Phosphine-Catalyzed 1,2-cis-Diboration of 1,3-Butadiynes.

Trialkyl phosphines PMe3 and PEt3 catalyze the 1,2-cis-diboration of 1,3-butadiynes to give 1,2-diboryl enynes. The products were utilized to synthesize 1,1,2,4-tetraaryl enynes using a Suzuki-Miyaura protocol and can readily undergo proto-deborylation.

Digital elevation models of the sea-ice surface from airborne laser scanning during MOSAiC.

Airborne laser scanners (ALS) are used to map the sea-ice surface at sub-meter resolution. We conducted 64 flights over the Arctic sea ice between September 2019 and September 2020 during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition to measure sea-ice surface elevation. The flights ranged from repeated, local-scale 5 × 5 km2 floe grid surveys to regional-scale transects more than 100 km long. We provide data at different processing levels: geolocated elevation point clouds and gridded segments of elevation and freeboard with a spatial resolution of 0.5 m. The latter product is corrected for atmospheric backscatter, sea-ice drift, and offset in elevation due to degraded INS/GNSS solutions > 85° N. For floe grid surveys, all data are combined to merged two-dimensional elevation maps. Other provided parameters include laser reflectance and echo width. The presented data offer a unique possibility to study the temporal evolution, spatial distribution, and variability of the snow and sea-ice surface and their properties in addition to validating satellite products.

Helicopter-borne RGB orthomosaics and photogrammetric digital elevation models from the MOSAiC Expedition.

The Multidisciplinary Drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition took place between October 2019 and September 2020 giving the rare opportunity to monitor sea-ice properties over a full annual cycle. Here we present 24 high-resolution orthomosaics and 14 photogrammetric digital elevation models of the sea-ice surface around the icebreaker RV Polarstern between March and September 2020. The dataset is based on >34.000 images acquired by a helicopter-borne optical camera system with survey flights covering areas between 1.8 and 96.5 km2 around the vessel. Depending on the flight pattern and altitude of the helicopter, ground resolutions of the orthomosaics range between 0.03 and 0.5 m. By combining the photogrammetric products with contemporaneously acquired airborne laser scanner reflectance measurements selected orthomosaics could be corrected for cloud shadows which facilitates their usage for sea-ice and melt pond classification algorithms. The presented dataset is a valuable data source for the interdisciplinary MOSAiC community building a temporal and spatially resolved baseline to accompany various remote sensing and in situ research projects.

Transition Metal-Free Regio- and Stereo-Selective trans Hydroboration of 1,3-Diynes: A Phosphine-Catalyzed Access to (E)-1-Boryl-1,3-Enynes.

We report a transition metal-free, regio- and stereo-selective, phosphine-catalyzed method for the trans hydroboration of 1,3-diynes with pinacolborane that affords (E)-1-boryl-1,3-enynes. The reaction proceeds with excellent selectivity for boron addition to the external carbon of the 1,3-diyne framework as unambiguously established by NMR and X-ray crystallographic studies. The reaction displays a broad substrate scope including unsymmetrical diynes to generate products in high yield (up to 95 %). Experimental and theoretical studies suggest that phosphine attack on the alkyne is a key process in the catalytic cycle.

Sea ice surface temperatures from helicopter-borne thermal infrared imaging during the MOSAiC expedition.

The sea ice surface temperature is important to understand the Arctic winter heat budget. We conducted 35 helicopter flights with an infrared camera in winter 2019/2020 during the Multidisciplinary Drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. The flights were performed from a local, 5 to 10 km scale up to a regional, 20 to 40 km scale. The infrared camera recorded thermal infrared brightness temperatures, which we converted to surface temperatures. More than 150000 images from all flights can be investigated individually. As an advanced data product, we created surface temperature maps for every flight with a 1 m resolution. We corrected image gradients, applied an ice drift correction, georeferenced all pixels, and corrected the surface temperature by its natural temporal drift, which results in time-fixed surface temperature maps for a consistent analysis of one flight. The temporal and spatial variability of sea ice characteristics is an important contribution to an increased understanding of the Arctic heat budget and, in particular, for the validation of satellite products.

