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.

How to Design a Spectrometer.

Designing a spectrometer requires knowledge of the problem to be solved, the molecules whose properties will contribute to a solution of that problem and skill in many subfields of science and engineering. A seemingly simple problem, design of an ultraviolet, visible, and near-infrared spectrometer, is used to show the reasoning behind the trade-offs in instrument design. Rather than reporting a fully optimized instrument, the Yin and Yang of design choices, leading to decisions about financial cost, materials choice, resolution, throughput, aperture, and layout are described. To limit scope, aspects such as grating blaze, electronics design, and light sources are not presented. The review illustrates the mixture of mathematical rigor, rule of thumb, esthetics, and availability of components that contribute to the art of spectrometer design.

Stacked, Mutually Rotated Diffraction Gratings as Enablers of Portable Visible Spectrometry.

Two-dimensional color CMOS cameras have become ubiquitous. They promise to support ubiquitous spectrometry. When raw illumination levels can be measured by such cameras, their use for spectrometry depends on using as many pixels as possible and on being able to calibrate images at point-of-use. Stacked, mutually rotated transmission diffraction gratings provide a means to generate multi-order, wide dynamic range dispersed visible spectra suitable for absorption, reflection, and fluorescence spectrometry. The theoretical basis for dispersion, resolution, and normalization of such spectra are derived, and initial characterization is reported.

Spectrometry with consumer-quality CMOS cameras.

Many modern spectrometric instruments use diode arrays, charge-coupled arrays, or CMOS cameras for detection and measurement. As portable or point-of-use instruments are desirable, one would expect that instruments using the cameras in cellular telephones and tablet computers would be the basis of numerous instruments. However, no mass market for such devices has yet developed. The difficulties in using megapixel CMOS cameras for scientific measurements are discussed, and promising avenues for instrument development reviewed. Inexpensive alternatives to use of the built-in camera are also mentioned, as the long-term question is whether it is better to overcome the constraints of CMOS cameras or to bypass them.

Mixing in colliding, ultrasonically levitated drops.

Lab-in-a-drop, using ultrasonic levitation, has been actively investigated for the last two decades. Benefits include lack of contact between solutions and an apparatus and a lack of sample cross-contamination. Understanding and controlling mixing in the levitated drop is necessary for using an acoustically levitated drop as a microreactor, particularly for studying kinetics. A pulsed electrostatic delivery system enables addition and mixing of a desired-volume droplet with the levitated drop. Measurement of mixing kinetics is obtained by high-speed video monitoring of a titration reaction. Drop heterogeneity is visualized as 370 nl of 0.25 M KOH (pH: 13.4) was added to 3.7 µL of 0.058 M HCl (pH: 1.24). Spontaneous mixing time is about 2 s. Following droplet impact, the mixed drop orbits the levitator axis at about 5 Hz during homogenization. The video's green channel (maximum response near 540 nm) shows the color change due to phenolphthalein absorption. While mixing is at least an order of magnitude faster in the levitated drop compared with three-dimensional diffusion, modulation of the acoustic waveform near the surface acoustic wave resonance frequency of the levitated drop does not substantially reduce mixing time.

Electrochemistry in an acoustically levitated drop.

Levitated drops show potential as microreactors, especially when radicals are present as reactants or products. Solid/liquid interfaces are absent or minimized, avoiding adsorption and interfacial reaction of conventional microfluidics. We report amperometric detection in an acoustically levitated drop with simultaneous ballistic addition of reactant. A gold microelectrode sensor was fabricated with a lithographic process; active electrode area was defined by a photosensitive polyimide mask. The microdisk gold working electrode of radius 19 µm was characterized using ferrocenemethanol in aqueous buffer. Using cyclic voltammetry, the electrochemically active surface area was estimated by combining a recessed microdisk electrode model with the Randles-Sevcik equation. Computer-controlled ballistic introduction of reactant droplets into the levitated drop was developed. Chronoamperometric measurements of ferrocyanide added ballistically demonstrate electrochemical monitoring using the microfabricated electrode in a levitated drop. Although concentration increases with time due to drop evaporation, the extent of concentration is predictable with a linear evaporation model. Comparison of diffusion-limited currents in pendant and levitated drops show that convection arising from acoustic levitation causes an enhancement of diffusion-limited current on the order of 16%.

