Factorial Design to Optimize Matrix Spraying Parameters for MALDI Mass Spectrometry Imaging.

Matrix deposition is a critical step in obtaining reproducible and spatially representative matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging data. To date, few limited studies have examined the optimization of matrix spraying parameters for maximizing analyte extraction while minimizing analyte delocalization. Herein, we present a study using automated pneumatic spraying with a heated sample-holder tray to determine an optimized model for mouse whole kidney lipid imaging using a 2,5-dihydroxybenzoic acid matrix in which the solvent flow rate, nozzle velocity, and sample heating were optimized using a two-level factorial experimental design. Parameters examined to determine the optimum model include the number of analytes, the matrix crystal size, off tissue delocalization, the signal intensity, and spray time. Our results show that sample heating using a heated tray while spraying improves the MALDI imaging performance. This improvement is possible because higher solvent flow rates can be used in the pneumatic sprayer, allowing for better sample extraction, while sample delocalization is minimized due to sample heating.

Pneumatically Sprayed Gold Nanoparticles for Mass Spectrometry Imaging of Neurotransmitters.

Using citrate-capped gold nanoparticles (AuNPs) for laser desorption ionization mass spectrometry (LDI-MS) is an approach that has demonstrated broad applicability to ionization of different classes of molecules. Here, we show a simple AuNP-based approach for the ionization of neurotransmitters. Specifically, the detection of acetylcholine, dopamine, epinephrine, glutamine, 4-aminobutyric acid, norepinephrine, octopamine, and serotonin was achieved at physiologically relevant concentrations in serum and homogenized tissue. Additionally, pneumatic spraying of AuNPs onto tissue sections facilitated mass spectrometry imaging (MSI) of rabbit brain tissue sections, zebrafish embryos, and neuroblastoma cells for several neurotransmitters simultaneously using this quick and simple sample preparation. AuNP LDI-MS achieved mapping of neurotransmitters in fine structures of zebrafish embryos and neuroblastoma cells at a lateral spatial resolution of 5 µm. The use of AuNPs to ionize small aminergic neurotransmitters in situ provides a fast, high-spatial resolution method for simultaneous detection of a class of molecules that typically evade comprehensive detection with traditional matrixes.

Correction: Transient response of the Northwestern Iberian upwelling regime.

[This corrects the article DOI: 10.1371/journal.pone.0197627.].

Transient response of the Northwestern Iberian upwelling regime.

The hydrography and dynamics of NW Iberian margin were explored for July 2009, based on a set of in situ and remote sensing observations. Zonal sections of standard CTD casts, towed CTD (SeaSoar), Acoustic Doppler Current Profilers (ADCP) and Lagrangian surveys were made to characterize cycles of upwelling and relaxation in this region. Two periods of northerly winds, bounded by relaxation periods, were responsible for the formation of an upwelling front extending to the shelf edge. An equatorward flow was quickly set up on the shelf responding to the northerly wind pulses. South of Cape Silleiro, the development and subsequent relaxation of an upwelling event was intensively surveyed in the shelf, following a Lagrangian drifter transported by the upwelling jet. This region is part of an upwelling center extending from Cape Silleiro to Porto, where the surface temperature was colder than the neighboring regions, under upwelling favorable winds. As these winds relaxed, persistent poleward flow developed, originating south of the upwelling center and consisting in an inner-shelf tongue of warm waters. During an event of strong southerly wind, the poleward flow was observed to extend to the whole continental shelf. Although the cruise was executed during summertime, the presence of river-plumes was observed over the shelf. The interaction of the plumes with the circulation on the shelf was also described in terms of coastal convergence and offshore advection. The sampling of the offshore and slope regions showed the presence of the Iberian poleward current offshore and a persistent equatorward flow over the upper slope.

Freshwater exchanges and surface salinity in the Colombian basin, Caribbean Sea.

Despite the heavy regional rainfall and considerable discharge of many rivers into the Colombian Basin, there have been few detailed studies about the dilution of Caribbean Surface Water and the variability of salinity in the southwestern Caribbean. An analysis of the precipitation, evaporation and runoff in relation to the climate variability demonstrates that although the salt balance in the Colombian Basin overall is in equilibrium, the area south of 12°N is an important dilution sub-basin. In the southwest of the basin, in the region of the Panama-Colombia Gyre, Caribbean Sea Water is diluted by precipitation and runoff year round, while in the northeast, off La Guajira, its salinity increases from December to May by upwelling. At the interannual scale, continental runoff is related to El Niño Southern Oscillation, and precipitation and evaporation south of 12°N are related to the Caribbean Low Level Jet. During El Niño years the maximum salinification occurs in the dry season (December-February) while in La Niña years the maximum dilution (or freshening), reaching La Guajira Coastal Zone, occurs in the wet season (September-November).

Effects of Geostrophic Kinetic Energy on the Distribution of Mesopelagic Fish Larvae in the Southern Gulf of California in Summer/Fall Stratified Seasons.

Effects of geostrophic kinetic energy flux on the three-dimensional distribution of fish larvae of mesopelagic species (Vinciguerria lucetia, Diogenichthys laternatus, Benthosema panamense and Triphoturus mexicanus) in the southern Gulf of California during summer and fall seasons of stronger stratification were analyzed. The greatest larval abundance was found at sampling stations in geostrophic kinetic energy-poor areas (<7.5 J/m3), where the distribution of the dominant species tended to be stratified. Larvae of V. lucetia (average abundance of 318 larvae/10m2) and B. panamense (174 larvae/10m2) were mostly located in and above the pycnocline (typically ~ 40 m depth). In contrast, larvae of D. laternatus (60 larvae/10m2) were mainly located in and below the pycnocline. On the other hand, in sampling stations from geostrophic kinetic energy-rich areas (> 21 J/m3), where mesoscale eddies were present, the larvae of the dominant species had low abundance and were spread more evenly through the water column, in spite of the water column stratification. For example, in a cyclonic eddy, V. lucetia larvae (34 larvae/10m2) extended their distribution to, at least, the limit of sampling 200 m depth below the pycnocline, while D. laternatus larvae (29 larvae/10m2) were found right up to the surface, both probably as a consequence mixing and secondary circulation in the eddy. Results showed that the level of the geostrophic kinetic energy flux affects the abundance and the three-dimensional distribution of mesopelagic fish larvae during the seasons of stronger stratification, indicating that areas with low geostrophic kinetic energy may be advantageous for feeding and development of mesopelagic fish larvae because of greater water column stability.