Effect of Louisiana sweet crude oil on a Pacific coral, Pocillopora damicornis.

Recent oil spill responses such as the Deepwater Horizon event have underscored the need for crude oil ecotoxicological threshold data for shallow water corals to assist in natural resource damage assessments. We determined the toxicity of a mechanically agitated oil-seawater mixture (high-energy water-accommodated fraction, HEWAF) of a sweet crude oil on a branched stony coral, Pocillopora damicornis. We report the results of two experiments: a 96 h static renewal exposure experiment and a "pulse-chase" experiment of three short-term exposure durations followed by a recovery period in artificial seawater. Five endpoints were used to determine ecotoxicological values: 1) algal symbiont chlorophyll fluorescence, 2) a tissue regeneration assay and a visual health metric with three endpoints: 3) tissue integrity, 4) tissue color, and 5) polyp behavior. The sum of 50 entrained polycyclic aromatic hydrocarbons (tPAH50) was used as a proxy for oil exposure. For the 96 h exposure dose response experiment, dark-adapted maximum quantum yield (Fv/Fm) of the dinoflagellate symbionts was least affected by crude oil (EC50 = 913 µg/L tPAH50); light-adapted effective quantum yield (EQY) was more sensitive (EC50 =  428 µg/L tPAH50). In the health assessment, polyp behavior (EC50 = 27 µg/L tPAH50) was more sensitive than tissue integrity (EC50 = 806 µg/L tPAH50) or tissue color (EC50 = 926 µg/L tPAH50). Tissue regeneration proved to be a particularly sensitive measurement for toxicity effects (EC50 = 10 µg/L tPAH50). Short duration (6-24 h) exposures using 503 µg/L tPAH50 (average concentration) resulted in negative impacts to P. damicornis and its symbionts. Recovery of chlorophyll a fluorescence levels for 6-24 h oil exposures was observed in a few hours (Fv/Fm) to several days (EQY) following recovery in fresh seawater. The coral health assessments for tissue integrity and tissue color were not affected following short-term oil exposure durations, but the 96 h treatment duration resulted in significant decreases for both. A reduction in polyp behavior (extension) was observed for all treatment durations, with recovery observed for the short-term (6-24 h) exposures within 1-2 days following placement in fresh seawater. Wounded and intact fragments exposed to oil treatments were particularly sensitive, with significant delays observed in tissue regeneration. Estimating ecotoxicological values for P. damicornis exposed to crude oil HEWAFs provides a basis for natural resource damage assessments for oil spills in reef ecosystems. These data, when combined with ecotoxicological values for other coral reef species, will contribute to the development of species sensitivity models.

Arctic warming interrupts the Transpolar Drift and affects long-range transport of sea ice and ice-rafted matter.

Sea ice is an important transport vehicle for gaseous, dissolved and particulate matter in the Arctic Ocean. Due to the recently observed acceleration in sea ice drift, it has been assumed that more matter is advected by the Transpolar Drift from shallow shelf waters to the central Arctic Ocean and beyond. However, this study provides first evidence that intensified melt in the marginal zones of the Arctic Ocean interrupts the transarctic conveyor belt and has led to a reduction of the survival rates of sea ice exported from the shallow Siberian shelves (-15% per decade). As a consequence, less and less ice formed in shallow water areas (<30 m) has reached Fram Strait (-17% per decade), and more ice and ice-rafted material is released in the northern Laptev Sea and central Arctic Ocean. Decreasing survival rates of first-year ice are visible all along the Russian shelves, but significant only in the Kara Sea, East Siberian Sea and western Laptev Sea. Identified changes affect biogeochemical fluxes and ecological processes in the central Arctic: A reduced long-range transport of sea ice alters transport and redistribution of climate relevant gases, and increases accumulation of sediments and contaminates in the central Arctic Ocean, with consequences for primary production, and the biodiversity of the Arctic Ocean.

