ALBERT

Beschreibung: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Baumgartner, M. F., Bonnell, J., Van Parijs, S. M., Corkeron, P. J., Hotchkin, C., Ball, K., Pelletier, L., Partan, J., Peters, D., Kemp, J., Pietro, J., Newhall, K., Stokes, A., Cole, T. V. N., Quintana, E., & Kraus, S. D. Persistent near real-time passive acoustic monitoring for baleen whales from a moored buoy: System description and evaluation. Methods in Ecology and Evolution, 10(9), (2019): 1476-1489, doi: 10.1111/2041-210X.13244.

Beschreibung: 1. Managing interactions between human activities and marine mammals often relies on an understanding of the real‐time distribution or occurrence of animals. Visual surveys typically cannot provide persistent monitoring because of expense and weather limitations, and while passive acoustic recorders can monitor continuously, the data they collect are often not accessible until the recorder is recovered. 2. We have developed a moored passive acoustic monitoring system that provides near real‐time occurrence estimates for humpback, sei, fin and North Atlantic right whales from a single site for a year, and makes those occurrence estimates available via a publicly accessible website, email and text messages, a smartphone/tablet app and the U.S. Coast Guard's maritime domain awareness software. We evaluated this system using a buoy deployed off the coast of Massachusetts during 2015–2016 and redeployed again during 2016–2017. Near real‐time estimates of whale occurrence were compared to simultaneously collected archived audio as well as whale sightings collected near the buoy by aerial surveys. 3. False detection rates for right, humpback and sei whales were 0% and nearly 0% for fin whales, whereas missed detection rates at daily time scales were modest (12%–42%). Missed detections were significantly associated with low calling rates for all species. We observed strong associations between right whale visual sightings and near real‐time acoustic detections over a monitoring range 30–40 km and temporal scales of 24–48 hr, suggesting that silent animals were not especially problematic for estimating occurrence of right whales in the study area. There was no association between acoustic detections and visual sightings of humpback whales. 4. The moored buoy has been used to reduce the risk of ship strikes for right whales in a U.S. Coast Guard gunnery range, and can be applied to other mitigation applications.

Beschreibung: We thank Annamaria Izzi, Danielle Cholewiak and Genevieve Davis of the NOAA NEFSC for assistance in developing the analyst protocol. We are grateful to the NOAA NEFSC aerial survey observers (Leah Crowe, Pete Duley, Jen Gatzke, Allison Henry, Christin Khan and Karen Vale) and the NEAq aerial survey observers (Angela Bostwick, Marianna Hagbloom and Paul Nagelkirk). Danielle Cholewiak and three anonymous reviewers provided constructive criticism on earlier drafts of the manuscript. Funding for this project was provided by the NOAA NEFSC, NOAA Advanced Sampling Technology Work Group, Environmental Security Technology Certification Program of the U.S. Department of Defense, the U.S. Navy's Living Marine Resources Program, Massachusetts Clean Energy Center and the Bureau of Ocean Energy Management. Funding from NOAA was facilitated by the Cooperative Institute for the North Atlantic Region (CINAR) under Cooperative Agreement NA14OAR4320158.

Beschreibung: Author Posting. © Royal Society, 2018. This article is posted here by permission of Royal Society for personal use, not for redistribution. The definitive version was published in Proceedings of the Royal Society Open Science 5(12) (2018): 181358. doi: 10.1098/rsos.181358.

Beschreibung: The settlement of reef-building corals is critical to the survival and recovery of reefs. Recent evidence indicates that coral larvae orient towards reef sound, yet the components of the acoustic environment that may attract coral larvae and induce settlement are unknown. Here we investigated the effects of ambient soundscapes on settlement of Porites astreoides coral larvae using in situ chambers on reefs differing in habitat quality (coral and fish abundance). Mean larval settlement was twice as high in an acoustic environment with high levels of low-frequency sounds, typical of a high-quality, healthy reef; this result was observed in both natural light and dark treatments. Overall, the enhancement of coral settlement by soundscapes typical of healthy reefs suggests a positive feedback where soundscape properties of reefs with elevated coral and fish abundance may facilitate coral recruitment.

Beschreibung: This study is funded by NSF Biological Oceanography award 15-36782 which supported all authors.

Beschreibung: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Capotondi, A., Jacox, M., Bowler, C., Kavanaugh, M., Lehodey, P., Barrie, D., Brodie, S., Chaffron, S., Cheng, W., Dias, D. F., Eveillard, D., Guidi, L., Iudicone, D., Lovenduski, N. S., Nye, J. A., Ortiz, I., Pirhalla, D., Buil, M. P., Saba, V., Sheridan, S., Siedlecki, S., Subramanian, A., de Vargas, C., Di Lorenzo, E., Doney, S. C., Hermann, A. J., Joyce, T., Merrifield, M., Miller, A. J., Not, F., & Pesant, S. Observational needs supporting marine ecosystems modeling and forecasting: from the global ocean to regional and coastal systems. Frontiers in Marine Science, 6, (2019): 623, doi:10.3389/fmars.2019.00623.

Beschreibung: Many coastal areas host rich marine ecosystems and are also centers of economic activities, including fishing, shipping and recreation. Due to the socioeconomic and ecological importance of these areas, predicting relevant indicators of the ecosystem state on sub-seasonal to interannual timescales is gaining increasing attention. Depending on the application, forecasts may be sought for variables and indicators spanning physics (e.g., sea level, temperature, currents), chemistry (e.g., nutrients, oxygen, pH), and biology (from viruses to top predators). Many components of the marine ecosystem are known to be influenced by leading modes of climate variability, which provide a physical basis for predictability. However, prediction capabilities remain limited by the lack of a clear understanding of the physical and biological processes involved, as well as by insufficient observations for forecast initialization and verification. The situation is further complicated by the influence of climate change on ocean conditions along coastal areas, including sea level rise, increased stratification, and shoaling of oxygen minimum zones. Observations are thus vital to all aspects of marine forecasting: statistical and/or dynamical model development, forecast initialization, and forecast validation, each of which has different observational requirements, which may be also specific to the study region. Here, we use examples from United States (U.S.) coastal applications to identify and describe the key requirements for an observational network that is needed to facilitate improved process understanding, as well as for sustaining operational ecosystem forecasting. We also describe new holistic observational approaches, e.g., approaches based on acoustics, inspired by Tara Oceans or by landscape ecology, which have the potential to support and expand ecosystem modeling and forecasting activities by bridging global and local observations.

