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The High-Resolution Rapid Refresh (HRRR) is a convection-allowing implementation of the Advanced Research version of the Weather Research and Forecast (WRF-ARW) Model that covers the conterminous United States and Alaska and runs hourly (for CONUS; every 3 h for Alaska) in real time at the National Centers for Environmental Prediction. The high-resolution forecasts support a variety of user applications including aviation, renewable energy, and prediction of many forms of severe weather. In this second of two articles, forecast performance is documented for a wide variety of forecast variables and across HRRR versions. HRRR performance varies across geographical domain, season, and time of day depending on both prevalence of particular meteorological phenomena and the availability of both conventional and nonconventional observations. Station-based verification of surface weather forecasts (2-m temperature and dewpoint temperature, 10-m winds, visibility, and cloud ceiling) highlights the ability of the HRRR to represent daily planetary boundary layer evolution and the development of convective and stratiform cloud systems, while gridded verification of simulated composite radar reflectivity and quantitative precipitation forecasts reveals HRRR predictive skill for summer and winter precipitation systems. Significant improvements in performance for specific forecast problems are documented for the upgrade versions of the HRRR (HRRRv2, v3, and v4) implemented in 2016, 2018, and 2020, respectively. Development of the HRRR model data assimilation and physics paves the way for future progress with operational convective-scale modeling. Significance Statement NOAA’s operational hourly updating convection-allowing model, the High-Resolution Rapid Refresh (HRRR), is a key tool for short-range weather forecasting and situational awareness. Improvements in assimilation of weather observations, as well as in physics parameterizations, has led to improvements in simulated radar reflectivity and quantitative precipitation forecasts since the initial implementation of HRRR in September 2014. Other targeted development has focused on improved representation of the diurnal cycle of the planetary boundary layer, resulting in improved near-surface temperature and humidity forecasts. Additional physics and data assimilation changes have led to improved treatment of the development and erosion of low-level clouds, including subgrid-scale clouds. The final version of HRRR features storm-scale ensemble data assimilation and explicit prediction of wildfire smoke plumes.

The High-Resolution Rapid Refresh (HRRR) is a convection-allowing implementation of the Advanced Research version of the Weather Research and Forecasting (WRF-ARW) Model with hourly data assimilation that covers the conterminous United States and Alaska and runs in real time at the NOAA/National Centers for Environmental Prediction (NCEP). Implemented operationally at NOAA/NCEP in 2014, the HRRR features 3-km horizontal grid spacing and frequent forecasts (hourly for CONUS and 3-hourly for Alaska). HRRR initialization is designed for optimal short-range forecast skill with a particular focus on the evolution of precipitating systems. Key components of the initialization are radar-reflectivity data assimilation, hybrid ensemble-variational assimilation of conventional weather observations, and a cloud analysis to initialize stratiform cloud layers. From this initial state, HRRR forecasts are produced out to 18 h every hour, and out to 48 h every 6 h, with boundary conditions provided by the Rapid Refresh system. Between 2014 and 2020, HRRR development was focused on reducing model bias errors and improving forecast realism and accuracy. Improved representation of the planetary boundary layer, subgrid-scale clouds, and land surface contributed extensively to overall HRRR improvements. The final version of the HRRR (HRRRv4), implemented in late 2020, also features hybrid data assimilation using flow-dependent covariances from a 3-km, 36-member ensemble (“HRRRDAS”) with explicit convective storms. HRRRv4 also includes prediction of wildfire smoke plumes. The HRRR provides a baseline capability for evaluating NOAA’s next-generation Rapid Refresh Forecast System, now under development. Significance Statement NOAA’s operational hourly updating, convection-allowing model, the High-Resolution Rapid Refresh (HRRR), is a key tool for short-range weather forecasting and situational awareness. Improvements in assimilation of weather observations, as well as in physics parameterizations, have led to improvements in simulated radar reflectivity and quantitative precipitation forecasts since the initial implementation of HRRR in September 2014. Other targeted development has focused on improved representation of the diurnal cycle of the planetary boundary layer, resulting in improved near-surface temperature and humidity forecasts. Additional physics and data assimilation changes have led to improved treatment of the development and erosion of low-level clouds, including subgrid-scale clouds. The final version of HRRR features storm-scale ensemble data assimilation and explicit prediction of wildfire smoke plumes.

A new hybrid, sigma-pressure vertical coordinate was recently added to the Weather Research and Forecasting (WRF) Model in an effort to reduce numerical noise in the model equations near complex terrain. Testing of this hybrid, terrain-following coordinate was undertaken in the WRF-based Rapid Refresh (RAP) and High-Resolution Rapid Refresh (HRRR) models to assess impacts on retrospective and real-time simulations. Initial cold-start simulations indicated that the majority of differences between the hybrid and traditional sigma coordinate were confined to regions downstream of mountainous terrain and focused in the upper levels. Week-long retrospective simulations generally resulted in small improvements for the RAP, and a neutral impact in the HRRR when the hybrid coordinate was used. However, one possibility is that the inclusion of data assimilation in the experiments may have minimized differences between the vertical coordinates. Finally, analysis of turbulence forecasts with the new hybrid coordinate indicate a significant reduction in spurious vertical motion over the full length of the Rocky Mountains. Overall, the results indicate a potential to improve forecast metrics through implementation of the hybrid coordinate, particularly at upper levels, and downstream of complex terrain.