The winter pack-ice zone provides a sheltered but food-poor habitat for larval Antarctic krill.

A dominant Antarctic ecological paradigm suggests that winter sea ice is generally the main feeding ground for krill larvae. Observations from our winter cruise to the southwest Atlantic sector of the Southern Ocean contradict this view and present the first evidence that the pack-ice zone is a food-poor habitat for larval development. In contrast, the more open marginal ice zone provides a more favourable food environment for high larval krill growth rates. We found that complex under-ice habitats are, however, vital for larval krill when water column productivity is limited by light, by providing structures that offer protection from predators and to collect organic material released from the ice. The larvae feed on this sparse ice-associated food during the day. After sunset, they migrate into the water below the ice (upper 20 m) and drift away from the ice areas where they have previously fed. Model analyses indicate that this behaviour increases both food uptake in a patchy food environment and the likelihood of overwinter transport to areas where feeding conditions are more favourable in spring.

Temporal patterns of Deepwater Horizon impacts on the benthic infauna of the northern Gulf of Mexico continental slope.

The Deepwater Horizon oil spill occurred in spring and summer 2010 in the northern Gulf of Mexico. Research cruises in 2010 (approximately 2-3 months after the well had been capped), 2011, and 2014 were conducted to determine the initial and subsequent effects of the oil spill on deep-sea soft-bottom infauna. A total of 34 stations were sampled from two zones: 20 stations in the "impact" zone versus 14 stations in the "non-impact" zone. Chemical contaminants were significantly different between the two zones. Polycyclic aromatic hydrocarbons averaged 218 ppb in the impact zone compared to 14 ppb in the non-impact zone. Total petroleum hydrocarbons averaged 1166 ppm in the impact zone compared to 102 ppm in the non-impact zone. While there was no difference between zones for meiofauna and macrofauna abundance, community diversity was significantly lower in the impact zone. Meiofauna taxa richness over the three sampling periods averaged 8 taxa/sample in the impact zone, compared to 10 taxa/sample in the non-impact zone; and macrofauna richness averaged 25 taxa/sample in the impact zone compared to 30 taxa/sample in the non-impact zone. Oil originating from the Deepwater Horizon oil spill reached the seafloor and had a persistent negative impact on diversity of soft-bottom, deep-sea benthic communities. While there are signs of recovery for some benthic community variables, full recovery has not yet occurred four years after the spill.

Sediment quality benchmarks for assessing oil-related impacts to the deep-sea benthos.

Paired sediment contaminant and benthic infaunal data from prior studies following the 2010 Deepwater Horizon (DWH) oil spill in the Gulf of Mexico were analyzed using logistic regression models (LRMs) to derive sediment quality benchmarks for assessing risks of oil-related impacts to the deep-sea benthos. Sediment total polycyclic aromatic hydrocarbon (PAH) and total petroleum hydrocarbon (TPH) concentrations were used as measures of oil exposure. Taxonomic richness (average number of taxa/sample) was selected as the primary benthic response variable. Data are from 37 stations (1300-1700 m water depth) in fine-grained sediments (92%-99% silt-clay) sampled within 200 km of the DWH wellhead (most within 40 km) in 2010 and 32 stations sampled in 2011 (29 of which were common to both years). Results suggest the likelihood of impacts to benthic macrofauna and meiofauna communities is low (<20%) at TPH concentrations of less than 606 mg kg-1 (ppm dry weight) and 700 mg kg-1 respectively, high (>80%) at concentrations greater than 2144 mg kg-1 and 2359 mg kg-1 respectively, and intermediate at concentrations in between. For total PAHs, the probability of impacts is low (<20%) at concentrations of less than 4.0 mg kg-1 (ppm) for both macrofauna and meiofauna, high (>80%) at concentrations greater than 24 mg kg-1 and 25 mg kg-1 for macrofauna and meiofauna, respectively, and intermediate at concentrations in between. Although numerical sediment quality guidelines (SQGs) are available for total PAHs and other chemical contaminants based on bioeffect data for shallower estuarine, marine, and freshwater biota, to our knowledge, none have been developed for measures of total oil (e.g., TPH) or specifically for deep-sea benthic applications. The benchmarks presented herein provide valuable screening tools for evaluating the biological significance of observed oil concentrations in similar deep-sea sediments following future spills and as potential restoration targets to aid in managing recovery. Integr Environ Assess Manag 2017;13:840-851. Published 2017. This article is a US Government work and is in the public domain in the USA.

