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The selection of optimum sampling configurations to measure the aspects of turbulent flow of water depends on the variable being measured, the applied measurement technique, the degree of e...

Dunes form critical agents of bedload transport in all of the world’s big rivers, and constitute appreciable sources of bed roughness and flow resistance. Dunes also generate stratification that is the most common depositional feature of ancient riverine sediments. However, current models of dune dynamics and stratification are conditioned by bedform geometries observed in small rivers and laboratory experiments. For these dunes, the downstream lee-side is often assumed to be simple in shape and sloping at the angle of repose. Here we show, using a unique compilation of high-resolution bathymetry from a range of large rivers, that dunes are instead characterized predominantly by low-angle lee-side slopes (

International audience; Repeated measures experiments can be conducted to empirically estimate the uncertainty of a stream gauging method, such as the widespread moving‐boat acoustic Doppler current profilers (ADCPs) approach. Previous ADCP repeated measures experiments, also known as interlaboratory comparisons, provided a credible range of uncertainty estimates reflecting the quality of the site conditions. However, the method, which is a one‐way analysis of variance, only addresses the uncertainty of one lumped factor that combines several distinct factors: instrument, operator, procedure, and cross‐section effects. To decompose the uncertainty of ADCP streamflow measurements due to cross‐section selection and team effects, a large repeated measures experiment has been conducted in the Taurion River (France). The experiment design was crossed and balanced, with two sets of 24 teams circulated over two sets of 12 cross sections. A constant flow rate was released from a dam, located immediately upstream of the experimental site. Prior to the statistical analysis, a data quality review was performed using the U.S. Geological Survey QRev software to clean the data set from avoidable errors and to homogenize the discharge computations. A two‐way analysis of variance was applied to quantify the cross‐section effect, the team effect, and their interaction, which was found to dominate the pure cross‐section effect. It was then possible to predict the average uncertainty of multiple‐transect ADCP discharge measurements, depending on the number of teams, cross sections, and repeated transects included in the discharge average. The method opens interesting avenues for documenting difficult‐to‐estimate uncertainty sources of stream gauging techniques in other measuring conditions, especially the most adverse ones.

Intermolecular C-C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent 'ene'-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. This active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.

Records of discharge for the connecting channels within the Great Lakes Basin are important to national governments of Canada and the United States and the various water management agencies...

Quantifying sediment flux within rivers is a challenge for many disciplines due, mainly, to difficulties inherent to traditional sediment sampling methods. These methods are operationally complex, high cost, and high risk. Additionally, the resulting data provide a low spatial and temporal resolution estimate of the total sediment flux, which has impeded advances in the understanding of the hydro-geomorphic characteristics of rivers. Acoustic technologies have been recognized as a leading tool for increasing the resolution of sediment data by relating their echo intensity level measurements to suspended sediment. Further effort is required to robustly test and develop these techniques across a wide range of conditions found in natural river systems. This article aims to evaluate the application of acoustic inversion techniques using commercially available, down-looking acoustic Doppler current profilers (ADCPs) in quantifying suspended sediment in a large sand bed river with varying bi-modal particle size distributions, wash load and suspended-sand ratios, and water stages. To achieve this objective, suspended sediment was physically sampled along the Paraná River, Argentina, under various hydro-sedimentological regimes. Two ADCPs emitting different sound frequencies were used to simultaneously profile echo intensity level within the water column. Using the sonar equation, calibrations were determined between suspended-sand concentrations and acoustic backscatter to solve the inverse problem. The study also analyzed the roles played by each term of the sonar equation, such as ADCP frequency, power supply, instrument constants, and particle size distributions typically found in sand bed rivers, on sediment attenuation and backscatter. Calibrations were successfully developed between corrected backscatter and suspended-sand concentrations for all sites and ADCP frequencies, resulting in mean suspendedsand concentration estimates within about 40% of the mean sampled concentrations. Noise values, calculated using the sonar equation and sediment sample characteristics, were fairly constant across evaluations, suggesting that they could be applied to other sand bed rivers.

A divergent strategy for assembling pyrone diterpenes is presented. Capitalizing on the unique stereo- and chemoselectivity features of radical-based chemistry, the core decalin of these structures is efficiently forged using an electrochemically assisted oxidative radical polycyclization while key peripheral substituents are appended using decarboxylative radical cross couplings. In this way, access to four natural products (subglutinols A/B, higginsianin A, and sesquicillin A) is achieved in a concise and stereocontrolled fashion that is modular and amenable to future medicinal chemistry explorations.