The primary goal of the Second Wind Forecast Improvement Project (WFIP2) is to advance the state-of-the-art of wind energy forecasting in complex terrain. To achieve this goal, a comprehensive 18-month field measurement campaign was conducted in the region of the Columbia River basin. The observations were used to diagnose and quantify systematic forecast errors in the operational High-Resolution Rapid Refresh (HRRR) model during weather events of particular concern to wind energy forecasting. Examples of such events are cold pools, gap flows, thermal troughs/marine pushes, mountain waves, and topographic wakes. WFIP2 model development has focused on the boundary layer and surface-layer schemes, cloud–radiation interaction, the representation of drag associated with subgrid-scale topography, and the representation of wind farms in the HRRR. Additionally, refinements to numerical methods have helped to improve some of the common forecast error modes, especially the high wind speed biases associated with early erosion of mountain–valley cold pools. This study describes the model development and testing undertaken during WFIP2 and demonstrates forecast improvements. Specifically, WFIP2 found that mean absolute errors in rotor-layer wind speed forecasts could be reduced by 5%–20% in winter by improving the turbulent mixing lengths, horizontal diffusion, and gravity wave drag. The model improvements made in WFIP2 are also shown to be applicable to regions outside of complex terrain. Ongoing and future challenges in model development will also be discussed.

Purpose Studies suggest ketogenic diets (KD) produce favorable outcomes (health and exercise performance); however, most rodent studies have used a low-protein KD, which does not reflect the normal- to high-protein KD used by humans. Liver has an important role in ketoadaptation due to its involvement in gluconeogenesis and ketogenesis. This study was designed to test the hypothesis that exercise training (ExTr) while consuming a normal-protein KD (NPKD) would induce additive/synergistic responses in liver metabolic pathways. Methods Lean, healthy male C57BL/6J mice were fed a low-fat control diet (15.9% kcal protein, 11.9% kcal fat, 72.2% kcal carbohydrate) or carbohydrate-deficient NPKD (16.1% protein, 83.9% kcal fat) for 6 wk. After 3 wk on the diet, half were subjected to 3-wk treadmill ExTr (5 d·wk−1, 60 min·d−1, moderate-vigorous intensity). Upon conclusion, metabolic and endocrine outcomes related to substrate metabolism were tested in liver and pancreas. Results NPKD-fed mice had higher circulating β-hydroxybutyrate and maintained glucose at rest and during exercise. Liver of NPKD-fed mice had lower pyruvate utilization and greater ketogenic potential as evidenced by higher oxidative rates to catabolize lipids (mitochondrial and peroxisomal) and ketogenic amino acids (leucine). ExTr had higher expression of the gluconeogenic gene, Pck1, but lower hepatic glycogen, pyruvate oxidation, incomplete fat oxidation, and total pancreas area. Interaction effects between the NPKD and ExTr were observed for intrahepatic triglycerides, as well as genes involved in gluconeogenesis, ketogenesis, mitochondrial fat oxidation, and peroxisomal markers; however, none were additive/synergistic. Rather, in each instance the interaction effects showed the NPKD and ExTr opposed each other. Conclusions An NPKD and an ExTr independently induce shifts in hepatic metabolic pathways, but changes do not seem to be additive/synergistic in healthy mice.

Adaptations in hepatic and skeletal muscle substrate metabolism following acute and chronic (6 wk; 5 days/wk; 1 h/day) low-intensity treadmill exercise were tested in healthy male C57BL/6J mice. Low-intensity exercise maximizes lipid utilization; therefore, we hypothesized pathways involved in lipid metabolism would be most robustly affected. Acute exercise nearly depleted liver glycogen immediately postexercise (0 h), whereas hepatic triglyceride (TAG) stores increased in the early stages after exercise (0–3 h). Also, hepatic peroxisome proliferator-activated receptor-γ coactivator-1α ( PGC-1α) gene expression and fat oxidation (mitochondrial and peroxisomal) increased immediately postexercise (0 h), whereas carbohydrate and amino acid oxidation in liver peaked 24–48 h later. Alternatively, skeletal muscle exhibited a less robust response to acute exercise as stored substrates (glycogen and TAG) remained unchanged, induction of PGC-1α gene expression was delayed (up at 3 h), and mitochondrial substrate oxidation pathways (carbohydrate, amino acid, and lipid) were largely unaltered. Peroxisomal lipid oxidation exhibited the most dynamic changes in skeletal muscle substrate metabolism after acute exercise; however, this response was also delayed (peaked 3–24 h postexercise), and expression of peroxisomal genes remained unaffected. Interestingly, 6 wk of training at a similar intensity limited weight gain, increased muscle glycogen, and reduced TAG accrual in liver and muscle; however, substrate oxidation pathways remained unaltered in both tissues. Collectively, these results suggest changes in substrate metabolism induced by an acute low-intensity exercise bout in healthy mice are more rapid and robust in liver than in skeletal muscle; however, training at a similar intensity for 6 wk is insufficient to induce remodeling of substrate metabolism pathways in either tissue. NEW & NOTEWORTHY Effects of low-intensity exercise on substrate metabolism pathways were tested in liver and skeletal muscle of healthy mice. This is the first study to describe exercise-induced adaptations in peroxisomal lipid metabolism and also reports comprehensive adaptations in mitochondrial substrate metabolism pathways (carbohydrate, lipid, and amino acid). Acute low-intensity exercise induced shifts in mitochondrial and peroxisomal metabolism in both tissues, but training at this intensity did not induce adaptive remodeling of metabolic pathways in healthy mice.

