A red tide in the pack ice of the Arctic Ocean.

In the Arctic Ocean ice algae constitute a key ecosystem component and the ice algal spring bloom a critical event in the annual production cycle. The bulk of ice algal biomass is usually found in the bottom few cm of the sea ice and dominated by pennate diatoms attached to the ice matrix. Here we report a red tide of the phototrophic ciliate Mesodinium rubrum located at the ice-water interface of newly formed pack ice of the high Arctic in early spring. These planktonic ciliates are not able to attach to the ice. Based on observations and theory of fluid dynamics, we propose that convection caused by brine rejection in growing sea ice enabled M. rubrum to bloom at the ice-water interface despite the relative flow between water and ice. We argue that red tides of M. rubrum are more likely to occur under the thinning Arctic sea ice regime.

Toolbox of Diverse Linkers for Navigating the Cellular Efficacy Landscape of Stapled Peptides.

Stapled peptides have great potential as modulators of protein-protein interactions (PPIs). However, there is a vast landscape of chemical features that can be varied for any given peptide, and identifying a set of features that maximizes cellular uptake and subsequent target engagement remains a key challenge. Herein, we present a systematic analysis of staple functionality on the peptide bioactivity landscape in cellular assays. Through application of a "toolbox" of diversified dialkynyl linkers to the stapling of MDM2-binding peptides via a double-click approach, we conducted a study of cellular uptake and p53 activation as a function of the linker. Minor changes in the linker motif and the specific pairing of linker with peptide sequence can lead to substantial differences in bioactivity, a finding which may have important design implications for peptide-based inhibitors of other PPIs. Given the complexity of the structure-activity relationships involved, the toolbox approach represents a generalizable strategy for optimization when progressing from in vitro binding assays to cellular efficacy studies.

The activity of nitrifying microorganisms in a high-altitude Andean wetland.

High-altitude wetland holds freshwater springs, evaporitic ponds and lagoon with variable salinity and nutrients, potentially influencing the ecology of nitrifying communities. In this study, nitrifying microorganisms in Salar de Huasco (Chile) were surveyed to determine bacterial and archaeal contribution to ammonium (AO), nitrite oxidation (NO), ammonium uptake (AU) during wet and dry seasons. The activity signals from these groups were assessed by specific amoA-qPCR transcription, 15N tracer studies and addition of group specific inhibitor experiments for nitrifying microorganisms (N1-guanyl-1, 7-diaminoheptane [GC7]-archaeal specific and allylthiourea [ATU]-bacterial specific). Nitrifying communities, i.e. Nitrosopumilus, Nitrosospira, Nitrosomonas, Kuenenia and Nitrospira, were more frequent (∼0.25% of 16S rRNA sequences) at low salinity sites. Bacterial amoA-qPCR transcripts also increased at low salinity and along in situ ammonium increase observed between wet/dry seasons. Nutrient changes through time and 15N tracer experiments results showed that AO and NO were detected and peaked mainly at low salinity-high ammonium sites (<37 000 µS cm-1 and >0.3 µM), whereas AU was predominant at evaporitic sites. Our results indicate that salinity and ammonium affect the nitrifying communities that are potentially more active at low-salinity sites but persistent at saltier evaporitic areas of the wetland when ammonium is available.

A Linker for the Solid-Phase Synthesis of Hydroxamic Acids and Identification of HDAC6 Inhibitors.

We herein present broadly useful, readily available and nonintegral hydroxylamine linkers for the routine solid-phase synthesis of hydroxamic acids. The developed protocols enable the efficient synthesis and release of a wide range of hydroxamic acids from various resins, relying on high control and flexibility with respect to reagents and synthetic processes. A trityl-based hydroxylamine linker was used to synthesize a library of peptide hydroxamic acids. The inhibitory effects of the compounds were examined for seven HDAC enzyme subtypes using a chemiluminescence-based assay.

Leads in Arctic pack ice enable early phytoplankton blooms below snow-covered sea ice.

The Arctic icescape is rapidly transforming from a thicker multiyear ice cover to a thinner and largely seasonal first-year ice cover with significant consequences for Arctic primary production. One critical challenge is to understand how productivity will change within the next decades. Recent studies have reported extensive phytoplankton blooms beneath ponded sea ice during summer, indicating that satellite-based Arctic annual primary production estimates may be significantly underestimated. Here we present a unique time-series of a phytoplankton spring bloom observed beneath snow-covered Arctic pack ice. The bloom, dominated by the haptophyte algae Phaeocystis pouchetii, caused near depletion of the surface nitrate inventory and a decline in dissolved inorganic carbon by 16 ± 6 g C m-2. Ocean circulation characteristics in the area indicated that the bloom developed in situ despite the snow-covered sea ice. Leads in the dynamic ice cover provided added sunlight necessary to initiate and sustain the bloom. Phytoplankton blooms beneath snow-covered ice might become more common and widespread in the future Arctic Ocean with frequent lead formation due to thinner and more dynamic sea ice despite projected increases in high-Arctic snowfall. This could alter productivity, marine food webs and carbon sequestration in the Arctic Ocean.