The catalytic desymmetrization of anhydrides with zinc reagents provides access to deoxypolypropionate and polypropionate synthons. A synthesis of ionomycin was pursued in which three of the four fragments were assembled using this methodology. Two of the strategies (enol silane/oxocarbenium coupling and reductive cyclization) were not successful at installing the C23 stereocenter, but this stereochemical issue was overcome through a reduction/SN2 approach. In addition to the synthesis of a protected diastereomer of ionomycin, the synthesis of a C17–C32 fragment constitutes a formal total synthesis.

The theory relating the acoustic backscatter from suspended sediments to the mass concentration of particles has been developed over several decades and is now routinely applied to provide measurements for commercial and scientific applications. Single-beam instruments, such as acoustic Doppler current profilers (ADCP), permit acquisition of backscatter along one-dimensional spatial profiles. However, commercially available multibeam echo-sounders (MBES), designed principally for bathymetric surveying, now offer water column backscatter data-logging across their two-dimensional interrogation swaths, enabling suspended sediment to be instantaneously imaged across much larger volumes. This paper addresses issues relating to the processing of suspended sediment backscatter recorded with an MBES system, drawing on the theory developed for single-beam instruments. A processing methodology is developed and the performance limits estimated from an analysis of the data acquired in the near-field of a Teledyne-RESON MBES in a controlled test facility. Results derived from the application of the methodology to field-data collected with an MBES and an ADCP in the Missouri River, USA, are presented that demonstrate the potential gains in spatial and temporal resolution and near-bed imaging than can be achieved by the use of an MBES system.

1,4-Benzoxazin-3-one is a scaffold which is found in a variety of biologically active molecules. Because of its unique structure and drug-like activities, 1,4-benzoxazin-3-ones have been widely used in drug discovery. However, just a few methods have been developed to access these molecules by catalytic asymmetric synthesis. We report herein the phase-transfer-catalysed asymmetric alkylation of 2-aryl-1,4-benzoxazin-3-ones as a new way for the highly enantioselective synthesis of 2,2-disubstituted 1,4-benzoxazin-3-ones.

The use of sidelooking acoustic Doppler velocity meters (ADVMs) to estimate fluvial suspended-sediment concentrations (SSC) by the U.S. Geological Survey has become more operational in recent years; however, direct transfer of these techniques to downlooking acoustic Doppler current profilers (ADCPs) currently is not feasible. The use of ADCPs to estimate SSC has been investigated by other researchers, but the requirements and limitations of an operational method that could be successfully applied at many locations are not well defined. In order to evaluate the efficacy of using ADCPs of multiple frequencies to estimate SSC, a dataset was collected on the Missouri River at St. Charles, Missouri, in July 2016. The Missouri River dataset is being compared to similar datasets to determine: 1) what factors influence successful use of downlooking ADCPs to estimate SSC, 2) what are the minimum datasets required to develop SSC calibrations, and 3) what modifications are needed to existing methods, instruments, and software tools.

Caution, alkyl acyl azides can rapidly decompose with heat to release large amounts of nitrogen. Care should be taken during handling: do not attempt to convert neat and avoid handling neat.

Pentafluorophenyl triazolium carbenes, widely used in NHC catalysis, can decompose by several mechanisms. Under high concentration conditions, the azolium may undergo a pentafluorophenyl exchange by a proposed SNAr mechanism to give an inactive salt. In the presence of appropriate substrates, cyclization on the ­ortho-position of the arene can occur, also by SNAr. These adducts provide a potential pathway for catalyst decomposition and serve as a caveat to the development of new reactions and catalysts.

The use of acoustic Doppler current profilers (ADCP) for discharge measurements and three-dimensional flow mapping has increased rapidly in recent years and has been primarily driven by advances in acoustic technology and signal processing. Recent research has developed a variety of methods for processing data obtained from a range of ADCP deployments and this paper builds on this progress by describing new software for processing and visualizing ADCP data collected along transects in rivers or other bodies of water. The new utility, the Velocity Mapping Toolbox (VMT), allows rapid processing (vector rotation, projection, averaging and smoothing), visualization (planform and cross-section vector and contouring), and analysis of a range of ADCP-derived datasets. The paper documents the data processing routines in the toolbox and presents a set of diverse examples that demonstrate its capabilities. The toolbox is applicable to the analysis of ADCP data collected in a wide range of aquatic environments and is made available as open-source code along with this publication. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.