Ronald Breslow was one of the leading organic chemists of his generation. He had received the perfect start in gaining a Harvard doctorate at the age of 24 supervised by the legendary Bob Woodward, followed by a year of postdoctoral work in Cambridge with the equally legendary, but scientifically distinct, Alexander Todd. An academic career of 62 years at Columbia University followed, starting in 1955, and scientific success arose quickly. He was a physical organic chemist, using this discipline as a vehicle for tackling all manner of scientific problems and venturing as needed into biology, physics or medicine. He prepared the simplest aromatic species, solved the mechanism of action of Vitamin B1, built bridges between organic chemistry and enzymology, and developed an anti-cancer drug with a distinct enzyme target. Rewards, honours and prestigious lecture invitations arrived throughout his career, in recognition of the scope and originality of his achievements. He met Esther at Harvard, and they married on completion of his PhD. After returning to the USA, she pursued a successful career in biochemistry at Weill Cornell Medical School in New York. They raised two daughters, Stephanie and Karen, who both became successful attorneys. He had strong family values and was very proud of all their achievements. Towards his co-workers, he was open, eager to engage in discussion and committed to supporting them, both during time at Columbia and thereafter. His warmth encouraged positive responses to his style of supervision, and lively discussions. He was an accomplished classical and jazz pianist, the family cook, and they scuba-dived on annual vacations.

Accurate cloud and precipitation forecasts are a fundamental component of short-range data assimilation/model prediction systems such as the NOAA 3-km High-Resolution Rapid Refresh (HRRR) or the 13-km Rapid Refresh (RAP). To reduce cloud and precipitation spin-up problems, a non-variational assimilation technique for stratiform clouds was developed within the Gridpoint Statistical Interpolation (GSI) data assimilation system. One goal of this technique is retention of observed stratiform cloudy and clear 3D volumes into the subsequent model forecast. The cloud observations used include cloud-top data from satellite brightness temperatures, surface-based ceilometer data, and surface visibility. Quality control, expansion into spatial information content, and forward operators are described for each observation type. The projection of data from these observation types into an observation-based cloud-information 3D gridded field is accomplished via identification of cloudy, clear, and cloud-unknown 3D volumes. Updating of forecast background fields is accomplished through clearing and building of cloud water and cloud ice with associated modifications to water vapor and temperature. Impact of the cloud assimilation on short-range forecasts is assessed with a set of retrospective experiments in warm and cold seasons using the RAPv5 model. Short-range (1-9h) forecast skill is improved in both seasons for cloud ceiling and visibility and for 2-m temperature in daytime and with mixed results for other measures. Two modifications were introduced and tested with success: use of prognostic subgrid-scale cloud fraction to condition cloud building (in response to a high bias) and removal of a WRF-based rebalancing.

Ketogenic diets (KDs) are reported to improve body weight, fat mass, and exercise performance in humans. Unfortunately, most rodent studies have used a low-protein KD, which does not recapitulate diets used by humans. Since skeletal muscle plays a critical role in responding to macronutrient perturbations induced by diet and exercise, the purpose of this study was to test if a normal-protein KD (NPKD) impacts shifts in skeletal muscle substrate oxidative capacity in response to exercise training (ExTr). A high fat, carbohydrate-deficient NPKD (16.1% protein, 83.9% fat, 0% carbohydrate) was given to C57BL/6J male mice for 6 wk, whereas controls (Con) received a low-fat diet with similar protein (15.9% protein, 11.9% fat, 72.2% carbohydrate). After 3 wk on the diet, mice began treadmill training 5 days/wk, 60 min/day for 3 wks. The NPKD increased body weight and fat mass, whereas ExTr negated a continued rise in adiposity. ExTr increased intramuscular glycogen, whereas the NPKD increased intramuscular triglycerides. Neither the NPKD nor ExTr alone altered mitochondrial content; however, in combination, the NPKD-ExTr group showed increases in PGC-1α and markers of mitochondrial fission/fusion. Pyruvate oxidative capacity was unchanged by either intervention, whereas ExTr increased leucine oxidation in NPKD-fed mice. Lipid metabolism pathways had the most notable changes as the NPKD and ExTr interventions both enhanced mitochondrial and peroxisomal lipid oxidation and many adaptations were additive or synergistic. Overall, these results suggest that a combination of a NPKD and ExTr induces additive and/or synergistic adaptations in skeletal muscle oxidative capacity. NEW & NOTEWORTHY A ketogenic diet with normal protein content (NPKD) increases body weight and fat mass, increases intramuscular triglyceride storage, and upregulates pathways related to protein metabolism. In combination with exercise training, a NPKD induces additive and/or synergistic activation of AMPK, PGC-1α, mitochondrial fission/fusion genes, mitochondrial fatty acid oxidation, and peroxisomal adaptations in skeletal muscle. Collectively, results from this study provide mechanistic insight into adaptations in skeletal muscle relevant to keto-adaptation.