Catalytic Enantioselective Synthesis of Tetrahydocarbazoles and Exocyclic Pictet-Spengler-Type Reactions.

A synthetic strategy for the synthesis of chiral tetrahydrocarbazoles (THCAs) has been developed. The strategy relies on two types of 6-exo-trig cyclization of 3-substituted indole substrates. Enantioselective domino Friedel-Crafts-type reactions leading to THCAs can be catalyzed by chiral phosphoric acid derivatives (with up to >99% ee), and the first examples of exocyclic Pictet-Spengler reactions to form THCAs are reported.

Microbial Activity Response to Solar Radiation across Contrasting Environmental Conditions in Salar de Huasco, Northern Chilean Altiplano.

In high altitude environments, extreme levels of solar radiation and important differences of ionic concentrations over narrow spatial scales may modulate microbial activity. In Salar de Huasco, a high-altitude wetland in the Andean mountains, the high diversity of microbial communities has been characterized and associated with strong environmental variability. Communities that differed in light history and environmental conditions, such as nutrient concentrations and salinity from different spatial locations, were assessed for bacterial secondary production (BSP, 3H-leucine incorporation) response from short-term exposures to solar radiation. We sampled during austral spring seven stations categorized as: (a) source stations, with recently emerged groundwater (no-previous solar exposure); (b) stream running water stations; (c) stations connected to source waters but far downstream from source points; and (d) isolated ponds disconnected from ground sources or streams with a longer isolation and solar exposure history. Very high values of 0.25 µE m-2 s-1, 72 W m-2 and 12 W m-2 were measured for PAR, UVA, and UVB incident solar radiation, respectively. The environmental factors measured formed two groups of stations reflected by principal component analyses (near to groundwater sources and isolated systems) where isolated ponds had the highest BSP and microbial abundance (35 microalgae taxa, picoeukaryotes, nanoflagellates, and bacteria) plus higher salinities and PO43- concentrations. BSP short-term response (4 h) to solar radiation was measured by 3H-leucine incorporation under four different solar conditions: full sun, no UVB, PAR, and dark. Microbial communities established in waters with the longest surface exposure (e.g., isolated ponds) had the lowest BSP response to solar radiation treatments, and thus were likely best adapted to solar radiation exposure contrary to ground source waters. These results support our light history (solar exposure) hypothesis where the more isolated the community is from ground water sources, the better adapted it is to solar radiation. We suggest that factors other than solar radiation (e.g., salinity, PO43-, NO3-) are also important in determining microbial productivity in heterogeneous environments such as the Salar de Huasco.

Development of a Multifunctional Benzophenone Linker for Peptide Stapling and Photoaffinity Labelling.

Photoaffinity labelling is a useful method for studying how proteins interact with ligands and biomolecules, and can help identify and characterise new targets for the development of new therapeutics. We present the design and synthesis of a novel multifunctional benzophenone linker that serves as both a photo-crosslinking motif and a peptide stapling reagent. Using double-click stapling, we attached the benzophenone to the peptide via the staple linker, rather than by modifying the peptide sequence with a photo-crosslinking amino acid. When applied to a p53-derived peptide, the resulting photoreactive stapled peptide was able to preferentially crosslink with MDM2 in the presence of competing protein. This multifunctional linker also features an extra alkyne handle for downstream applications such as pull-down assays, and can be used to investigate the target selectivity of stapled peptides.

Titanium uptake and incorporation into silica nanostructures by the diatom Pinnularia sp. (Bacillariophyceae).

Diatoms are an ecologically successful group within the phytoplankton, and their special feature is a biofabricated silica cell encasement called a frustule. These frustules attract interest in material technology, and one potential application is to use them in solar cell technology. The silica frustule with its nanoscaled pattern is interesting per se, but the utility is enhanced if we succeed in incorporating other elements. Titanium is an interesting element because its oxide is a semi-conductor with a high band gap. However, doping with relevant elements through bioincorporation is challenging, and it is necessary to understand the biology involved in element uptake and incorporation. Here we present data on bioincorporation of Ti into the silica frustules of the pennate diatom Pinnularia sp. (Ehrenberg) and show that the distribution of the incorporated Ti is inhomogeneous both between and within valves. More than a tenfold increase of Ti in newly synthesised valves was achieved, and increased Ti around the pores was confirmed by both EDS and EELS analyses. HAADF STEM spectroscopy revealed a grainy surface with amorphous silica particles of 4 to 5 nm in size. These observations are explained by what is known from the physico-chemical processes involved in biosilification and frustule formation, looking into it from a biological point of view.

Prey-predator dynamics in rotifers: density-dependent consequences of spatial heterogeneity due to surface attachment.