This paper presents a model for quantifying the random errors (i.e., variance) of acoustic Doppler current profiler (ADCP) discharge measurements from moving platforms associated with different sampling times. The model focuses on the random processes in the sampled flow field and has been developed using statistical methods that are currently available for the uncertainty analysis of velocity time series. Analysis of field data that were collected using ADCP from moving platforms from three natural rivers of varying sizes and flow conditions shows that, even though the estimate of the integral time scale of the actual turbulent flow field is larger than the sampling interval, the integral time scale of the sampled flow field is in keeping with the sampling interval. Thus, an equation for computing the variance error in discharge measurements associated with different sampling times, assuming uncorrelated flow fields, is appropriate. The approach is used to help define optimal sampling strategies ...

The lake levels in Lake Michigan-Huron have recently fallen to near historical lows, as has the elevation difference between Lake Michigan-Huron compared to Lake Erie. This decline in lake levels has the potential to cause detrimental impacts on the lake ecosystems, together with social and economic impacts on communities in the entire Great Lakes region. Results from past work suggest that morphological changes in the St Clair River, which is the only natural outlet for Lake Michigan-Huron, could be an appreciable factor in the recent trends of lake level decline. A key research question is whether bed erosion within the river has caused an increase in water conveyance, therefore, contributed to the falling lake level. In this paper, a numerical modeling approach with field data is used to investigate the possibility of sediment movement in the St Clair River and assess the likelihood of morphological change under the current flow regime. A two-dimensional numerical model was used to study flow structure, bed shear stress, and sediment mobility/armoring over a range of flow discharges. Boundary conditions for the numerical model were provided by detailed field measurements that included high-resolution bathymetry and three-dimensional flow velocities. The results indicate that, without considering other effects, under the current range of flow conditions, the shear stresses produced by the river flow are too low to transport most of the coarse bed sediment within the reach and are too low to cause substantial bed erosion or bed scour. However, the detailed maps of the bed show mobile bedforms in the upper St Clair River that are indicative of sediment transport. Relatively high shear stresses near a constriction at the upstream end of the river and at channel bends could cause local scour and deposition. Ship-induced propeller wake erosion also is a likely cause of sediment movement in the entire reach. Other factors that may promote sediment movement, such as ice cover and dredging in the lower river, require further investigation. Copyright © 2012 John Wiley & Sons, Ltd.

An enantioselective isomerization of 4-iminocrotonates catalyzed by a rhodium(I)/phosphoramidite complex is described. This reaction uses widely available amines to couple with 4-oxocrotonate to provide a convenient access to a central chiral building block in good yield and high enantioselectivity. Although the mechanism of this new transformation remains unclear, both Rh and the phosphoramidite play a central role.

An integrated multibeam echo sounder and acoustic Doppler current profiler field survey was conducted in July 2008 to investigate the morphodynamics of the St. Clair River at the outlet of Lake Huron. The principal morphological features of the upper St. Clair River included flow-transverse bedforms that appear weakly mobile, erosive bedforms in cohesive muds, thin non-cohesive veneers of weakly mobile sediment that cover an underlying cohesive (till or glacio-lacustrine) surface, and vegetation that covers the bed. The flow was characterized by acceleration as the banks constrict from Lake Huron into the St. Clair River, an approximately 1500-m long region of flow separation downstream from the Blue Water Bridge, and secondary flow connected to: i) channel curvature; ii) forcing of the flow by local bed topography, and iii) flow wakes in the lee side of ship wrecks. Nearshore, sand-sized, sediment from Lake Huron was capable of being transported into, and principally along, the banks of the upper St. Clair River by the measured flow. A comparison of bathymetric surveys conducted in 2007 and 2008 identifies that the gravel bed does undergo slow downstream movement, but that this movement does not appear to be generated by the mean flow, and could possibly be caused by ship-propeller-induced turbulence. The study results suggest that the measured mean flow and dredging within the channel have not produced major scour of the upper St. Clair River and that the recent fall in the level of Lake Huron is unlikely to have been caused by these mechanisms.