Beschreibung: This study was supported by the NOAA’s Climate Program Office’s Modeling, Analysis, Predictions, and Projections (MAPP) Program through grants NA17OAR4310106, NA17OAR4310104, NA17OAR4310108, NA17OAR4310109, NA17OAR4310110, NA17OAR4310111, NA17OAR4310112, and NA17OAR4310113. This manuscript is a product of the NOAA/MAPP Marine Prediction Task Force. The Tara Oceans consortium acknowledges support from the CNRS Research Federation FR2022 Global Ocean Systems Ecology and Evolution, and OCEANOMICS (grant agreement ‘Investissement d’Avenir’ ANR-11-BTBR-0008). This is article number 95 of the Tara Oceans consortium. MK and SD acknowledge support from NASA grant NNX14AP62A “National Marine Sanctuaries as Sentinel Sites for a Demonstration Marine Biodiversity Observation Network (MBON)” funded under the National Ocean Partnership Program (NOPP RFP NOAA-NOS-IOOS-2014-2003803 in partnership between NOAA, BOEM, and NASA), and the NOAA Integrated Ocean Observing System (IOOS) Program Office. WC, IO, and AH acknowledge partial support from the Joint Institute for the Study of the Atmosphere and Ocean (JISAO) under NOAA Cooperative Agreement NA15OAR4320063, Contribution No. 2019-1029. This study received support from the European H2020 International Cooperation project MESOPP (Mesopelagic Southern Ocean Prey and Predators), grant agreement no. 692173.

Beschreibung: The NASA Glenn Research Centers DGEN Aeropropulsion Research Turbofan (DART) is based on the Price Induction DGEN380a small, ~500-lbf thrust class, high-bypass, geared-turbofan engine with a separate flow nozzle. The general characteristics of the DART make it an ideal candidate for utilization as a test bed for engine aeroacoustic research in a relevant performance environment. The DART was used to document the efficacy of acoustic liners installed in the inlet of the DGEN380. An advanced multi-degree-of-freedom liner (MDOF) was designed and tested, along with a traditional single-degree-of- freedom liner (SDOF), and those results compared to a hard-wall baseline inlet. Farfield acoustic data were acquired from an external array, evaluated, and reported here-in terms of overall, broadband, and tonal components of the insertion loss.

Beschreibung: The purpose of this study is to characterize auditory filters at low frequencies, defined as below about 100 Hz. Three experiments were designed and executed. They were conducted in the Exterior Effects Room at the NASA Langley Research Center, a psychoacoustic facility designed for presentation of aircraft flyover sounds to groups of test subjects. The first experiment measured 36 subjects hearing threshold for pure tones (at 25, 31.5, 40, 50, 63 and 80 Hz) in quiet conditions. The subjects, male and female, had a wide age range. This experiment allowed the performance of the test facility to be assessed and also provided screened test subjects for participation in subsequent experiments. The second and third experiments used 20 and 10 test subjects, respectively, and measured psychophysical tuning curves (PTCs) that describe auditory filters with center frequencies of approximately 63 and 50 Hz. The latter is assumed to be the lowest (bottom) auditory filter; thus, sounds at frequencies below about 50 Hz are perceived via the lower skirt of this lowest filter. All experiments used an adaptive, three-alternative forced-choice test procedure using either variable level tones or variable level, narrowband noise maskers. Measured PTCs were found to be very similar to other recently published data, both in terms of mean values and intersubject variation, despite different experimental protocols, different test facilities, and a wide range in subjects age.

Beschreibung: The purpose of this presentation is to give an overview of our findings, lessons learned, engineering controls implemented, and results of sound mitigation implementation at NASA Space Environments Complex in relation to Thermal Vacuum Testing.

Beschreibung: Aeroacoustic predictions of slat noise from the 30P30N three-element high-lift system at high angles of attack are presented using a zonal hybrid RANS-LES method. The simulations are part of the 5th AIAA Benchmark problems for Airframe Noise Computations (BANC-V) Workshop. An economical approach utilizing structured overset grids with spatially varying span-wise grid resolution and a high-order accurate finite difference method is described. The method is utilized for near-field predictions at three angles of attack: = 5.5, 9.5, and 14.0 degrees. Far-field noise is obtained by propagating the near-field solution using a permeable surface Ffowcs Williams-Hawkings (FWH) method. Good agreement is obtained with both near-field and far-field Power Spectral Density (PSD) data from an experimental study of the 30P30N in the 2m x 2m Kevlar-wall wind tunnel at the Japan Aerospace Exploration Agency (JAXA). Specifically, the reduction in narrow band peaks and overall broadband noise levels with increasing angle of attack is captured well using the zonal hybrid RANS-LES method.

Beschreibung: This report documents the technical accomplishments of the project, Acoustic Emission- Based Health Monitoring of Space Launch System Structures, sponsored by the National Aeronautics and Space Administration (Award No. NNM13AA12G). As the project title suggests, the goal of the project was to develop a structural health monitoring (SHM) system for Space Launch System (SLS) vehicles based on acoustic emission (AE) or AE-like signals. Such a system will enhance SLS reliability by identifying the damage locations and type of damage when the damage is initiated. This SHM system would also lead to reduced maintenance costs by enabling ground support equipment to inspect only SLS elements or parts that are likely to be damaged. Finally, it will facilitate lean designs that meet tolerance levels specified by barely detectable damage. By avoiding excess conservatism in this manner, this SHM system will further reduce manufacturing costs of SLS vehicles.

Beschreibung: No abstract available

Beschreibung: No abstract available

Beschreibung: The existing ban on commercial supersonic flight overland is largely due to the effects of loud and startling sonic booms on communities. NASA is planning a nationwide campaign of community response surveys using the experimental X-59 Quiet SuperSonic Technology (X-59 QueSST) aircraft to understand how communities perceive the sounds of quiet supersonic flight. The X-59 community response survey data will be presented to noise regulators, who are considering replacing the ban with a noise-based certification limit so quiet supersonic vehicles can fly over land. In this document, we use pilot community response survey data to explore and assess multiple approaches to statistically model the dose-response relationship between single-event sonic boom sound exposure and human annoyance. The models have two primary functionsestimating two types of quantities that support setting regulations and experimental design of future surveys.

Beschreibung: No abstract available

Beschreibung: The Advanced Noise Control Fan (ne Active Noise Control Fan - ANCF) was utilized in the design, test, and evaluation for technical risk mitigation of most of the innovative fan noise reduction technologies developed by NASA over the past 20 years. The ANCF is a low-speed, ducted fan, testbed for measuring and understanding fan-generated aeroacoustics, duct propagation, and radiation to the farfield. It is considered a low Technology Readiness Level testbed. The international aeroacoustics research community employed the ANCF to facilitate advancement of multiple noise reduction and measurement technologies, and for code validation. From 1994 to 2016, it was located in the NASA Glenn Research Centers Aero-Acoustic Propulsion Laboratory. In 2016 the ANCF was transferred to the University of Notre Dame where it is expected to continue to positively impact ducted fan aeroacoustic research and provide STEM support. This paper summarizes the capabilities and contributions of the ANCF to the field by documenting its history. Limited data is presented, focusing on a description of the configurations, goals, and objectives of representative ANCF tests. This provides an overview of the progress of aeroacosustic research as implemented on the ANCF, as well as a background for its continued usage.