International audience; This paper describes the synthesis, structure, conformation and configurational stability of novel 8-atom meta-meta’ linked biaryls, as models for controlling the ratio of atropisomers through remote central chirality. The synthesis of model compounds is described where the configuration of the linker is provided by reduced C4 and C6 sugars. Their properties have been examined by X-ray, NMR and ECD. Taken together, they provide information on the conformation of the linking chain in each case and indicate a barrier to atropisomerisation in the region of 55 kJ mol−1. For the diastereomeric C6 compounds, the preferred atropisomer is defined by the configuration of the backbone secondary methyl groups. Computational analysis confirms the direction of axial chirality from ECD spectra and offers a model for the distinction between the (R,R,R,R) and (S,R,R,S) C6-isomers..

H-bond to deliver fluoride Simple fluoride salts are theoretically convenient reagents for carbon-fluorine bond formation. In practice, they are often insoluble in the solvents that dissolve their reaction partners. Pupo et al. developed urea-based catalysts that make fluoride soluble through hydrogen bonding. Moreover, their chiral substituents bias the reaction toward one of two mirror image products of C–F bond formation. This strategy should be applicable to the asymmetric addition of other salts, too. Science , this issue p. 638

The laser magnetic resonance (LMR) spectroscopic technique has been used to reinvestigate the mid-infrared spectrum of the NCN free radical in its 3 Σ g - ground electronic state. A liquid nitrogen-cooled carbon monoxide (CO) laser was used as a source of strong coherent radiation in the 1442 to 1484 cm-1 region of the infrared. Vibration-rotation transitions were brought into resonance with the laser frequency using magnetic flux densities up to 1.4 T. Spectra were recorded in both parallel (ΔMJ = 0) and perpendicular (ΔMJ = ±1) polarizations with ten CO laser lines. Over one hundred new absorption lines were observed in the LMR spectra and have been subsequently assigned to transitions in either the 3 0 1 fundamental band (near 1466.5 cm-1) or the 2 1 1 3 0 1 hot band (near 1455.6 cm-1) of NCN in the 3 Σ g - ground state. An improved set of molecular parameters for NCN has been determined from a least-squares fit of all the available data on the infrared spectrum, provided by Fourier transform and LMR spectra. In the wake of an exhaustive analysis of the LMR spectra, several additional lines remain. Although chemical tests indicate these lines do not belong to NCN, it has not proved possible to identify their carrier(s).

This study describes the initial application of radiance bias correction and channel selection in the hourly updated Rapid Refresh model. For this initial application, data from the Atmospheric Infrared Sounder (AIRS) are used; this dataset gives atmospheric temperature and water vapor information at higher vertical resolution and accuracy than previously launched low-spectral resolution satellite systems. In this preliminary study, data from AIRS are shown to add skill to short-range weather forecasts over a relatively data-rich area. Two 1-month retrospective runs were conducted to evaluate the impact of assimilating clear-sky AIRS radiance data on 1–12-h forecasts using a research version of the National Oceanic and Atmospheric Administration (NOAA) Rapid Refresh (RAP) regional mesoscale model already assimilating conventional and other radiance [AMSU-A, Microwave Humidity Sounder (MHS), HIRS-4] data. Prior to performing the assimilation, a channel selection and bias-correction spinup procedure was conducted that was appropriate for the RAP configuration. RAP forecasts initialized from analyses with and without AIRS data were verified against radiosonde, surface atmosphere, precipitation, and satellite radiance observations. Results show that the impact from AIRS radiance data on short-range forecast skill in the RAP system is small but positive and statistically significant at the 95% confidence level. The RAP-specific channel selection and bias correction procedures described in this study were the basis for similar applications to other radiance datasets now assimilated in version 3 of RAP implemented at NOAA’s National Centers for Environmental Prediction (NCEP) in August 2016.

A stochastic parameter perturbation (SPP) scheme consisting of spatially and temporally varying perturbations of uncertain parameters in the Grell–Freitas convective scheme and the Mellor–Yamada–Nakanishi–Niino planetary boundary scheme was developed within the Rapid Refresh ensemble system based on the Weather Research and Forecasting Model. Alone the stochastic parameter perturbations generate insufficient spread to be an alternative to the operational configuration that utilizes combinations of multiple parameterization schemes. However, when combined with other stochastic parameterization schemes, such as the stochastic kinetic energy backscatter (SKEB) scheme or the stochastic perturbation of physics tendencies (SPPT) scheme, the stochastic ensemble system has comparable forecast performance. An additional analysis quantifies the added value of combining SPP and SPPT over an ensemble that uses SPPT only, which is generally beneficial, especially for surface variables. The ensemble combining all three stochastic methods consistently produces the best spread–skill ratio and generally outperforms the multiphysics ensemble. The results of this study indicate that using a single-physics suite ensemble together with stochastic methods is an attractive alternative to multiphysics ensembles and should be considered in the design of future high-resolution regional and global ensembles.