Classical models of prey-predator interactions assume that per capita prey consumption is dependent on prey density alone and that prey consumption (functional response) and consumer proliferation (numerical response) operate on the same timescales and without time lags. Several modifications have been proposed for resolving this timescale discrepancy, including variants where the functional response depends on both prey and predator densities. A microcosm system with the rotifer Brachionus 'Nevada' feeding on the prasinophyte Tetraselmis sp. showed significant (P < 0.0005) increases in steady-state biomasses of both prey and predators with increasing carrying capacity (represented by total phosphorus of the growth medium), which is inconsistent with predictions based on the traditional prey-only-dependent functional response. We provide data indicating that surfaces where the predator can attach provide a high-quality habitat for rotifers, which can result in a predator-dependent functional response. We also show that partitioning between the attached and free-swimming habitats was fast compared to the timescale of the numerical response. When attached to surfaces, rotifers maximized net energy gain by avoiding the high cost of swimming and by increased food capture due to reduced viscous drag. A mathematical model with prey-dependent functional response and wall-attached and free-swimming fractions of the population describes our data adequately. We discuss the implications of this finding for extrapolating microcosm experiments to systems with other surface-to-volume ratios, and to what extent our findings may apply to other popular model organisms for prey-predator interaction.

Iridium- and ruthenium-catalysed synthesis of 2,3-disubstituted indoles from anilines and vicinal diols.

A straightforward and atom-economical method is described for the synthesis of 2,3-disubstituted indoles. Anilines and 1,2-diols are condensed under neat conditions with catalytic amounts of either [Cp*IrCl(2)](2)/MsOH or RuCl(3)·xH(2)O/phosphine (phosphine = PPh(3) or xantphos). The reaction does not require any stoichiometric additives and only produces water and dihydrogen as byproducts. Anilines containing methyl, methoxy, chloro and fluoro substituents can participate in the cyclocondensation. Meta-substituted anilines give good regioselectivity for 6-substituted indoles, while unsymmetrical diols afford excellent regioselectivity for the indole isomer with an aryl or large alkyl group in the 2-position. The mechanism for the cyclocondensation presumably involves initial formation of the α-hydroxyketone from the diol. The ketone subsequently reacts with aniline to generate the α-hydroxyimine which rearranges to the corresponding α-aminoketone. Acid- or metal-catalysed electrophilic ring-closure with the release of water then furnishes the indole product.

TEMPERATURE EFFECTS ON MICROALGAL PHOTOSYNTHESIS-LIGHT RESPONSES MEASURED BY O2 PRODUCTION, PULSE-AMPLITUDE-MODULATED FLUORESCENCE, AND (14) C ASSIMILATION(1).

Short-term temperature effects on photosynthesis were investigated by measuring O2 production, PSII-fluorescence kinetics, and (14) C-incorporation rates in monocultures of the marine phytoplankton species Prorocentrum minimum (Pavill.) J. Schiller (Dinophyceae), Prymnesium parvum f. patelliferum (J. C. Green, D. J. Hibberd et Pienaar) A. Larsen (Coccolithophyceae), and Phaeodactylum tricornutum Bohlin (Bacillariophyceae), grown at 15°C and 80 µmol photons ·â€Šm(-2)  ·â€Šs(-1) . Photosynthesis versus irradiance curves were measured at seven temperatures (0°C-30°C) by all three approaches. The maximum photosynthetic rate (P(C) max ) was strongly stimulated by temperature, reached an optimum for Pro. minimum only (20°C-25°C), and showed a similar relative temperature response for the three applied methods, with Q10 ranging from 1.7 to 3.5. The maximum light utilization coefficient (α(C) ) was insensitive or decreased slightly with increasing temperature. Absolute rates of O2 production were calculated from pulse-amplitude-modulated (PAM) fluorometry measurements in combination with biooptical determination of absorbed quanta in PSII. The relationship between PAM-based O2 production and measured O2 production and (14) C assimilation showed a species-specific correlation, with 1.2-3.3 times higher absolute values of P(C) max and α(C) when calculated from PAM data for Pry. parvum and Ph. tricornutum but equivalent for Pro. minimum. The offset seemed to be temperature insensitive and could be explained by a lower quantum yield for O2 production than the theoretical maximum (due to Mehler-type reactions). Conclusively, the PAM technique can be used to study temperature responses of photosynthesis in microalgae when paying attention to the absorption properties in PSII.

Is phosphorus limitation of planktonic heterotrophic bacteria and accumulation of degradable DOC a normal phenomenon in phosphorus-limited systems? A microcosm study.

A dual isotope labelling technique was used to follow the distribution of carbon and phosphorus in plankton microcosms containing autotrophs (Tetraselmis sp.), heterotrophic bacteria and herbivores (Brachionus plicatilis) at eight different total-P concentrations. P:C ratios of algae, bacteria and dissolved matter, as well as the general accumulation of degradable dissolved organic carbon, indicated that both the autotrophs and heterotrophic bacteria were P-limited in all microcosms. According to the theory, such coexistence should only be possible if bacteria have higher predation losses than algae, which was definitely not the case in our experiment. However, data are consistent with the assumption that bacteria are superior in P uptake but have a poor ability to retain acquired P, which would promote coexistence in a patchy P-supply environment resulting from nutrient regeneration by metazoan grazers.