Beschreibung: The Advanced Noise Control Fan (ANCF) (formerly the Active Noise Control Fan) was utilized in the design, test, and evaluation for technical risk mitigation of most of the innovative fan noise reduction technologies developed by NASA over the past 20 years (Figure 3). The ANCF is a low-speed ducted-fan testbed for measuring and understanding fan-generated aeroacoustics, duct propagation, and radiation to the far field. It is considered a low technology readiness level (TRL) testbed. The international aeroacoustics research community employed the ANCF to facilitate advancement of multiple noise reduction and measurement technologies and for code validation. From 1994 to 2016, it was located in the NASA Glenn Research Centers Aero-Acoustic Propulsion Laboratory (AAPL). In 2016, the ANCF was transferred to the University of Notre Dame (UND) where it is expected to continue to positively impact ducted-fan aeroacoustic research. This paper summarizes the capabilities and contributions of the ANCF to the field by documenting its history.

Beschreibung: Recent interest in commercial supersonic flight has highlighted the need to accurately predict Effective Perceived Noise Levels (EPNL) for aircraft and, since the dominant noise source at takeoff will likely be jet noise, specifically jet noise contributions. The current study compares predictions from historical jet-noise models within NASAs Aircraft Noise Prediction Program and scale-model data to measurements made in a Learjet 25 flight test. The noise levels from the predictions and scale-model data were below those for the flight data by 2.5 3.5, 1 2, and 3 5 EPNdB for the SAE model, the Stone Jet model, and the scale-model data, respectively. Tones and broadband haystacks were identified in the flight spectra that are not associated with jet noise which increased the flight EPNL by at least 0.5 EPNdB over that computed from spectra with the tones and haystacks removed. The study highlights the need for accurate exhaust temperature measurements, aircraft flight position information, and averaging data across a line of microphones in flight tests. For example, a 100 F to 200 F difference in jet exhaust temperature is enough to explain the differences between flight, model scale, and prediction comparisons.

Beschreibung: A model-scale exhaust system was tested to validate low-noise concepts and noise prediction methods. The tests involved far-field acoustics, translating phased array, and particle image velocimetry; this report covers the far-field acoustic measurements. Data were acquired for a series of nozzles with different chevron designs, both uninstalled and installed on a representative aircraft planform. The impact of the various chevron treatments on the far-field noise was documented, along with the impact of the pylon and planform. For the baseline nozzle, installation produced a 2EPNdB reduction, as assumed in system studies. Chevrons were used to shift noise sources upstream to maximize the installation benefits and to reduce unshielded sources downstream. These resulted in reductions of 4-5EPNdB relative to the uninstalled baseline nozzle. Detailed analysis of spectral directivities behind the integrated EPNL metric gave insight into how well these concepts actually work. When correlated with particle image velocimetry measurements and phased array measurements, reported in companion papers, the explanation of acoustic benefits from top-mounted propulsion is clear as is the path toward optimization of the concept.

Beschreibung: A model-scale exhaust system was tested to validate low-noise propulsion concepts and noise prediction methods. The tests involved far-field acoustics, phased array, and particle image velocimetry (PIV). This paper covers the particle image velocimetry portion. Data was acquired at NASA Glenn's Aero-Acoustic Propulsion Lab for a series of nozzles with different chevron designs, both uninstalled and installed on a representative aircraft planform. The impact of the various chevron treatments on the turbulent velocity field was documented, along with the impact of the pylon and planform. When correlated with far-field acoustic measurements and phased array measurements, reported in companion papers, the explanation of acoustic benefits from top-mounted propulsion is clear as is the path toward optimization of the concept.

Beschreibung: Reynolds-Averaged Navier-Stokes simulations have been performed on a three-stream invertedvelocity profile nozzle with and without various configurations of chevrons attached.The nozzle was mounted on a planform to imitate an engine mounted above a wing, shieldingground observers from engine noise. Several chevron designs intended to aggressively mix thejet and move noise sources upstream for shielding were examined to investigate their effects onnoise and thrust. Numerical results for the baseline nozzle and one chevron configuration werecompared with far-field noise and particle image velocimetry data obtained in NASA GlennResearch Centers Aero-Acoustic Propulsion Laboratory. A configuration in which chevronsalternate penetration into the primary stream and tertiary fan stream was explored using theModern Design of Experiments approach. Short, high-penetration chevrons demonstrated asignificant noise reduction for a relatively small thrust penalty.

Beschreibung: An application program interface (API) has been developed for the creation and access of structured data files generated by microphone phased arrays utilized in aeroacoustics research. Two structured binary file formats are supported, namely NetCDF (Network Common Data Form) and HDF5 (Hierarchical Data Format) files. The API consists of a library of routines callable from C, Fortran or Matlab, with native versions of the API provided for each language. The libraries are divided into categories for file handling, file definition and initialization, data writing, data recovery, and error handling. The API is intended to provide a mechanism for generating self-describing binary files for long-term archiving of raw and processed data generated by phased array systems.