Silyl-substituted aromatic compounds can participate as the electrophilic component in palladium-catalysed cross-couplings, and reactivity is enhanced by a neighbouring silyl-group. Products analogous to those obtained from C–H activation chemistry are accessible by this means with the additional benefit of regiochemistry defined by the site of silyl substitution. DFT studies described here show that the mechanism of C–Si cleavage is distinct from previously recognised mechanisms for C–H cleavage, with a cascade of silyl intermediates en route to a stable product. The amide directing-groups are involved only in the stabilisation of palladacyclic intermediates, and are never disposed to activate silicon directly. 5-Membered and 6-membered palladacycles are known to behave differently in coupling reactions and the calculations reveal underlying reasons in the cationic pathways studied here.

The land surface model (LSM) described in this manuscript was originally developed as part of the NOAA Rapid Update Cycle (RUC) model development effort; with ongoing modifications, it is now used as an option for the WRF community model. The RUC model and its WRF-based NOAA successor, the Rapid Refresh (RAP), are hourly updated and have an emphasis on short-range, near-surface forecasts including aviation-impact variables and preconvective environment. Therefore, coupling to this LSM (hereafter the RUC LSM) has been critical to provide more accurate lower boundary conditions. This paper describes changes made to the RUC LSM since earlier descriptions, including extension from six to nine levels, improved snow treatment, and new land-use data from MODIS.The RUC LSM became operational at the NOAA/National Centers for Environmental Prediction (NCEP) as part of the RUC from 1998–2012 and as part of the RAP from 2012 through the present. The simple treatments of basic land surface processes in the RUC LSM have proven to be physically robust and capable of realistically representing the evolution of soil moisture, soil temperature, and snow in cycled models. Extension of the RAP domain to encompass all of North America and adjacent high-latitude ocean areas necessitated further development of the RUC LSM for application in the tundra permafrost regions and over Arctic sea ice. Other modifications include refinements in the snow model and a more accurate specification of albedo, roughness length, and other surface properties. These recent modifications in the RUC LSM are described and evaluated in this paper.

The Rapid Refresh (RAP), an hourly updated assimilation and model forecast system, replaced the Rapid Update Cycle (RUC) as an operational regional analysis and forecast system among the suite of models at the NOAA/National Centers for Environmental Prediction (NCEP) in 2012. The need for an effective hourly updated assimilation and modeling system for the United States for situational awareness and related decision-making has continued to increase for various applications including aviation (and transportation in general), severe weather, and energy. The RAP is distinct from the previous RUC in three primary aspects: a larger geographical domain (covering North America), use of the community-based Advanced Research version of the Weather Research and Forecasting (WRF) Model (ARW) replacing the RUC forecast model, and use of the Gridpoint Statistical Interpolation analysis system (GSI) instead of the RUC three-dimensional variational data assimilation (3DVar). As part of the RAP development, modifications have been made to the community ARW model (especially in model physics) and GSI assimilation systems, some based on previous model and assimilation design innovations developed initially with the RUC. Upper-air comparison is included for forecast verification against both rawinsondes and aircraft reports, the latter allowing hourly verification. In general, the RAP produces superior forecasts to those from the RUC, and its skill has continued to increase from 2012 up to RAP version 3 as of 2015. In addition, the RAP can improve on persistence forecasts for the 1–3-h forecast range for surface, upper-air, and ceiling forecasts.

The Rapid Refresh (RAP) and High-Resolution Rapid Refresh (HRRR), both operational at NOAA’s National Centers for Environmental Prediction (NCEP) use the Thompson et al. mixed-phase bulk cloud microphysics scheme. This scheme permits predicted surface precipitation to simultaneously consist of rain, snow, and graupel at the same location under certain conditions. Here, the explicit precipitation-type diagnostic method is described as used in conjunction with the Thompson et al. scheme in the RAP and HRRR models. The postprocessing logic combines the explicitly predicted multispecies hydrometeor data and other information from the model forecasts to produce fields of surface precipitation type that distinguish between rain and freezing rain, and to also portray areas of mixed precipitation. This explicit precipitation-type diagnostic method is used with the NOAA operational RAP and HRRR models. Verification from two winter seasons from 2013 to 2015 is provided against METAR surface observations. An example of this product from a January 2015 south-central United States winter storm is also shown.

C-H activation plays a central role in organometallic catalysis. Concerted metallation-deprotonation (CMD) has been dominant as the pathway for C-H bond cleavage. In the course of studying the mechanism of C-H activation of arylamides and arylureas with Pd complexes as part of catalytic oxidative Heck reactions, DFT calculations were carried out. The turnover-limiting C-H activation is acid-catalysed and can occur readily in the absence of acetate or other coordinating bases. The calculations simulated experiment, so that ligated sulfonate and water, both previously observed by X-ray characterization, were incorporated in the model. A Wheland-type complex between acetanilide and Pd was readily located, but the reactive C-H and the coordinated sulfonate were poorly placed for intramolecular proton transfer. Involvement of a water molecule coordinated to sulfonate provides a low-energy pathway to the palladacycle. The relative reactivity of substituted acetanilides and arylureas according to this model fits well with existing literature. General-base catalysis as described here has broader potential.

