but then the thinking, experimental details, theoretical underpinnings and instrumental innovations of the original work must be sacrificed. In the present compilation, this dilemma is overcome by assembling the most impactful publications in the area of analytical atomic spectrometry. Each entry was proposed by at least one current expert in the field and supported by a narrative that justifies its inclusion. The entries were then assembled into a coherent sequence and returned to contributors for a round-robin review.

Wireless Data Acquisition of Transient Signals for Mobile Spectrometry Applications.

Wireless data acquisition using smartphones or handhelds offers increased mobility, it provides reduced size and weight, it has low electrical power requirements, and (in some cases) it has an ability to access the internet. Thus, it is well suited for mobile spectrometry applications using miniaturized, field-portable spectrometers, or detectors for chemical analysis in the field (i.e., on-site). There are four main wireless communications standards that can be used for wireless data acquisition, namely ZigBee, Bluetooth, Wi-Fi, and UWB (ultra-wide band). These are briefly reviewed and are evaluated for applicability to data acquisition of transient signals (i.e., time-domain) in the field (i.e., on-site) from a miniaturized, field-portable photomultiplier tube detector and from a photodiode array detector installed in a miniaturized, field-portable fiber optic spectrometer. These are two of the most widely used detectors for optical measurements in the ultraviolet-visible range of the spectrum. A miniaturized, 3D-printed, battery-operated microplasma-on-a-chip was used for generation of transient optical emission signals. Elemental analysis from liquid microsamples, a microplasma, and a handheld or a smartphone will be used as examples. Development and potential applicability of wireless data acquisition of transient optical emission signals for taking part of the lab to the sample types of mobile, field-portable spectrometry applications will be discussed. The examples presented are drawn from past and ongoing work in the authors' laboratory. A handheld or a smartphone were used as the mobile computing devices of choice.

Battery-operated, argon-hydrogen microplasma on hybrid, postage stamp-sized plastic-quartz chips for elemental analysis of liquid microsamples using a portable optical emission spectrometer.

A battery-operated, atmospheric pressure, self-igniting, planar geometry Ar-H(2) microplasma for elemental analysis of liquid microsamples is described. The inexpensive microplasma device (MPD) fabricated for this work was a hybrid plastic-quartz structure that was formed on chips with an area (roughly) equal to that of a small-sized postage stamp (MPD footprint, 12.5-mm width by 38-mm length). Plastic substrates were chosen due to their low cost, for rapid prototyping purposes, and for a speedy microplasma device evaluation. To enhance portability, the microplasma was operated from an 18-V rechargeable battery. To facilitate portability even further, it was demonstrated that the battery can be recharged by a portable solar panel. The battery-supplied dc voltage was converted to a high-voltage ac. The ~750-µm (diameter) and 12-mm (long) Ar-H(2) (3% H(2)) microplasma was formed by applying the high-voltage ac between two needle electrodes. Spectral interference from the electrode materials or from the plastic substrate was not observed. Operating conditions were found to be key to igniting and sustaining a microplasma that was simply "warm" to the touch (thus alleviating the need for cooling or other thermal management) and that had a stable background emission. A small-sized (900 µL internal volume) electrothermal vaporization system (40-W max power) was used for microsample introduction. Microplasma background emission in the spectral region between 200 and 850 nm obtained using a portable fiber-optic spectrometer is reported and the effect of the operating conditions is described. Analyte emission from microliter volumes of dilute single-element standard solutions of Cd, Cu, K, Li, Mg, Mn, Na, Pb, and Zn is documented. The majority of spectral lines observed for the elements tested were from neutral atoms. The relative lack of emission from ion lines simplified the spectra, thus facilitating the use of a portable spectrometer. Despite the relative spectral simplicity, some spectral interference effects were noted when running a multi-element solution. An example of how interference in the spectral domain can be resolved in the time domain using selective thermal vaporization is provided. Analytical utility and performance characteristics are reported; for example, K concentrations in diluted (~30 times) bottled water were determined to be 4.1 ± 1.0 µg/mL (4 µg/mL was the stated concentration), precision was about 25%, and the estimated detection limits were in the picogram range (or in nanograms per milliliter in relative units).