Beschreibung: The main purpose of this study is to examine the audibility of multiple, low-frequency tones that are placed in distinct auditory channels. Three experiments are described, the goals of which are to determine if the presence of sound in multiple channels results in enhanced audibility and to assess the applicability of the Statistical Summation Model (SSM) to this frequency range. This model predicts that for the case of multiple signals that are in separate auditory channels, implying statistical independence, each with sensitivity value d prime of i, the resulting total sensitivity is given by the square root of the sum of the squares of the individual d prime of i values. In common with previous studies conducted at higher frequencies, the signals are pure tones and the maskers are broadband noise. The requirement that low frequency tones be placed in separate auditory filters limited the number of tones to a maximum of three. The first of the three experiments measured the change in masked thresholds for two- and three-tone signals relative to the level of the equally-detectable single tones. The multiple tone signals were composed of combinations of 55, 120 and 200 Hz tones. The measured changes in thresholds exceeded those predicted by the SSM, although they did not differ statistically from the model predictions. The second experiment employed the same overall approach but acquired more data and concentrated on the three-tone signal. Once again, the measured changes in masked threshold exceeded the model predictions, this time to a statistically-significant degree. Two issues were postulated with the potential to yield inflated changes in masked threshold: interaction between tones resulting in perceptible intermodulation/difference tones, and the assumption that the tones were in distinct auditory filters and statistically independent of one another. The third experiment used two sets of three-tone signals to address these latter concerns. The first set of three tones was composed of harmonically related tone frequencies of 55, 110 and 165 Hz, which was an attempt to reduce effects of intermodulation difference tones. The second set of three tones was chosen to be 110, 220 and 330 Hz, again reducing effects of difference tones, but also providing greater separation between tones. Results for the first set of three tones compared to those of the earlier experiments indicated that intermodulation was not an important effect. The second set of three tones (110, 220, 330 Hz) yielded changes in masked thresholds that, on average, were in good agreement with the SSM, although intersubject variability was large and prohibited a definitive conclusion regarding the concern that tone spacing was inadequate. The results of the three experiments showed that the masked threshold of sounds with multiple (two or three) equally-detectable low frequency tones was lower than those of the single tones. In other words, it is clear that audibility is enhanced by the presence of signals in multiple auditory filters. This finding is consistent with most previous research conducted at higher frequencies. In contrast with previous research, test subjects were, on average, able to detect multitone sounds at lower levels than those predicted using the SSM. Analyses that included Monte Carlo simulations showed that normally distributed errors in the single tone thresholds result in biased estimates of the thresholds of multitone sounds. This phenomenon is likely responsible for at least a substantial fraction of the unexpected deviation of measurements from SSM predictions.

Beschreibung: The Advanced Noise Control Fan (Active Noise Control Fan - ANCF) was utilized in the design, test, and evaluation for technical risk mitigation of most of the innovative fan noise reduction technologies developed by NASA over the past 20 years. The ANCF is a low-speed ducted fan test bed for measuring and understanding fan-generated aeroacoustics, duct propagation, and radiation to the farfield. It is considered a low Technology Readiness Level testbed. The international aeroacoustics research community employed the ANCF to facilitate advancement of multiple noise reduction and measurement technologies, and for code validation. From 1994 to 2016, it was located in the NASA Glenn Research Center's Applied Aero Propulsion Laboratory. In 2016 the ANCF was transferred to the University of Notre Dame where it is expected to continue to positively impact ducted fan aeroacoustic research. This paper summarizes the capabilities and contributions of the ANCF to the field by documenting its history.

Beschreibung: 0Genetic polymorphism by means of biochemical genetic markers using polyacrylamide gel electrophoresis system in four barbus fish species has been investigated. Species scientific name were Barbus sharpeyi ; Gunther, 1847 , Barbus grypus ; Heckel, 1843, Barbus xanthopterus ; Heckel, 1843 and Barbus esocinus ; Heckel, 1843.Sampling site and location were mainly in the rivers located in Khoozestan province such as Karoon and Karkheh rivers and the Dez dam. Different organs such as blood, muscle, kidney, eye and heart were sampled and analysed for the presence of tf, es, sod and pgm alleles. High polymorphism and presence of different alleles scored, but populations were not in the H-W equilibrium. Considring results, using current and avaiable genetic markers such as microsattelits is recommended for future works.

Beschreibung: Iranian Fisheries Science Research Institute

Beschreibung: Published

Beschreibung: Cheshmehkileh River and adjacent mountainous streams, play a strategic role as a historical axis for anthropogenic civilization, human welfare also habitat and migration pathway of commercial – biologic valuable fishes e.g. Caspian trout, Caspian kuttum, members of Cyprinidae family in south Caspian Sea drainage. Treats such as overfishing of Caspian trout and Red spotted trout stocks in mountainous headwaters, barriers construction and manipulations those are out of river carrying capacity developed by human activities, affected normal function of river as well. Sand mining big factories establishment next to the river, legal and illegal trade of river sediments, direct entry of Tonekabon landfill leakage into the river, development of Rainbow trout farms since 3 decades and huge effluents into the river containing dead fish and types of solids, escapement of cultured Rainbow trouts into the river, … are major minimum factors which needs basic information for integrating inclusively drainage management system. Cheshmehkileh River contains Headwaters of Dohezar (Daryasar & Nusha), Sehezar and Valamroud rivers during 13 monthly sampling phases between September 2009 and October 2010 based on macrozoobenthoses investigations by EPT, EPT/C EPA protocols, measurements of nominated physic-chemical and microbiologic parameters. Probability of Rainbow trouts escapement and invasion, existence, nutrition in Cheshmehkileh environment indeed investigated. Data analysis explained significant differences (P〈0.05) between groups of measured parameters in different sampling stations. Dendogram of clustered analysis based on consolidation of major biologic/ physic-chemical and microbiologic parameters, separated stations No. 1, 3, 2, 4 in one group and remained classified in different groups. Station 8 and 9 similarly separated which expressed general similarities according to Sehezar river environment which were differs in comparison with other stations. Station 11 separated according to its natural quality of water and environment. Similarities between station 10 to Sehezar river stations 8 and 9 expressed general influence of Sehezar River more than Dohezar River in Cheshmehkileh condition especially in station No. 10. High scores of EPT and EPT/C indices in upstream stations 1, 3 and 8 also low score of indices in stations 7, 13 and 6 expressed levels of environment quality between these groups of stations. Maximum average biomass of macroinvertebrates belongs to Trichoptera order in Cheshmehkileh River. Significant decrease of biomass in stations 11, 12 and 13 in comparison with other stations stated environment degradation in mentioned stations relevant to excessive sand mining as well. Pollution resistant groups of invertebrates significantly increased in downstreams against upstream stations. Also disappearing of Plecoptera order in station No. 7, 9, 10 and 13 stated low quality of environment in comparison with upstream stations. Confirmation of effects quality and quantity for point and non-point sources of imported pollutants require specific management considerations in order to present exploitations, pollutants control and emergencies for river monitoring in forthcoming years.

Beschreibung: Iranian Fisheries Science Research Institute

Beschreibung: Published

Beschreibung: To determine the best acoustic sampling period for obtaining fish biomass estimates of a Mediterranean deep reservoir in Tunisia, we carried out day and night surveys in each of four seasons [spring (April), summer (September), autumn (December) and winter (March)]. A Simrad EK60 echosounder, equipped with two 120 kHz split-beam transducers for simultaneous horizontal and vertical beaming, was used to sample the entire water column. Data collected in December were not usable because fish merged with methane gas bubbles. However, fish abundance varied across the other seasons with a peak in acoustic biomass observed during summer nighttime hours that was associated with high water temperatures. Across seasons, the fish occupied the entire water column, and fish schools were rarely observed. The preferential timeframe (i.e. maximum fish detectability and low gas flux) for acoustic sampling was nighttime hours in summer and daytime hours during spring and winter. Our findings highlight the importance of collecting data across seasons and photoperiods when determining an acoustic sampling strategy.