Assessing the footprint and volume of oil deposited in deep-sea sediments following the Deepwater Horizon oil spill.

The lateral and vertical extents of Macondo oil in deep-sea sediments resulting from the 2010 Deepwater Horizon oil spill were determined using chemical forensics and geostatistical kriging of data from 2397 sediment samples from 875 cores collected in 2010/2011 and 2014. The total mass of Macondo-derived hopane on the seafloor in 2010/2011 was conservatively estimated between 2.00 and 2.26metric tons, derived from 219,000 to 247,000barrels of oil; or 6.9 to 7.7% of the 3.19millionbarrels spilled. Macondo-derived hopane was deposited over 1030 to 1910km2 of the seafloor, mostly (>97%) in surface (0-1cm) and near-surface (1-3cm) sediments, which is consistent with short-term oil deposition. Although Macondo oil was still present in surface sediments in 2014, the total mass of Macondo-derived hopane was significantly lower (~80 to 90%) than in 2010/2011, affirming an acute impact from the spill and not long-term deposition from natural seeps.

Macondo oil in deep-sea sediments: Part 2 - Distribution and distinction from background and natural oil seeps.

Following the Deepwater Horizon oil spill, the spilled Macondo oil was severely weathered during its transport within the deep-sea plume as discrete particles, which were subsequently deposited on the seafloor. The Macondo oil deposited in deep-sea sediments was distinguished from ambient (background) hydrocarbons and naturally-seeped and genetically-similar oils in the Mississippi Canyon region using a forensic method based upon a systematic, multi-year study of 724 deep-sea sediment cores collected in late 2010 and 2011. The method relied upon: (1) chemical fingerprinting of the distinct features of the wax-rich, severely-weathered Macondo oil; (2) hydrocarbon concentrations, considering a core's proximity to the Macondo well or to known or apparent natural oil seeps, and also vertically within a core; and (3) results from proximal cores and flocculent material from core supernatants and slurp gun filters. The results presented herein establish the geographic extent of "fingerprintable" Macondo oil recognized on the seafloor in 2010/2011.

A comparative evaluation of arterial blood flow and the healing response after femoral artery closure using angio-seal STS Plus and StarClose in a porcine model.

OBJECTIVES: This study prospectively evaluated the acute and chronic arterial blood flow and vascular pathology after vessel closure using two commonly used closure devices controlled by deploying both devices in each animal. BACKGROUND: Several vessel closure systems are approved for clinical use; however, few direct comparisons have ever been performed and no randomized case controlled study has been published using FDA-approved devices. METHODS: Nineteen Sous Scroufulae pigs underwent bilateral percutaneous arteriotomies using ultrasound-guided 6 Fr sheath insertion in both common femoral arteries. The femoral access site was then closed using either an Angio-Seal STS Plus, an absorbable collagen sponge, or StarClose, a self-closing nitinol clip. Angiograms and ultrasound of the site were performed prior to closure and immediately afterwards. At follow-up, ultrasound was performed at the site and the specimens were sent for histopathology. RESULTS: Baseline femoral artery diameters (centimeters) were similar in both groups by U/S (5.2 +/- 0.3, 5.3 +/- 0.3) and quantitative angiography (4.6 +/- 0.7, 4.6 +/- 0.8). Postdeployment angiograms showed a vessel diameter stenosis of 65%+/- 24% with Angio-Seal (n = 18) and 50%+/- 22% with StarClose (n = 18), P = 0.04. 2D U/S performed immediately postdeployment showed vessel diameter stenosis of 59%+/- 33.0 with Angio-Seal (n = 19), and 35%+/- 20 with StarClose (n = 19), P = 0.01. At 7-, 30-, and 60-day follow-up, no appreciable differences in the vessel diameter were observed by U/S. At early follow-up (7 and 30 days), Angio-Seal arteriotomy closure sites were associated with higher inflammatory and hemorrhage scores, but no difference was seen at late (60-day) follow-up. CONCLUSIONS: The StarClose closure device is associated with less short-term vessel injury compared to Angio-Seal STS Plus; however, this difference was not statistically significant after 60 days.