Nonamyloid aggregates arising from mature copper/zinc superoxide dismutases resemble those observed in amyotrophic lateral sclerosis.

Protein aggregation is a hallmark of many diseases, including amyotrophic lateral sclerosis (ALS) where aggregation of copper/zinc superoxide dismutase (SOD1) is implicated in pathogenesis. We report here that fully metallated (holo) SOD1 under physiologically relevant solution conditions can undergo changes in metallation and/or dimerization over time and form aggregates that do not exhibit classical characteristics of amyloid. The relevance of the observed aggregation to disease is demonstrated by structural and tinctorial analyses, including the novel observation of binding of an anti-SOD1 antibody that specifically recognizes aggregates in ALS patients and mice models. ALS-associated SOD1 mutations can promote aggregation but are not essential. The SOD1 aggregation is characterized by a lag phase, which is diminished by self- or cross-seeding and by heterogeneous nucleation. We interpret these findings in terms of an expanded aggregation mechanism consistent with other in vitro and in vivo findings that point to multiple pathways for the formation of toxic aggregates by different forms of SOD1.

Helium-hydrogen microplasma device (MPD) on postage-stamp-size plastic-quartz chips.

A new design of a miniaturized, atmospheric-pressure, low-power (e.g., battery-operated), self-igniting, planar-geometry microplasma device (MPD) for use with liquid microsamples is described. The inexpensive MPD was a hybrid, three-substrate quartz-plastic-plastic structure and it was formed on chips with area the size of a small postage stamp. The substrates were chosen for rapid prototyping and for speedy device-geometry testing and evaluation. The approximately 700-microm (diameter) and 7-mm (long) He-H(2) (3% H(2)) microplasma was formed by applying high-voltage ac between two needle electrodes. Operating conditions were found to be critical in sustaining stable microplasma on plastic substrates. Spectral interference from the electrode materials was not observed. A small-size, electrothermal vaporization system was used for introduction of microliter volumes of liquids into the MPD. The microplasma was operated from an inexpensive power supply. And, operation from a 14.4-V battery has been demonstrated. Microplasma background emission in the spectral range between 200 and 850 nm obtained using a portable, fiber-optic spectrometer is reported. Analyte emission from microliter volumes of dilute single-element standard solutions of Cd, Cu, K, Li, Mg, Mn, Na, Pb, and Zn is documented. Element-dependent precision was between 10-25% (the average was 15%) and detection limits ranged between 1.5 and 350 ng. The system was used for the determination of Na in diluted bottled-water samples.

Micromachined, planar-geometry, atmospheric-pressure, battery-operated microplasma devices (MPDs) on chips for analysis of microsamples of liquids, solids, or gases by optical-emission spectrometry.

Because of their desirable characteristics, for example small size, lightness, low power and gas consumption, and potential for portability, miniaturized plasma sources are receiving significant attention in the scientific literature. To take advantage of these characteristics we micromachined and fabricated new, planar-geometry, self-igniting, atmospheric-pressure microplasma devices (MPDs) on chips. These microplasmas required such low power for their operation they could be operated from a re-chargeable battery (of the type used in cordless power-tools). Despite their advantages, most miniaturized plasma sources reported in the literature have not performed well with liquid samples; analysis of powders or solids that can be converted to a powder (and processed and used as slurries) is even more difficult. To address these shortcomings we coupled an electrothermal, mini-in-torch vaporization (mini-ITV) "dry" sample-introduction system to the low-power planar microplasma devices we developed. In this preliminary investigation, absolute detection limits obtained from microsamples of single-element liquid standards and optical emission spectrometry with photomultiplier-tube detection and a spectral bandpass similar to that of portable, commercially available fiber-optic spectrometers were in the low-pg to ng range, for example 2 pg (for K) to 25 ng (for Pb). Mini-ITV also enabled (as far as we are aware, for the first time) measurement of analyte emission from microsamples of powdered solids (as slurries). In addition to the 3% H2 in Ar mixtures, the ac-operated microplasmas were sustained by use of a variety of electrode materials and different plasma-support gases (e.g. Ar, He and 3% H2 in He) thus indicating fabrication versatility and operational flexibility. Such flexibility has the potential to enable microplasmas to be tailored to analytical problems, and this is demonstrated by using a He MPD and chlorine emission measurements (837.594 nm) from gaseous microsamples as an example.

