A durable and inexpensive pump profiler to monitor stratified water columns with high vertical resolution.

A pump profiling system for real time sample collection has been constructed for a cost of <$1000 (USD) and mated with a ship's rosette that has conductivity, temperature, depth (CTD) and other sensors. The system permits the collection of ~15 L of water in one minute without exposure to O2 from air for discrete sampling of chemical, microbial and other constituents as well as for real time analyses using sensors. We also coupled a shipboard voltammetry system with solid-state microelectrodes to detect dissolved O2 and H2S. Electrode O2 detection limits (DL) are ~3 µM and compare well with in situ Clark electrode O2 data (DL ~2 µM) from the ship's CTD rosette system. H2S measurements also were reliable, based on previously compared methods. Best resolution of the profiling system can be as small as its orifice of 2.54 cm (0.0254 m) in a quiet sea state, which is an improvement over the maximum resolution achievable using 10 L Niskin bottles that are 1 m in length.

A 1,2,3-dithiazolyl-o-naphthoquinone: a neutral radical with isolable cation and anion oxidation states.

Under aprotic conditions, the reaction of 4-amino-1,2-naphthoquinone with excess S2Cl2 generates 4,5-dioxo-naphtho[1,2-d][1,2,3]dithiazol-2-ium chloride in a typical Herz condensation. By contrast, prior literature reports an imine (NH) product, 4,5-dioxo-1H-naphtho[1,2-d][1,2,3]dithiazole, for the same reaction performed in acetic acid. Herein, the cation product is isolated with four different counter-anions (Cl(-), GaCl4(-), FeCl4(-) and OTf(-)). Reduction of the cation generates a neutral radical 1,2,3-dithiazolyl-o-naphthoquinone, with potential ligand properties. Further reduction generates a closed shell anion, isolated as a water-stable Li(+) complex and exhibiting O,O-bidentate chelation. The hydroxy (OH) isomer of the original imine (NH) product is reported, and this can be readily deprotonated and acylated (OAc). All species are structurally characterized. Solution redox behaviour and EPR are discussed where appropriate.

Using in situ voltammetry as a tool to identify and characterize habitats of iron-oxidizing bacteria: from fresh water wetlands to hydrothermal vent sites.

Iron-oxidizing bacteria (FeOB) likely play a large role in the biogeochemistry of iron, making the detection and understanding of the biogeochemical processes FeOB are involved in of critical importance. By deploying our in situ voltammetry system, we are able to measure a variety of redox species, specifically Fe(ii) and O2, simultaneously. This technique provides significant advantages in both characterizing the environments in which microaerophilic FeOB are found, and finding diverse conditions in which FeOB could potentially thrive. Described here are four environments with different salinities [one fresh groundwater seep site, one beach-groundwater mixing site, one hydrothermal vent site (Mid-Atlantic Ridge), and one estuary (Chesapeake Bay)] where in situ voltammetry was deployed, and where the presence of FeOB were confirmed by either culturing methods or molecular data. The sites varied in both O2 and Fe(ii) content with O2 ranging from below the 3 µM detection limit of the electrodes at the Chesapeake Bay suboxic zone, to as high 150 µM O2 at the vent site. In addition, a range of Fe(ii) concentrations supported FeOB communities, from 3 µM Fe(ii) in the Chesapeake Bay to 300 µM in the beach aquifer. In situ electrochemistry provides the means to quickly measure these redox gradients at appropriate resolution, making it possible in real time to detect niches likely inhabited by microaerophilic FeOB, then accurately sample for proof of FeOB presence and activity. This study demonstrates the utility of this approach while also greatly expanding our knowledge of FeOB habitats.

Phototrophic sulfide oxidation: environmental insights and a method for kinetic analysis.