Options for rapid analysis of peptides and proteins, using wide-pore, superficially porous, high-performance liquid chromatography particles with unique bonded-phase ligands.

The large size and complexity of many proteins constrains the reversed-phase high-performance liquid chromatography packings that are useful for their separation. Wide-pore, superficially porous, silica-based packings with solid 4.5-microm cores and a 0.25-microm porous outer layer (Poroshell) demonstrate a variety of characteristics that are beneficial for the separation of proteins. A shorter diffusion distance allows separations of large molecules at high linear velocities. This benefit over totally porous particles is clearly shown using separations of a peptide-protein standard. The structure and reduced surface area (4.5 m2/g) of these superficially porous particles simplifies interactions with its surface, resulting in improved peak shapes and resolution. Specialized bonding chemistries for low- and high-pH operation may be used to change band-spacing and achieve atypical separations. These rapid analysis options are demonstrated using protein standards and very high molecular weight glycosylated proteins including intact monoclonal antibodies, IgM, alpha2-macroglobulin, and glycophorin. In liquid chromatography-mass spectrometry analysis of a myoglobin peptide digest, bidentate-C18-bonded superficially porous packings achieve complete runs in 4 min and demonstrate an elution pattern that is unique from that of material bonded with sterically protected C18 ligands.

Vibratory Stimulation of Ejaculation Yields Increased Motile Spermatozoa, Compared with Electroejaculation, in Squirrel Monkeys (Saimiri boliviensis).

Semen sample collection in squirrel monkeys has traditionally relied on electroejaculation (EE) via the rectum; how- ever, the yield is low when anesthesia is used. An alternative method has been advocated for men with spinal cord injury that relies on penile vibratory afferent stimulation. Vibratory stimulation (VS) physiologically coordinates emission and ejaculation without requiring anesthesia; this procedure was investigated in squirrel monkeys. During the breeding season, 10 donor males were evenly allotted to two groups; one received VS, and the other received EE. Three days later, treatments were reversed. For VS, a clinical unit was adapted to hold a 1.8-ml microcentrifuge tube as an artificial vagina. Unanesthetized, manually restrained animals were positioned in ventral recumbency. Vibratory stimulation consisted of a I-mm amplitude, 75-Hz stimulation for 1 min, rest for 1 min, then continued stimulation at 1.8-mm amplitude, 90 Hz for 1 min. For EE, animals were anesthetized by administration of Telazol(3.5 mg/kg of body weight, IM) and stimulated by EE via the rectum, using a 5- to 7.5-V, 60-Hz sine wave for 1 minute of 1 sec on/ I sec off and a probe with two longitudinal electrodes and a temperature monitor. Stimulation was repeated after 1 minute s rest. Semen samples were diluted, incubated, centrifuged, and evaluated for spermatozoal count and motility. Nine of 10 monkeys responded to VS with semen samples, all of which contained spermatozoa. Mean motility was 79.8% and total mean motile spermatozoa yield was 26.1 (range, 0.4 to 110) million. By use of EE, all monkeys produced semen samples, but only 6 samples contained spermatozoa, with mean motility of 70% and low yield of 0.534 (range, 0.038 to 2.2) million motile spermatozoa. In conclusion, penile VS was superior with regard to quantity of motile spermatozoa obtained. Additionally, no anesthesia was necessary for this relatively benign procedure.