Beschreibung: This is the pre-peer reviewed version of the following article: [Djemali I., Laouar H. Acoustic fish biomass assessment in a deep Tunisian reservoir: effects of season and diel rhythm on survey results. in: African Journal of Aquatic Science. 2017. IN PRESS], which has been published in final form at [https://doi.org/10.2989/16085914.2016.1277181]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

Beschreibung: In Press

Beschreibung: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution September 2018

Beschreibung: Many chemical constituents are removed from the ocean by attachment to settling particles, a process referred to as “scavenging.” Radioisotopes of thorium, a highly particle-reactive element, have been used extensively to study scavenging in the ocean. However, this process is complicated by the highly variable chemical composition and concentration of particles in oceanic waters. This thesis focuses on understanding the cycling of thorium as affected by particle concentration and particle composition in the North Atlantic. This objective is addressed using (i) the distributions 228,230,234Th, their radioactive parents, particle composition, and bulk particle concentration, as measured or estimated along the GEOTRACES North Atlantic Transect (GA03) and (ii) a model for the reversible exchange of thorium with particles. Model parameters are either estimated by inversion (chapter 2-4), or prescribed in order to simulate 230Th in a circulation model (chapter 5). The major findings of this thesis follow. In chapters 2 and 3, I find that the rate parameters of the reversible exchange model show systematic variations along GA03. In particular, 𝑘1, the apparent first-order rate "constant" of Th adsorption onto particles, generally presents maxima in the mesopelagic zone and minima below. A positive correlation between 𝑘1 and bulk particle concentration is found, consistent with the notion that the specific rate at which a metal in solution attaches to particles increases with the number of surface sites available for adsorption. In chapter 4, I show that Mn (oxyhydr)oxides and biogenic particles most strongly influence 𝑘1 west of the Mauritanian upwelling, but that biogenic particles dominate 𝑘1 in this region. In chapter 5, I find that dissolved 230Th data are best represented by a model that assumes enhanced values of 𝑘1 near the seafloor. Collectively, my findings suggest that spatial variations in Th radioisotope activities observed in the North Atlantic reflect at least partly variations in the rate at which Th is removed from the water column.

Beschreibung: This work was supported by the US National Science Foundation. Two US NSF grants have supported the research in this thesis (OCE-1232578 and OCE-155644).

Beschreibung: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Frontiers in Marine Science 5 (2018): 158, doi:10.3389/fmars.2018.00158.

Beschreibung: In autumn 2015, several sources reported observations of large amounts of gelatinous material in a large north Norwegian fjord system, either caught when trawling for other organisms or fouling fishing gear. The responsible organism was identified as a physonect siphonophore, Nanomia cara, while a ctenophore, Beroe cucumis, and a hydromedusa, Modeeria rotunda, were also registered in high abundances on a couple of occasions. To document the phenomena, we have compiled a variety of data from concurrent fisheries surveys and local fishermen, including physical samples, trawl catch, and acoustic data, photo and video evidence, and environmental data. Because of the gas-filled pneumatophore, characteristic for these types of siphonophores, acoustics provided detailed and unique insight to the horizontal and vertical distribution and potential abundances (~0.2–20 colonies·m−3) of N. cara with the highest concentrations observed in the near bottom region at ~320 m depth in the study area. This suggests that these animals were retained and accumulated in the deep basins of the fjord system possibly blooming here because of favorable environmental conditions and potentially higher prey availability compared to the shallower shelf areas to the north. Few cues as to the origin and onset of the bloom were found, but it may have originated from locally resident siphonophores. The characteristics of the deep-water masses in the fjord basins were different compared to the deep water outside the fjord system, suggesting no recent deep-water import to the fjords. However, water-masses containing siphonophores (not necessarily very abundant), may have been additionally introduced to the fjords at intermediate depths, with the animals subsequently trapped in the deeper fjord basins. The simultaneous observations of abundant siphonophores, hydromedusae, and ctenophores in the Lyngen-Kvænangen fjord system are intriguing, but difficult to provide a unified explanation for, as the organisms differ in their biology and ecology. Nanomia and Beroe spp. are holopelagic, while M. rotunda has a benthic hydroid stage. The species also have different trophic ecologies and dietary preferences. Only by combining information from acoustics, trawling, genetics, and local fishermen, were the identity, abundance, and the vertical and horizontal distribution of the physonect siphonophore, N. cara, established.

Beschreibung: The work was funded by the Ministry of Fisheries and Coastal Affairs through the Institute of Marine Research (IMR), while the Research Council of Norway (RCN) is thanked for the financial support through the project The Arctic Ocean Ecosystem—(SI_ARCTIC, RCN 228896). AH was supported by the Norwegian Taxonony Initiative (NTI 70184233) and ForBio Research School funding (RCN 248799 and NTI 70184215).

Beschreibung: The comment and response concerning the report of oxidation of methane to methanol by water (Reports, 5 May 2017, p. 523) do not fully capture the implications of thermodynamic limitations. A nonisothermal process in which each cycle requires a large temperature swing and permits only substoichiometric methane conversion surely could not be carried out on any practical scale.

Beschreibung: Labinger argues that stepwise reaction of methane with water to produce methanol and hydrogen will never be commercially feasible because of its substoichiometric basis with respect to the active site and the requirement of a large temperature swing. This comment is not touching any new ground, beyond describing the thermodynamic feasibility, thermal cycling, and the role of water as discussed previously. Most important, it does not have a solid numerical basis.

Beschreibung: Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium–weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond–forming reactions, including carbon-hydrogen (C–H) insertion into unactivated sp 3 C–H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C–H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.

Beschreibung: It is commonly assumed that recognition and discrimination of chirality, both in nature and in artificial systems, depend solely on spatial effects. However, recent studies have suggested that charge redistribution in chiral molecules manifests an enantiospecific preference in electron spin orientation. We therefore reasoned that the induced spin polarization may affect enantiorecognition through exchange interactions. Here we show experimentally that the interaction of chiral molecules with a perpendicularly magnetized substrate is enantiospecific. Thus, one enantiomer adsorbs preferentially when the magnetic dipole is pointing up, whereas the other adsorbs faster for the opposite alignment of the magnetization. The interaction is not controlled by the magnetic field per se, but rather by the electron spin orientations, and opens prospects for a distinct approach to enantiomeric separations.