Acryloyl and vinyl monomers functionalized with a chiral oxazolidinone auxiliary have been successfully polymerized in a stereospecific fashion to highly isotactic, optically active polymers, through either the previously established isospecific coordination polymerization (for acryloyl monomers) or a novel isospecific cationic polymerization (for vinyl monomers). Specifically, conjugated chiral acryloyloxazolidinones, N-acryloyl-(R or S)-4-phenyl-2-oxazolidinone [(R or S)-AOZ], are readily polymerized by chiral ansa-zirconocenium coordination catalysts, (R,R-, S,S-, or R,R/S,S)-[C2H4(η5-Ind)2]Zr+(THF)[OC(OiPr)═CMe2][MeB(C6F5)3]− (1), in an isospecific manner through a catalyst-site-controlled mechanism, producing the corresponding optically active chiral polymers, (R or S)-PAOZ. Owing to the nature of stereocontrol dictated by the chiral catalyst site, even the coordination polymerization of the parent AOZ, without the chiral side group, also affords PAOZ with nearly quantitative isotacticity. A series o...

The discovery and development of the asymmetric rhodium-catalyzed [2 + 2 + 2] cycloaddition of alkenyl isocyanates and exogenous alkynes to form indolizinone and quinolizinone scaffolds is described. This methodology has been expanded to include substituted alkenes and dienes, a variety of sterically and electronically diverse alkynes, and carbodiimides in place of the isocyanate. Through X-ray analysis of Rh(cod)/phosphoramidite complexes additives that modify the enantio-determining step, and other experimental data, a mechanism has been proposed that explains lactam, vinylogous amide, and pyridone products and the factors governing their formation. Finally, we have applied this methodology to the synthesis of (+)-lasubine II and (–)-209D.

This manuscript describes the development and scope of the asymmetric rhodium-catalyzed [2 + 2 + 2] cycloaddition of terminal alkynes and alkenyl isocyanates leading to the formation of indolizidine and quinolizidine scaffolds. The use of phosphoramidite ligands proved crucial for avoiding competitive terminal alkyne dimerization. Both aliphatic and aromatic terminal alkynes participate well, with product selectivity a function of both the steric and electronic character of the alkyne. Manipulation of the phosphoramidite ligand leads to tuning of enantio- and product selectivity, with a complete turnover in product selectivity seen with aliphatic alkynes when moving from Taddol-based to biphenol-based phosphoramidites. Terminal and 1,1-disubstituted olefins are tolerated with nearly equal efficacy. Examination of a series of competition experiments in combination with analysis of reaction outcome shed considerable light on the operative catalytic cycle. Through a detailed study of a series of X-ray structures of rhodium(cod)chloride/phosphoramidite complexes, we have formulated a mechanistic hypothesis that rationalizes the observed product selectivity.

A highly regioselective rhodium-catalyzed intermolecular [2+2+2] cycloaddition of terminal alkynes with a variety of isocyanates to provide 2- and 4-pyridones has been developed. This reaction proceeds in good to excellent yields and overcomes the problem of dimerization and trimerization through the use of phosphoramidite ligands. A CO migration in the metallacycle is proposed to account for the formation of 4-pyridone.

Bidirectional flows in a river system can occur under stratified flow conditions and in addition to creating significant errors in discharge estimates, the upstream propagating currents are capable of transporting contaminants and affecting water quality. Detailed field observations of bidirectional flows were made in the Chicago River in Chicago, Illinois in the winter of 2005-06. Using multiple acoustic Doppler current profilers simultaneously with a water-quality profiler, the formation of upstream propagating density currents within the Chicago River both as an underflow and an overflow was observed on three occasions. Density differences driving the flow primarily arise from salinity differences between intersecting branches of the Chicago River, whereas water temperature is secondary in the creation of these currents. Deicing salts appear to be the primary source of salinity in the North Branch of the Chicago River, entering the waterway through direct runoff and effluent from a wastewater-treatment plant in a large metropolitan area primarily served by combined sewers. Water-quality assessments of the Chicago River may underestimate (or overestimate) the impairment of the river because standard water-quality monitoring practices do not account for density-driven underflows (or overflows). Chloride concentrations near the riverbed can significantly exceed concentrations at the river surface during underflows indicating that full-depth parameter profiles are necessary for accurate water-quality assessments in urban environments where application of deicing salt is common.

