Annual Review of Analytical Chemistry - Volume 5, 2012

Following a brief overview of the history of analysis of artists' pigments, I discuss the illustrative example of lead-tin yellow. Recent advances in our knowledge of artists' use of red lakes, glassy pigments, and metallic pigments in works of cultural heritage, particularly European paintings, as determined from chemical analyses are described.

Transformational advances in the performance of nanowire-based chemical sensors and biosensors have been achieved over the past two to three years. These advances have arisen from a better understanding of the mechanisms of transduction operating in these devices, innovations in nanowire fabrication, and improved methods for incorporating receptors into or onto nanowires. Nanowire-based biosensors have detected DNA in undiluted physiological saline. For silicon nanowire nucleic acid sensors, higher sensitivities have been obtained by eliminating the passivating oxide layer on the nanowire surface and by substituting uncharged protein nucleic acids for DNA as the capture strands. Biosensors for peptide and protein cancer markers, based on both semiconductor nanowires and nanowires of conductive polymers, have detected these targets at physiologically relevant concentrations in both blood plasma and whole blood. Nanowire chemical sensors have also detected several gases at the parts-per-million level. This review discusses these and other recent advances, concentrating on work published in the past three years.

Distance-of-flight mass spectrometry (DOFMS) offers the advantages of physical separation of ions, array detection of ions, focusing of initial ion energy, great simplicity, and a truly unlimited mass range. DOFMS instrumentation is similar to that of time-of-flight mass spectrometry (TOFMS) and shares its ion-source versatility, batch analysis, and rapid spectral-generation rate. With constant-momentum ion acceleration and an ion mirror, there is a time at which ions of all mass-to-charge values are energy focused at their particular distances along the flight path. A pulsed field orthogonal to the flight path drives the ions to reach the detector array at this specific time. Results from a 0.29-m proof-of-principle instrument verify the theoretically predicted energy focus and demonstrate how the range of mass-to-charge values that impinge on the detector array can be readily changed. DOFMS could be combined sequentially with TOFMS to enable simultaneous scanless tandem mass spectrometry.

The blood-brain barrier (BBB) is an important interface between the peripheral and central nervous systems. It protects the brain against the infiltration of harmful substances and regulates the permeation of beneficial endogenous substances from the blood into the extracellular fluid of the brain. It can also present a major obstacle in the development of drugs that are targeted for the central nervous system. Several methods have been developed to investigate the transport and metabolism of drugs, peptides, and endogenous compounds at the BBB. In vivo methods include intravenous injection, brain perfusion, positron emission tomography, and microdialysis sampling. Researchers have also developed in vitro cell-culture models that can be employed to investigate transport and metabolism at the BBB without the complication of systemic involvement. All these methods require sensitive and selective analytical methods to monitor the transport and metabolism of the compounds of interest at the BBB.