Potential of levitated drops to serve as microreactors for biophysical measurements.

Microreactors are desirable for exploring chemical and biological processes, as reactant consumption is minimal and safety issues are easily managed. Levitated drops are a class of microreactors for which mixing is continuous and solid/liquid interfaces are absent or of lesser importance than in channeled microfabricated flow reactors. Thus, reactant adsorption or wall catalysis possibly of importance in ordinary microfluidic systems is absent in levitated drops. Transport of gaseous reactants or products is facile. Levitated drop microreactors are amenable to batch or continuous flow study of biochemical reactions. The possibility of studying oscillatory enzyme-catalyzed reactions in drops is apparent. This review explains the physics and chemistry of levitated drop microreactors and describes practical aspects of their design, fabrication, implementation, and optimization. Such considerations as drop evaporation, thermal control, protein behavior at the gas/liquid interface, and observation with spectroscopic and electrochemical probes are discussed.

Teaching, learning, and using spectroscopy with commercial, off-the-shelf technology.

The astonishing propagation of sophisticated electronics across the globe has attracted the attention of many for developing disease diagnoses, water purity measurements, and security applications using cellular telephones and the complementary metal oxide semiconductor (CMOS) cameras with which many are equipped. This Focal Point article builds on the theme of using technology already in the hands of students/consumers to teach spectrophotometry and, by extension, to suggest how one might inexpensively develop an instrumental analysis curriculum at extraordinarily low cost. A grating spectrophotometer using a white light-emitting diode (LED) light source, plastic sample cuvette, holographic transmission grating, and any camera that produces JPG files as output is described. Optical characteristics are explained and a sample working curve provided. The raw data for that curve are available as Supplementary Material on-line. The behavior of the "Cell Phone Spectrometer" is inadequate for routine analysis but outstanding for teaching the workings of optical instrumentation components and systems.

Sample handling and chemical kinetics in an acoustically levitated drop microreactor.

Accurate measurement of enzyme kinetics is an essential part of understanding the mechanisms of biochemical reactions. The typical means of studying such systems use stirred cuvettes, stopped-flow apparatus, microfluidic systems, or other small sample containers. These methods may prove to be problematic if reactants or products adsorb to or react with the container's surface. As an alternative approach, we have developed an acoustically-levitated drop reactor eventually intended to study enzyme-catalyzed reaction kinetics related to free radical and oxidative stress chemistry. Microliter-scale droplet generation, reactant introduction, maintenance, and fluid removal are all important aspects in conducting reactions in a levitated drop. A three capillary bundle system has been developed to address these needs. We report kinetic measurements for both luminol chemiluminescence and the reaction of pyruvate with nicotinamide adenine dinucleotide, catalyzed by lactate dehydrogenase, to demonstrate the feasibility of using a levitated drop in conjunction with the developed capillary sample handling system as a microreactor.

Design and implementation of an efficient acoustically levitated drop reactor for in stillo measurements.

We present the details necessary for building an efficient acoustic drop levitator with reduced electrical power consumption and greater drop stability compared to previous designs. The system is optimized so that the levitated drop may be used as a chemical reactor. By introducing a temperature, pressure, and relative humidity sensor for feedback control of a linear actuator for adjusting resonator length, we have built a completely automated system capable of continuous levitation for extended periods of time. The result is a system capable of portable operation and interfacing with a variety of detection instrumentation for in stillo (in drop) measurements.

Biofilm effects on the peroxidase-oxidase reaction.

In experiments on the kinetics of the peroxidase-oxidase oscillatory reaction in pH 5.l acetate buffer, biofilms form in less than 48 h on the quartz reactor surface. The nominally homogeneous peroxidase system shows dynamical changes in response to this biofilm growth, partially explaining subtle differences among dynamics observed over time and between laboratories. Kinetics data and model computations are correlated with micrographs of biofilm formation. It is evident that bare quartz also interacts with reaction species, so that the surface area-to-volume ratio is an important parameter on which observed dynamics depend.