Quantifying mesoscale-driven nitrate supply: a case study

The supply of nitrate to surface waters plays a crucial role in maintaining marine life. Physical processes at the mesoscale (~10-100?km) and smaller have been advocated to provide a major fraction of the global supply. Whilst observational studies have focussed on well-defined features, such as isolated eddies, the vertical circulation and nutrient supply in a typical 100-200?km square of ocean will involve a turbulent spectrum of interacting, evolving and decaying features. A crucial step in closing the ocean nitrogen budget is to be able to rank the importance of mesoscale fluxes against other sources of nitrate for surface waters for a representative area of open ocean. While this has been done using models, the vital observational equivalent is still lacking.To illustrate the difficulties that prevent us from putting a global estimate on the significance of the mesoscale observationally, we use data from a cruise in the Iceland Basin where vertical velocity and nitrate observations were made simultaneously at the same high spatial resolution. Local mesoscale nitrate flux is found to be an order of magnitude greater than that due to small-scale vertical mixing and exceeds coincident nitrate uptake rates and estimates of nitrate supply due to winter convection. However, a non-zero net vertical velocity for the region introduces a significant bias in regional estimates of the mesoscale vertical nitrate transport. The need for synopticity means that a more accurate estimate can not be simply found by using a larger survey area. It is argued that time-series, rather than spatial surveys, may be the best means to quantify the contribution of mesoscale processes to the nitrate budget of the surface ocean

New Structural and Functional Contexts of the Dx[DN]xDG Linear Motif: Insights into Evolution of Calcium-Binding Proteins

Binding of calcium ions (Ca2+) to proteins can have profound effects on their structure and function. Common roles of calcium binding include structure stabilization and regulation of activity. It is known that diverse families – EF-hands being one of at least twelve – use a Dx[DN]xDG linear motif to bind calcium in near-identical fashion. Here, four novel structural contexts for the motif are described. Existing experimental data for one of them, a thermophilic archaeal subtilisin, demonstrate for the first time a role for Dx[DN]xDG-bound calcium in protein folding. An integrin-like embedding of the motif in the blade of a β-propeller fold – here named the calcium blade – is discovered in structures of bacterial and fungal proteins. Furthermore, sensitive database searches suggest a common origin for the calcium blade in β-propeller structures of different sizes and a pan-kingdom distribution of these proteins. Factors favouring the multiple convergent evolution of the motif appear to include its general Asp-richness, the regular spacing of the Asp residues and the fact that change of Asp into Gly and vice versa can occur though a single nucleotide change. Among the known structural contexts for the Dx[DN]xDG motif, only the calcium blade and the EF-hand are currently found intracellularly in large numbers, perhaps because the higher extracellular concentration of Ca2+ allows for easier fixing of newly evolved motifs that have acquired useful functions. The analysis presented here will inform ongoing efforts toward prediction of similar calcium-binding motifs from sequence information alone

Kryptoracemates

Racemic crystals normally crystallise in centrosymmetric spacegroups containing equal numbers of enantiomers. More rarely, racemates may crystallise in non-centrosymmetric space-groups having glide symmetry or, even more rarely, in space-groups devoid of a centre of inversion, having no rotary-inversion axes nor glide plane. The latter class of crystals form the subject of the present bibliographic review – a survey of kryptoracemic behaviour. The term kryptoracemic alludes to the presence of a hidden or non-crystallographic centre of inversion between two molecules that might otherwise be expected to crystallise in an achiral space-group, often about a centre of inversion. Herein, examples of molecules with stereogenic centres crystallising in one of the 65 Sohncke space-groups are described. Genuine kryptoracemates, i.e. crystals comprising only enantiomorphous pairs are described followed by an overview of non-genuine kryptoracemates whereby the crystal also contains other species such as solvent and/or counterions. A full range, i.e. one to six, stereogenic centres are noted in genuine kryptoracemates. Examples will also be described whereby there are more that one enantiomeric pair of molecules in the crystallographic asymmetric unit. A more diverse range of examples are available for non-genuine kryptoracemates. There are unbalanced species where in addition to the enantiomeric pair of molecules, there is another enantiomeric molecule present. There are examples of genuine co-crystals, solvated species and of salts. Finally, special examples will be highlighted where the counterions are chiral and where they are disparate, both circumstances promoting kryptoracemic behaviour

A mesoscale eddy driving spatial and temporal heterogeneity in the productivity of the euphotic zone of the northeast Atlantic

In this paper we show how different water masses from a similar geographic region provide an explanation for perturbations in the signal of declining productivity at the Porcupine Abyssal Plain (PAP) study site in the Northeast Atlantic. Furthermore we show that the passage of these different water masses is affected by the filamentary instabilities of a cyclonic eddy just southwest of the PAP site. We describe a high-resolution spatial hydrographic survey conducted with a towed instrument package, complemented by biogeochemical sampling. Maximum rates of primary production of 110 mmol C m-2 d-1 seen at the centre of the survey area were associated with the passage of an eddy filament and were enhanced 3 fold relative to far-field conditions (not, vert, similar36 mmol C m-2 d-1). The rotation and stirring influence of the eddy resulted in the sequential passage of 3 distinct water masses past the observation point. This understanding of the lateral stirring around the site enabled us to explain the sharp changes observed in daily primary production rates and other biogeochemical parameters. The spatial survey also revealed a fluorescence maxima associated with the cyclonic eddy that was laterally displaced northwards away from the core, an observation supportive of recent modelling studies

3-hydroxysalicylaldoxime

The structure of the title compound, C7H7NO3, is based on oximic hydrogen-bonded chains, which are linked together by further phenolic intermolecular hydrogen bonds that form an R-4(4)(14) ring motif

3-fluorosalicylaldoxime

In contrast with many salicylaldoxime derivatives, which form crystal structures based on hydrogen-bonded ring motifs, 3-fluorosalicylaldoxime, C7H6FNO2, forms hydrogen-bonded chains. Each chain interacts with two chains above and two chains below viaπ–π stacking contacts [centroid–centroid distance = 3.6353 (1) Å]

Salicylaldoxime-III at 150 K

Salicylaldoxime derivatives crystallize in either hydrogen-bonded ring or chain motifs. A polymorph of the parent compound, salicylaldoxime, characterized by ring formation, has been known for some time. We now report a new polymorph of salicylaldoxime (2-hydroxybenzaldehyde oxime, C7H7NO2), which exhibits chain formation and which has two molecules per asymmetric unit. pi-pi stacking interactions occur between the chains. We refer to this polymorph as salicylaldoxime-III