Beschreibung: Theory has established the importance of geometric phase (GP) effects in the adiabatic dynamics of molecular systems with a conical intersection connecting the ground- and excited-state potential energy surfaces, but direct observation of their manifestation in chemical reactions remains a major challenge. Here, we report a high-resolution crossed molecular beams study of the H + HD -〉 H 2 + D reaction at a collision energy slightly above the conical intersection. Velocity map ion imaging revealed fast angular oscillations in product quantum state–resolved differential cross sections in the forward scattering direction for H 2 products at specific rovibrational levels. The experimental results agree with adiabatic quantum dynamical calculations only when the GP effect is included.

Beschreibung: The chemistry of the carbonyl group is essential to modern organic synthesis. The preparation of substituted, enantioenriched 1,3- or 1,5-dicarbonyls is well developed, as their disconnection naturally follows from the intrinsic polarity of the carbonyl group. By contrast, a general enantioselective access to quaternary stereocenters in acyclic 1,4-dicarbonyl systems remains an unresolved problem, despite the tremendous importance of 2,3-substituted 1,4-dicarbonyl motifs in natural products and drug scaffolds. Here we present a broad enantioselective and stereodivergent strategy to access acyclic, polysubstituted 1,4-dicarbonyls via acid-catalyzed [3,3]-sulfonium rearrangement starting from vinyl sulfoxides and ynamides. The stereochemistry at sulfur governs the absolute sense of chiral induction, whereas the double bond geometry dictates the relative configuration of the final products.

Beschreibung: With the recent soaring production of natural gas, the use of methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report the development of photocatalytic C–H amination, alkylation, and arylation of methane, ethane, and higher alkanes under visible light irradiation at ambient temperature. High catalytic efficiency (turnover numbers up to 2900 for methane and 9700 for ethane) and selectivity were achieved using abundant, inexpensive cerium salts as photocatalysts. Ligand-to-metal charge transfer excitation generated alkoxy radicals from simple alcohols that in turn acted as hydrogen atom transfer catalysts. The mixed-phase gas/liquid reaction was adapted to continuous flow, enabling the efficient use of gaseous feedstocks in scalable photocatalytic transformations.

Beschreibung: Intrigued by the potential of nanoscale machines, scientists have long attempted to control molecular motion. We monitored the individual 0.7-nanometer steps of a single molecular hopper as it moved in an electric field along a track in a nanopore controlled by a chemical ratchet. The hopper demonstrated characteristics desired in a moving molecule: defined start and end points, processivity, no chemical fuel requirement, directional motion, and external control. The hopper was readily functionalized to carry cargos. For example, a DNA molecule could be ratcheted along the track in either direction, a prerequisite for nanopore sequencing.

Beschreibung: Phosphorothioate nucleotides have emerged as powerful pharmacological substitutes of their native phosphodiester analogs with important translational applications in antisense oligonucleotide (ASO) therapeutics and cyclic dinucleotide (CDN) synthesis. Stereocontrolled installation of this chiral motif has long been hampered by the systemic use of phosphorus(III) [P(III)]–based reagent systems as the sole practical means of oligonucleotide assembly. A fundamentally different approach is described herein: the invention of a P(V)-based reagent platform for programmable, traceless, diastereoselective phosphorus-sulfur incorporation. The power of this reagent system is demonstrated through the robust and stereocontrolled synthesis of various nucleotidic architectures, including ASOs and CDNs, via an efficient, inexpensive, and operationally simple protocol.

Beschreibung: Here we report an anomalous porous molecular crystal built of C–H···N-bonded double-layered roof-floor components and wall components of a segregatively interdigitated architecture. This complicated porous structure consists of only one type of fully aromatic multijoint molecule carrying three identical dipyridylphenyl wedges. Despite its high symmetry, this molecule accomplishes difficult tasks by using two of its three wedges for roof-floor formation and using its other wedge for wall formation. Although a C–H···N bond is extremely labile, the porous crystal maintains its porosity until thermal breakdown of the C–H···N bonds at 202°C occurs, affording a nonporous polymorph. Though this nonporous crystal survives even at 325°C, it can retrieve the parent porosity under acetonitrile vapor. These findings show how one can translate simplicity into ultrahigh complexity.

Beschreibung: Some of the simplest and most powerful carbon-carbon bond forming strategies take advantage of readily accessible ubiquitous motifs: carbonyls and olefins. Here we report a fundamentally distinct mode of reactivity between carbonyls and olefins that differs from established acid-catalyzed carbonyl-ene, Prins, and carbonyl-olefin metathesis reaction paths. A range of epsilon, zeta-unsaturated ketones undergo Brønsted acid–catalyzed intramolecular cyclization to provide tetrahydrofluorene products via the formation of two new carbon-carbon bonds. Theoretical calculations and accompanying mechanistic studies suggest that this carbocyclization reaction proceeds through the intermediacy of a transient oxetane formed by oxygen atom transfer. The complex polycyclic frameworks in this product class appear as common substructures in organic materials, bioactive natural products, and recently developed pharmaceuticals.

Beschreibung: Alkene aminoarylation with a single, bifunctional reagent is a concise synthetic strategy. We report a catalytic protocol for the addition of arylsulfonylacetamides across electron-rich alkenes with complete anti-Markovnikov regioselectivity and excellent diastereoselectivity to provide 2,2-diarylethylamines. In this process, single-electron alkene oxidation enables carbon-nitrogen bond formation to provide a key benzylic radical poised for a Smiles-Truce 1,5-aryl shift. This reaction is redox-neutral, exhibits broad functional group compatibility, and occurs at room temperature with loss of sulfur dioxide. As this process is driven by visible light, uses readily available starting materials, and demonstrates convergent synthesis, it is well suited for use in a variety of synthetic endeavors.

Beschreibung: Photocatalysis based on optically active, "plasmonic" metal nanoparticles has emerged as a promising approach to facilitate light-driven chemical conversions under far milder conditions than thermal catalysis. However, an understanding of the relation between thermal and electronic excitations has been lacking. We report the substantial light-induced reduction of the thermal activation barrier for ammonia decomposition on a plasmonic photocatalyst. We introduce the concept of a light-dependent activation barrier to account for the effect of light illumination on electronic and thermal excitations in a single unified picture. This framework provides insight into the specific role of hot carriers in plasmon-mediated photochemistry, which is critically important for designing energy-efficient plasmonic photocatalysts.

Beschreibung: Single-electron reduction of a carbonyl to a ketyl enables access to a polarity-reversed platform of reactivity for this cornerstone functional group. However, the synthetic utility of the ketyl radical is hindered by the strong reductants necessary for its generation, which also limit its reactivity to net reductive mechanisms. We report a strategy for net redox-neutral generation and reaction of ketyl radicals. The in situ conversion of aldehydes to α-acetoxy iodides lowers their reduction potential by more than 1 volt, allowing for milder access to the corresponding ketyl radicals and an oxidative termination event. Upon subjecting these iodides to a dimanganese decacarbonyl precatalyst and visible light irradiation, an atom transfer radical addition (ATRA) mechanism affords a broad scope of vinyl iodide products with high Z -selectivity.