Because of limitations of variational and ensemble data assimilation schemes, resulting analysis fields exhibit some noise from imbalance in subsequent model forecasts. Controlling finescale noise is desirable in the NOAA’s Rapid Refresh (RAP) assimilation/forecast system, which uses an hourly data assimilation cycle. Hence, a digital filter initialization (DFI) capability has been introduced into the Weather Research and Forecasting Model and applied operationally in the RAP, for which hourly intermittent assimilation makes DFI essential. A brief overview of the DFI approach, its implementation, and some of its advantages are discussed. Results from a 1-week impact test with and without DFI demonstrate that DFI is effective at reducing high-frequency noise in short-term operational forecasts as well as providing evidence of reduced errors in the 1-h mass and momentum fields. However, DFI is also shown to reduce the strength of parameterized deep moist convection during the first hour of the forecast.

The Mesoscale Predictability Experiment (MPEX) was conducted from 15 May to 15 June 2013 in the central United States. MPEX was motivated by the basic question of whether experimental, subsynoptic observations can extend convective-scale predictability and otherwise enhance skill in short-term regional numerical weather prediction. Observational tools for MPEX included the National Science Foundation (NSF)–National Center for Atmospheric Research (NCAR) Gulfstream V aircraft (GV), which featured the Airborne Vertical Atmospheric Profiling System mini-dropsonde system and a microwave temperature-profiling (MTP) system as well as several ground-based mobile upsonde systems. Basic operations involved two missions per day: an early morning mission with the GV, well upstream of anticipated convective storms, and an afternoon and early evening mission with the mobile sounding units to sample the initiation and upscale feedbacks of the convection. A total of 18 intensive observing periods (IOPs) were completed during the field phase, representing a wide spectrum of synoptic regimes and convective events, including several major severe weather and/or tornado outbreak days. The novel observational strategy employed during MPEX is documented herein, as is the unique role of the ensemble modeling efforts—which included an ensemble sensitivity analysis—to both guide the observational strategies and help address the potential impacts of such enhanced observations on short-term convective forecasting. Preliminary results of retrospective data assimilation experiments are discussed, as are data analyses showing upscale convective feedbacks.

A hydrostatic global weather prediction model based on an icosahedral horizontal grid and a hybrid terrain-following/isentropic vertical coordinate is described. The model is an extension to three spatial dimensions of a previously developed, icosahedral, shallow-water model featuring user-selectable horizontal resolution and employing indirect addressing techniques. The vertical grid is adaptive to maximize the portion of the atmosphere mapped into the isentropic coordinate subdomain. The model, best described as a stacked shallow-water model, is being tested extensively on real-time medium-range forecasts to ready it for possible inclusion in operational multimodel ensembles for medium-range to seasonal prediction.

The nucleophilic reactivity of fluoride ion is altered in the presence of hydrogen-bond donors, including alcohols. Relatively little is known about the coordination involved; to rectify this, the X-ray structures of fourteen novel fluoride–alcohol complexes with tetrabutylammonium as the counterion have been determined. The coordination number varies from two to four depending on the steric bulk of the alcohol and is closely linked to trends in reactivity. This diversity in coordination stoichiometry is unprecedented but significant, as it implies differences in the ability of the fluoride–alcohol complexes to dissociate in solution with release of a more active and/or selective fluoride source.

The need for effective cross-cultural training has been recognized throughout the United States Army, Department of Defense, and the wider business and education community as critical to successful international relationships. However, achieving effective cross-cultural capability training currently requires long-term immersion into foreign culture which is a large investment of both time and resources. This paper will focus on the development of key cultural stress points, analyzed by Hofstede's cultural dimensions, that will provide the cultural groundwork for a computer-based, linguistically-sophisticate, real-world-oriented virtual simulator to achieve the same goals of developing cross-cultural expertise as from long-term immersion but without the same initial investment requirement. This paper will develop the socio-cultural basis for the virtual, computer-based, Chinese-language simulator and will serve as a framework on which similar projects could be undertaken for various other global cultures. By isolating these cultural stress points, the specific aspects of culture that cause conflict between American and Chinese perspectives, this paper will develop socio-cultural content that will make the simulator culturally significant. This research and the associated fieldwork conducted both in mainland China and on Taiwan are broken up into four components. This paper, sequentially, focuses on the relevant cross-cultural competency theories and previous cultural education research, significant historical cultural norms and traditions that are unique to the Chinese-speaking world, and then how these unique aspects of Chinese culture manifest in modern China in both informal and formal interactions. This research, coupled with fieldwork, will isolate cultural stress points between American and Chinese culture and target scenarios in which these stress points are exposed. The end result is the development of Chinese-language dialogue trees of these stress-point exposure, real-world cultural scenarios that can be incorporated into the development and improvement of the virtual simulator.