Previously, we presented data that indicated microbial sulfide oxidation would out-compete strictly chemical, abiotic sulfide oxidation reactions under nearly all conditions relevant to extant ecosystems (Luther et al., 2011). In particular, we showed how anaerobic microbial sulfide oxidation rates were several orders of magnitude higher than even metal catalyzed aerobic sulfide oxidation processes. The fact that biotic anaerobic sulfide oxidation is kinetically superior to abiotic reactions implies that nearly all anaerobic and sulfidic environments should host microbial populations that oxidize sulfide at appreciable rates. This was likely an important biogeochemical process during long stretches of euxinia in the oceans suggested by the geologic record. In particular, phototrophic sulfide oxidation allows the utilization of carbon dioxide as the electron acceptor suggesting that this process should be particularly widespread rather than relying on the presence of other chemical oxidants. Using the Chesapeake Bay as an example, we argue that phototrophic sulfide oxidation may be more important in many environments than is currently appreciated. Finally, we present methodological considerations to assist other groups that wish to study this process.

Metal complexes of bridging neutral radical ligands: pymDTDA and pymDSDA.

Metal complexes of the 4-(2'-pyrimidyl)-1,2,3,5-dithiadiazolyl (pymDTDA) neutral radical ligand and its selenium analogue (pymDSDA) are presented. The following series of metal ions has been studied using M(hfac)(2) as the coordination fragment of choice (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato): Mn(II), Co(II), Ni(II), and Zn(II). The binuclear cobalt and nickel complexes of pymDTDA both exhibit ferromagnetic (FM) coupling between the unpaired electrons on the ligand and the metal ion, while the binuclear zinc complex of pymDTDA is presented as a comparative example incorporating a diamagnetic metal ion. The binuclear manganese complex of pymDTDA, reported in a preliminary communication, is compared to the pymDSDA analogue, and new insight into the magnetic behavior reveals that intermolecular magnetic coupling, mediated by chalcogen-oxygen contacts, gives rise to a significant increase in the χT product at low temperature. Surprisingly, the binuclear nickel complex of pymDSDA forms dimers in the solid state, as do the mononuclear complexes of cobalt and nickel with pymDTDA. In addition, mixed mononuclear/binuclear complexes of Mn- and Zn(pymDTDA) have been identified.

Thermodynamics and kinetics of sulfide oxidation by oxygen: a look at inorganically controlled reactions and biologically mediated processes in the environment.

The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H(2)S and HS• as well as O(2), reactive oxygen species, nitrate, nitrite, and NO(x) species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment.

A new polymorph of dichloridotriphenylantimony.

In a new polymorphic form of dichloridotriphenylantimony, [Sb(C(6)H(5))(3)Cl(2)], there are two crystallographically unique molecules in the asymmetric unit and it has been determined that this polymorph is one of two kinetically favoured phases of pure dichloridotriphenylantimony, both of which have Z' > 1. A third polymorph, corresponding to (C(6)H(5))(3)SbCl(1.8)F(0.2), is also known and has Z' = 2. By contrast, the thermodynamically preferred polymorph of pure (C(6)H(5))(3)SbCl(2) has Z' = 1. A brief comparison of the known polymorphic forms of dichloridotriphenylantimony is presented.

Fiber-optic scanning two-photon fluorescence endoscope.

We report on the development of a miniature, flexible, fiber-optic scanning endoscope for two-photon fluorescence imaging. The endoscope uses a tubular piezoelectric actuator for achieving two-dimensional beam scanning and a double-clad fiber for delivery of the excitation light and collection of two-photon fluorescence. Real-time imaging of fluorescent beads and cancer cells has been performed.

Real-time in vivo blood-flow imaging by moving-scatterer-sensitive spectral-domain optical Doppler tomography.

We present a moving-scatterer-sensitive optical Doppler tomography (MSS-ODT) technique for in vivo blood flow imaging in real time by using a spectral-domain optical coherence tomography system. In MSS-ODT the influence of stationary scatterers is suppressed by subtracting adjacent complex axial scans before calculating the Doppler frequency shift. We demonstrate that MSS-ODT is a useful technique for accurate determination of blood vessel size by imaging flow in a small capillary tube with a 75 microm inner diameter. The flow profile obtained with MSS-ODT yields a substantially more accurate tube diameter than that obtained with the conventional phase-resolved method, which underestimates the diameter by about 23%. We also demonstrate that MSS-ODT provides improved sensitivity over the conventional phase-resolved method for imaging in vivo blood flow in small vessels in a mouse ear.