Beschreibung: Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert -butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.

Beschreibung: Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation [(Cp i Pr5 )Dy(Cp*)] + (Cp i Pr5 , penta-iso-propylcyclopentadienyl; Cp *, pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of U eff = 1541 wave number is also measured. The magnetic blocking temperature of T B = 80 kelvin for this cation overcomes an essential barrier toward the development of nanomagnet devices that function at practical temperatures.

Beschreibung: The development of highly reactive and stereoselective catalytic systems is required not only to improve existing synthetic methods but also to invent distinct chemical reactions. Herein, a homogenized combination of nickel-based Lewis acid–surfactant-combined catalysts and single-walled carbon nanotubes is shown to exhibit substantial activity in water. In addition to the enhanced reactivity, stereoselective performance and long-term stability were demonstrated in asymmetric conjugate addition reactions of aldoximes to furnish chiral nitrones in high yields with excellent selectivities. The practical and straightforward application of the designed catalysts in water provides an expedient, environmentally benign, and highly efficient pathway to access optically active compounds.

Beschreibung: Exploration of intermediates that enable chemoselective cycloaddition reactions and expeditious construction of fused- or bridged-ring systems is a continuous challenge for organic synthesis. As an intermediate of interest, the oxyallyl cation has been harnessed to synthesize architectures containing seven-membered rings via (4+3) cycloaddition. However, its potential to access five-membered skeletons is underdeveloped, largely due to the thermally forbidden (3+2) pathway. Here, the combination of a tailored precursor and a Pd(0) catalyst generates a Pd-oxyallyl intermediate that cyclizes with conjugated dienes to produce a diverse array of tetrahydrofuran skeletons. The cycloaddition overrides conventional (4+3) selectivity by proceeding through a stepwise pathway involving a Pd-allyl transfer and ring closure sequence. Subsequent treatment of the (3+2) adducts with a palladium catalyst converts the heterocycles to the carbocyclic cyclopentanones.

Beschreibung: Understanding the practical limitations of chemical reactions is critically important for efficiently planning the synthesis of compounds in pharmaceutical, agrochemical, and specialty chemical research and development. However, literature reports of the scope of new reactions are often cursory and biased toward successful results, severely limiting the ability to predict reaction outcomes for untested substrates. We herein illustrate strategies for carrying out large-scale surveys of chemical reactivity by using a material-sparing nanomole-scale automated synthesis platform with greatly expanded synthetic scope combined with ultrahigh-throughput matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry (MALDI-TOF MS).

Beschreibung: Researchers around the world have observed the formation of molecularly ordered structures of unknown origin on the surface of titanium dioxide (TiO 2 ) photocatalysts exposed to air and solution. Using a combination of atomic-scale microscopy and spectroscopy, we show that TiO 2 selectively adsorbs atmospheric carboxylic acids that are typically present in parts-per-billion concentrations while effectively repelling other adsorbates, such as alcohols, that are present in much higher concentrations. The high affinity of the surface for carboxylic acids is attributed to their bidentate binding. These self-assembled monolayers have the unusual property of being both hydrophobic and highly water-soluble, which may contribute to the self-cleaning properties of TiO 2 . This finding is relevant to TiO 2 photocatalysis, because the self-assembled carboxylate monolayers block the undercoordinated surface cation sites typically implicated in photocatalysis.

Beschreibung: The alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) typically engage in chemical bonding as classical main-group elements through their n s and n p valence orbitals, where n is the principal quantum number. Here we report the isolation and spectroscopic characterization of eight-coordinate carbonyl complexes M(CO) 8 (where M = Ca, Sr, or Ba) in a low-temperature neon matrix. Analysis of the electronic structure of these cubic O h -symmetric complexes reveals that the metal–carbon monoxide (CO) bonds arise mainly from [M(d )] -〉 (CO) 8 backdonation, which explains the strong observed red shift of the C-O stretching frequencies. The corresponding radical cation complexes were also prepared in gas phase and characterized by mass-selected infrared photodissociation spectroscopy, confirming adherence to the 18-electron rule more conventionally associated with transition metal chemistry.

Beschreibung: Mystery surrounds the transition from gas-phase hydrocarbon precursors to terrestrial soot and interstellar dust, which are carbonaceous particles formed under similar conditions. Although polycyclic aromatic hydrocarbons (PAHs) are known precursors to high-temperature carbonaceous-particle formation, the molecular pathways that initiate particle formation are unknown. We present experimental and theoretical evidence for rapid molecular clustering–reaction pathways involving radicals with extended conjugation. These radicals react with other hydrocarbon species to form covalently bound complexes that promote further growth and clustering by regenerating resonance-stabilized radicals through low-barrier hydrogen-abstraction and hydrogen-ejection reactions. Such radical–chain reaction pathways may lead to covalently bound clusters of PAHs and other hydrocarbons that would otherwise be too small to condense at high temperatures, thus providing the key mechanistic steps for rapid particle formation and surface growth by hydrocarbon chemisorption.

Beschreibung: Basic heteroarenes are a ubiquitous feature of pharmaceuticals and bioactive molecules, and Minisci-type additions of radical nucleophiles are a leading method for their elaboration. Despite many Minisci-type protocols that result in the formation of stereocenters, exerting control over the absolute stereochemistry at these centers remains an unmet challenge. We report a process for addition of prochiral radicals, generated from amino acid derivatives, to pyridines and quinolines. Our method offers excellent control of both enantioselectivity and regioselectivity. An enantiopure chiral Brønsted acid catalyst serves both to activate the substrate and induce asymmetry, while an iridium photocatalyst mediates the required electron transfer processes. We anticipate that this method will expedite access to enantioenriched small-molecule building blocks bearing versatile basic heterocycles.

Beschreibung: Primary amines are essential constituents of biologically active molecules and versatile intermediates in the synthesis of drugs and agrochemicals. However, their preparation from easily accessible alkenes remains challenging. Here, we report a general strategy to access primary amines from alkenes through an operationally simple iron-catalyzed aminochlorination reaction. A stable hydroxylamine derivative and benign sodium chloride act as the respective nitrogen and chlorine sources. The reaction proceeds at room temperature under air; tolerates a large scope of aliphatic and conjugated alkenes, including densely functionalized substrates; and provides excellent anti-Markovnikov regioselectivity with respect to the amino group. The reactivity of the 2-chloroalkylamine products, an understudied class of amphoteric molecules, enables facile access to linear or branched aliphatic amines, aziridines, aminonitriles, azido amines, and homoallylic amines.