Hydrogen-bonding with fluoride is a key interaction encountered when analyzing the mode of action of 5'-fluoro-5'-deoxyadenosine synthase, the only known enzyme capable of catalyzing the formation of a C-F bond from F-. Further understanding of the effect of hydrogen-bonding on the structure and reactivity of complexed fluoride is therefore important for catalysis and numerous other applications, such as anion supramolecular chemistry. Herein we disclose a detailed study examining the structure of 18 novel urea-fluoride complexes in the solid state, by X-ray and neutron diffraction, and in solution phase and explore the reactivity of these complexes as a fluoride source in SN2 chemistry. Experimental data show that the structure, coordination strength and reactivity of the urea-fluoride complexes are tunable by modifying substituents on the urea receptor. Hammett analysis of aryl groups on the urea indicates that fluoride bind-ing is dependent on [sigma]p and [sigma]m parameters with stronger binding being observed for electron-deficient urea ligands. For the first time, defined urea-fluoride complexes are used as fluoride-binding reagents for the nucleophilic substitution of a model alkyl bromide. The reaction is slower in comparison with known alcohol-fluoride complexes, but SN2 is largely favored over E2, at a ratio surpassing all hydrogen-bonded complexes documented in the literature for the model alkyl bromide employed. Increased second-order rate constants at higher dilution support the hypothesis that the reactive species is a 1:1 urea-fluoride complex of type [UF]- (U = urea) resulting from partial dissociation of the parent compound [U2F]- . The dissociation processes can be quantified through a combination of UV and NMR assays, including DOSY and HOESY analyses that illuminate the complexation state and H-bonding in solution.

The field of asymmetric hydrogenation grew rapidly after the early 1970s. What had begun as a demonstration of enantioselectivity in catalysis by purely chemical means became an important tool both for academic research and for industry. Right from the beginning, a question was posed as to how relatively simple catalysts were able to generate such unprecedented levels of stereoselectivity. This article provides an account of Oxford-based contributions to the field of rhodium complex catalyzed asymmetric hydrogenation from 1978 onward, when the initial realization of this practical catalytic method for synthesis of single enantiomers had already been achieved. NMR-based experiments that help to elucidate the structures of reactive intermediates in catalysis are strongly emphasized here and linked to the present understanding of the mechanism of a reaction that has sustained interest over the intervening years.

New transcatheter devices are being developed to reduce tricuspid regurgitation (TR) and improve clinical outcomes in selected patients. The FORMA early feasibility study (EFS) was conducted to evaluate the safety and device performance of the FORMA system (Edwards Lifesciences, Irvine, California

Over the past 100 years, the collaborative effort of the international science community, including government weather services and the media, along with the associated proliferation of environmental observations, improved scientific understanding, and growth of technology, has radically transformed weather forecasting into an effective global and regional environmental prediction capability. This chapter traces the evolution of forecasting, starting in 1919 [when the American Meteorological Society (AMS) was founded], over four eras separated by breakpoints at 1939, 1956, and 1985. The current state of forecasting could not have been achieved without essential collaboration within and among countries in pursuing the common weather and Earth-system prediction challenge. AMS itself has had a strong role in enabling this international collaboration.

The laser excitation spectrum of the 327 nm band system of CoCl2, formed in a free-jet expansion, has been recorded at a rotational temperature of approximately 10 K. The spectrum is congested and suffers extensive perturbations. A progression in the excited state symmetric stretching vibration has been identified. The decrease in the symmetric stretching vibrational wave number on excitation is considerable [nu1 '=195.7(12), nu1 (")=358.1(17) cm(-1)]. Despite widespread perturbations in the rotational structure of these vibronic bands, they can be confidently assigned to a parallel Omega=72-72 transition, consistent with an inverted 4Deltag ground electronic state. The rotational constant for Co35Cl2 in the ground state is determined to be 0.056 65(11) cm(-1), which corresponds to a value for the zero-point averaged Co-Cl bond length r0 of 2.062 8(40) A. The perturbations are found to be strongly isotopomer dependent.

Thalidomide comes in two forms: a left-handed compound which is a powerful tranquilizer, and a right-handed version which can disrupt fetal development causing severe handicap. As a necessary consequence of synthetic methods available in the early 1960s the two forms were present in equal proportions in the manufactured drug, with catastrophic consequences. The thalidomide story is perhaps the most painful reminder of the importance of stereochemistry—the spatial ordering of groups in a molecule can be as influential as the chemical nature of the groups themselves. A principal problem in organic synthesis is, therefore, the development of methods for producing complex molecules with a stereochemically defined structure.

A series of racemic or stereochemically labile chiral borate anions based on the 2,2′-biphenol motif was investigated. All borates were homochiral in the solid state, although in some cases the heterochiral diastereomers were computed to be thermodynamically preferred (DFT). The crystallographic preference for the homochiral diastereomer was attributed to its lower bulk, higher molecular symmetry, and the therewith associated better packing ability.