Purification and characterization of an iron-containing alcohol dehydrogenase in extremely thermophilic bacterium Thermotoga hypogea.

Thermotoga hypogea is an extremely thermophilic anaerobic bacterium capable of growing at 90 degrees C. It uses carbohydrates and peptides as carbon and energy sources to produce acetate, CO(2), H(2), L-alanine and ethanol as end products. Alcohol dehydrogenase activity was found to be present in the soluble fraction of T. hypogea. The alcohol dehydrogenase was purified to homogeneity, which appeared to be a homodimer with a subunit molecular mass of 40 +/- 1 kDa revealed by SDS-PAGE analyses. A fully active enzyme contained iron of 1.02 +/- 0.06 g-atoms/subunit. It was oxygen sensitive; however, loss of enzyme activity by exposure to oxygen could be recovered by incubation with dithiothreitol and Fe(2+). The enzyme was thermostable with a half-life of about 10 h at 70 degrees C, and its catalytic activity increased along with the rise of temperature up to 95 degrees C. Optimal pH values for production and oxidation of alcohol were 8.0 and 11.0, respectively. The enzyme had a broad specificity to use primary alcohols and aldehydes as substrates. Apparent K (m) values for ethanol and 1-butanol were much higher than that of acetaldehyde and butyraldehyde. It was concluded that the physiological role of this enzyme is likely to catalyze the reduction of aldehydes to alcohols.

68Zn isotope exchange experiments reveal an unusual kinetic lability of the metal ions in the di-zinc form of IMP-1 metallo-beta-lactamase.

The apparently paradoxical behaviour of facile exchange (kinetic lability) of tightly bound (thermodynamic stability) zinc ions in the enzyme IMP-1 metallo-beta-lactamase with Zn-68 and cadmium ions, as indicated by in-torch vaporization inductively-coupled plasma mass spectrometry (ITV-ICP-MS) and electrospray-ionization mass spectrometry (ESI-MS), is consistent with the involvement of a third metal ion in promoting Lewis acid/base type exchange processes.

Simultaneous determination of the Cd and Zn total body burden of individual, nearly microscopic, nanoliter-volume aquatic organisms ( Hyalella azteca) by rhenium-cup in-torch vaporization (ITV) sample introduction and axially viewed ICP-AES.

The Cd and Zn total body burden of individual, up to 7-day-old aquatic organisms (Hyalella azteca benthic amphipod) with an average volume of approximately 100 nL was determined simultaneously by using rhenium-cup (Re-cup) in-torch vaporization (ITV) sample introduction and an axially viewed inductively coupled plasma atomic emission spectrometry (ICP-AES) system. The direct elemental analysis capabilities of this system (i.e., no sample digestion) reduced sample preparation time, eliminated contamination concerns from the digestion reagent and, owing to its detection limits (e.g., in the low pg range for Cd and Zn), vit enabled simultaneous determinations of Cd and Zn in individual, neonate and young juvenile specimens barely visible to the unaided eye (e.g., nearly microscopic). As for calibration, liquid standards and the standard additions method were tested. Both methods gave comparable results, thus indicating that in this case liquid standards can be employed for calibration, and in the process making use of the standard additions method unnecessary. Overall, the ITV-ICP-AES approach by-passed the time-consuming acid digestions, eliminated the potential for contamination from the digestion reagents, improved considerably the speed of acquisition of analytical information and enabled simultaneous determinations of two elements using individual biological specimens.