Beschreibung: Despite the enormous potential for the use of stereospecific cross-coupling reactions to rationally manipulate the three-dimensional structure of organic molecules, the factors that control the transfer of stereochemistry in these reactions remain poorly understood. Here we report a mechanistic and synthetic investigation into the use of enantioenriched alkylboron nucleophiles in stereospecific Pd-catalyzed Suzuki cross-coupling reactions. By developing a suite of molecular descriptors of phosphine ligands, we could apply predictive statistical models to select or design distinct ligands that respectively promoted stereoinvertive and stereoretentive cross-coupling reactions. Stereodefined branched structures were thereby accessed through the predictable manipulation of absolute stereochemistry, and a general model for the mechanism of alkylboron transmetallation was proposed.

Beschreibung: Heterobiaryls composed of pyridine and diazine rings are key components of pharmaceuticals and are often central to pharmacological function. We present an alternative approach to metal-catalyzed cross-coupling to make heterobiaryls using contractive phosphorus C–C couplings, also termed phosphorus ligand coupling reactions. The process starts by regioselective phosphorus substitution of the C–H bonds para to nitrogen in two successive heterocycles; ligand coupling is then triggered via acidic alcohol solutions to form the heterobiaryl bond. Mechanistic studies imply that ligand coupling is an asynchronous process involving migration of one heterocycle to the ipso position of the other around a central pentacoordinate P(V) atom. The strategy can be applied to complex drug-like molecules containing multiple reactive sites and polar functional groups, and also enables convergent coupling of drug fragments and late-stage heteroarylation of pharmaceuticals.

Beschreibung: Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF 3 I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF 3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.

Beschreibung: Common anionic nucleophiles such as those derived from inorganic salts have not been used for enantioselective catalysis because of their insolubility. Here, we report that merging hydrogen bonding and phase-transfer catalysis provides an effective mode of activation for nucleophiles that are insoluble in organic solvents. This catalytic manifold relies on hydrogen bonding complexation to render nucleophiles soluble and reactive, while simultaneously inducing asymmetry in the ensuing transformation. We demonstrate the concept using a chiral bis-urea catalyst to form a tridentate hydrogen bonding complex with fluoride from its cesium salt, thereby enabling highly efficient enantioselective ring opening of episulfonium ion. This fluorination method is synthetically valuable considering the scarcity of alternative protocols and points the way to wider application of the catalytic approach with diverse anionic nucleophiles.

Beschreibung: Carbon dioxide (CO 2 ) electroreduction could provide a useful source of ethylene, but low conversion efficiency, low production rates, and low catalyst stability limit current systems. Here we report that a copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO 2 to ethylene with 70% faradaic efficiency at a potential of –0.55 volts versus a reversible hydrogen electrode (RHE). Hydroxide ions on or near the copper surface lower the CO 2 reduction and carbon monoxide (CO)–CO coupling activation energy barriers; as a result, onset of ethylene evolution at –0.165 volts versus an RHE in 10 molar potassium hydroxide occurs almost simultaneously with CO production. Operational stability was enhanced via the introduction of a polymer-based gas diffusion layer that sandwiches the reaction interface between separate hydrophobic and conductive supports, providing constant ethylene selectivity for an initial 150 operating hours.

Beschreibung: White phosphorus, generated in the legacy thermal process for phosphate rock upgrading, has long been the key industrial intermediate for the synthesis of phosphorus-containing chemicals, including herbicides, flame-retardants, catalyst ligands, battery electrolytes, pharmaceuticals, and detergents. In contrast, phosphate fertilizers are made on a much larger scale from phosphoric acid, obtained by treating phosphate rock with sulfuric acid. Dehydration of phosphoric acid using sodium chloride gives trimetaphosphate, and here we report that trichlorosilane, primarily used for the production of high-purity silicon, reduces trimetaphosphate to the previously unknown bis(trichlorosilyl)phosphide anion. This anion offers an entry point to value-added organophosphorus chemicals such as primary and secondary alkyl phosphines, and thus to organophosphinates, and can also be used to prepare phosphine gas and the hexafluorophosphate anion, all previously available only downstream from white phosphorus.

Beschreibung: Cross-coupling chemistry is widely applied to carbon-carbon bond formation in the synthesis of medicines, agrochemicals, and other functional materials. Recently, single-electron–induced variants of this reaction class have proven particularly useful in the formation of C(sp 2 )–C(sp 3 ) linkages, although certain compound classes have remained a challenge. Here, we report the use of sulfones to activate the alkyl coupling partner in nickel-catalyzed radical cross-coupling with aryl zinc reagents. This method’s tolerance of fluoroalkyl substituents proved particularly advantageous for the streamlined preparation of pharmaceutically oriented fluorinated scaffolds that previously required multiple steps, toxic reagents, and nonmodular retrosynthetic blueprints. Five specific sulfone reagents facilitate the rapid assembly of a vast set of compounds, many of which contain challenging fluorination patterns.

Beschreibung: Plasmon-induced chemical reactions of molecules adsorbed on metal nanostructures are attracting increased attention for photocatalytic reactions. However, the mechanism remains controversial because of the difficulty of direct observation of the chemical reactions in the plasmonic field, which is strongly localized near the metal surface. We used a scanning tunneling microscope (STM) to achieve real-space and real-time observation of a plasmon-induced chemical reaction at the single-molecule level. A single dimethyl disulfide molecule on silver and copper surfaces was dissociated by the optically excited plasmon at the STM junction. The STM study combined with theoretical calculations shows that this plasmon-induced chemical reaction occurred by a direct intramolecular excitation mechanism.

Beschreibung: Identifying catalyst activation modes that exploit one-electron chemistry and overcome associated deactivation pathways will be transformative for developing first-row transition metal catalysts with performance equal or, ideally, superior to precious metals. Here we describe a zinc-activation method compatible with high-throughput reaction discovery that identified scores of cobalt-phosphine combinations for the asymmetric hydrogenation of functionalized alkenes. An optimized catalyst prepared from ( R , R )-Ph-BPE {Ph-BPE, 1,2-bis[(2 R ,5 R )-2,5-diphenylphospholano]ethane} and cobalt chloride [CoCl 2 ·6H 2 O] exhibited high activity and enantioselectivity in protic media and enabled the asymmetric synthesis of the epilepsy medication levetiracetam at 200-gram scale with 0.08 mole % catalyst loading. Stoichiometric studies established that the cobalt (II) catalyst precursor ( R , R )-Ph-BPECoCl 2 underwent ligand displacement by methanol, and zinc promoted facile one-electron reduction to cobalt (I), which more stably bound the phosphine.

Beschreibung: Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.