A synthesis of the title phosphinamine (PHENAP) is described, following previously established methodology, Resolution via the C,N-palladocycle derived from ( R )-N,N-dimethyl-α-methyl-1-naphthylamine led to two crystallographically defined complexes with the ( R , S )-form posessing a chelated ligand and the ( R , R )-form open with only the phosphine coordinated. Palladium allyl complexes of the ligand were strikingly different from those of the corresponding isoquinoline ligand QUINAP, and the differences could be rationalised by recourse to molecular models, with the additional fused arene ring of PHENAP playing a critical part in defining the coordination sphere through its steric pressure. A brief appraisal of Pd-catalysed allylic alkylation reactions was performed with the new ligand.

Allyl fluorides are reactive toward Pt-catalyzed alkylation with malonate and likewise toward N- and O-nucleophiles under mild conditions. The reactivity of fluoride as a leaving group equals or exceeds that of the esters and carbonates commonly employed in allylic alkylation. The order of leaving-group ability with Pt catalysts was found to be F ≥ OCO 2Me ≫ OBz ≥ OAc. This discouraged the application of platinum catalysts for the reverse reaction, fluorination of allylic substrates. Fluoride displacement involves predominant or complete retention of configuration in all the observed cases, and this was confirmed as a general feature of Pt catalysis, the stereochemical integrity being as high or higher as in Pd catalysis for the examples chosen. © 2012 American Chemical Society.

Reactive intermediates in the asymmetric Heck reaction between aryl electrophiles and 2,3-dihydrofuran have been identified by NMR and mass spectrometry, with BINAP or the achiral diphosphanes dppp and dppf as ligands. The major cationic species observed is an alkylpalladium produced by addition of PdAr to the alkene followed by two further PdH-mediated isomerisation steps. This last species has been characterised at - 60° by 1H-, 13C-, and 31P-NMR, including HMQC techniques. The regiochemistry of PdAr and PdH addition to the reactant are opposite as defined by the reaction with (2-2H1)-2,3-dihydrofuran. DFT Calculations on the reaction pathway between [CH2(PH2)]PdPh+ and 2,3-dihydrofuran reveal several structurally interesting intermediates involving agostic β-H-atom, ipso-Ph or reactant O-atom bonded to the Pd-atom, and elucidate the isomerisation pathway.

Transcatheter valve implantation in the mitral position with severe calcific mitral stenosis has been described in patients who are at an increased risk for conventional mitral valve surgical procedures. We report the direct deployment of the Sapien 3 valve in the mitral position with severe mitral annular calcification through a sternotomy in an arrested heart in two cases.

Objective The study objective was to determine the effects of implementing a blood conservation algorithm on blood product use and outcomes in a community cardiac surgery program. Methods A blood management strategy including lower hemoglobin transfusion threshold and algorithm-driven decisions was adopted. Intraoperatively, point-of-care testing was used to avoid inappropriate component transfusion. A low prime perfusion circuit was adopted. Blood was withdrawn from patients before initiating bypass when possible. Patients undergoing coronary and valve procedures were included. Outlier patients receiving more than 10 units packed red blood cells were excluded. Data were collected for 6 months as a baseline group (group I). A 3-month period of program implementation was allotted. Data were subsequently collected for 6 months and comprised the study patients (group II). Prospective data were collected on demographics, blood use, and outcomes. Results Group I comprised 481 patients, and group II comprised 551 patients. Group II received fewer units of packed red blood cells, fresh-frozen plasma, and cryoprecipitate than group I. There was no difference in platelets transfused. Total blood product use was reduced by 40% in group II ( P 001). The overall 30-day mortality was 1.3%. There were no differences in mortality, reoperation for bleeding, or other postoperative outcomes between the groups. Conclusions Implementation of a comprehensive blood conservation algorithm can be rapidly introduced, leading to reductions in blood and component use with no detrimental effect on early outcomes. Point-of-care testing can direct component transfusion in coagulopathic cases, with most coagulopathic patients requiring platelets. Further research will determine the effects of reduced transfusions on long-term outcomes.

A method for the preparation of diphosphineruthenium complexes from a range of diphosphine precursors is described. The stable products, of general formula P2Ru(allyl)acac (P = phosphine ligand), do not catalyse the hydrogenation of alkenes but can easily be converted into catalytically active species by reaction with trimethylsilyl trifluoromethanesulfonate. The chemistry involved in this transformation is discussed. Catalysis of the hydrogenation of a range of alkenes, and direct comparison with related rhodium reductions, is described. Some mechanistic insights are gained through additions of D2 to alkenes and parallel hydrogenations on deuterated solvent, supporting the intervention of conventional dihydride and alkyl hydride intermediates which undergo exchange with solvent at both stages.

The conformations of two classes of 7-ring diphosphine metal chelate have been analysed, based on DIOP- or BINAP-type structures. A combination of X-ray analysis, DFT calculations, data analysis based on the CDS structure database and solution NMR studies has been employed. The conformational flexibility of DIOP-type structures has been endorsed, and the scope of BINAP complex flexibility defined. BINAP complexes possess an intrinsic conformational mobility. Analysis of the metal-adjacent torsion angles C-P-M-P′ and C′-P′-M-P provides a useful probe for the ligand-metal environment, and may be more generally useful. © 2010 Elsevier Ltd. All rights reserved.