The USGS Office of Surface Water (OSW) previously validated the use of Teledyne RD Instruments (TRDI) Rio Grande (in 2007), StreamPro (in 2006), and Broadband (in 1996) acoustic Doppler current profilers (ADCPs) for streamflow (discharge) measurements made by the USGS. Two new ADCPs, the SonTek M9 and the TRDI RiverRay, were first used in the USGS Water Mission Area programs in 2009. Since 2009, the OSW and USGS Water Science Centers (WSCs) have been conducting field measurements as part of their stream-gauging program using these ADCPs. The purpose of this paper is to document the results of USGS OSW analyses for validation of M9 and RiverRay ADCP streamflow measurements. The OSW required each participating WSC to make comparison measurements over the range of operating conditions in which the instruments were used until sufficient measurements were available. The performance of these ADCPs was evaluated for validation and to identify any present and potential problems. Statistical analyses of st...

The U.S. Geological Survey and other international agencies have collaborated to conduct laboratory and field validations of acoustic Doppler current profiler (ADCP) measurements of streamflow. Laboratory validations made in a large towing basin show that the mean differences between tow cart velocity and ADCP bottom-track and water-track velocities were −0.51 and −1.10% , respectively. Field validations of commercially available ADCPs were conducted by comparing streamflow measurements made with ADCPs to reference streamflow measurements obtained from concurrent mechanical current-meter measurements, stable rating curves, salt-dilution measurements, or acoustic velocity meters. Data from 1,032 transects, comprising 100 discharge measurements, were analyzed from 22 sites in the United States, Canada, Sweden, and The Netherlands. Results of these analyses show that broadband ADCP streamflow measurements are unbiased when compared to the reference discharges regardless of the water mode used for making the ...

To test the ability of acoustic Doppler current profilers (ADCPs) to measure turbulence, profiles measured with two pulse-to-pulse coherent ADCPs in a laboratory flume were compared to profiles measured with an acoustic Doppler velocimeter, and time series measured in the acoustic beam of the ADCPs were examined. A four-beam ADCP was used at a downstream station, while a three-beam ADCP was used at a downstream station and an upstream station. At the downstream station, where the turbulence intensity was low, both ADCPs reproduced the mean velocity profile well away from the flume boundaries; errors near the boundaries were due to transducer ringing, flow disturbance, and sidelobe interference. At the upstream station, where the turbulence intensity was higher, errors in the mean velocity were large. The four-beam ADCP measured the Reynolds stress profile accurately away from the bottom boundary, and these measurements can be used to estimate shear velocity. Estimates of Reynolds stress with a three-beam ADCP and turbulent kinetic energy with both ADCPs cannot be computed without further assumptions, and they are affected by flow inhomogeneity. Neither ADCP measured integral time scales to within 60%.

Acoustic Doppler current profilers (ADCPs) are commonly used to measure streamflow and water velocities in rivers and streams. This paper presents laboratory, field, and numerical model evidence of errors in ADCP measurements caused by flow disturbance. A state-of-the-art three-dimensional computational fluid dynamic model is validated with and used to complement field and laboratory observations of flow disturbance and its effect on measured velocities. Results show that near the instrument, flow velocities measured by the ADCP are neither the undisturbed stream velocity nor the velocity of the flow field around the ADCP. The velocities measured by the ADCP are biased low due to the downward flow near the upstream face of the ADCP and upward recovering flow in the path of downstream transducer, which violate the flow homogeneity assumption used to transform beam velocities into Cartesian velocity components. The magnitude of the bias is dependent on the deployment configuration, the diameter of the instrument, and the approach velocity, and was observed to range from more than 25% at 5 cm from the transducers to less than 1% at about 50 cm from the transducers for the scenarios simulated.

A unique set of observations of stratified flow phenomena in the Chicago River was made using an upward-looking acoustic Doppler current profiler (ADCP) during the period November 20, 2003 to February 1, 2004. Water density differences between the Chicago River and its North Branch (NB) seem to be responsible for the development of gravity currents. With the objective of characterizing the occurrence, frequency, and evolution of such currents, the ADCP was configured to continuously collect high-resolution water velocity and echo intensity profiles in the Chicago River at Columbus Drive. During the observation period, 28 gravity current events were identified, lasting a total of 77% of the time. Sixteen of these events were generated by underflows from the NB and 12 of these events were generated by overflows from the NB. On average, the duration of the underflow and overflow events was 52.3 and 42.1 h , respectively. A detailed analysis of one underflow event, which started on January 7, 2004, and lasted...

A broad spectrum of iminocrotonates bearing N-alkyl substituents is transformed to pyrrolin-2-one structures bearing an 5-alkoxy residue.

For many patients, rectal catheters are an effective means to manage bowel incontinence. Unfortunately, the incidence of catheter leakage in these patients remains troublingly high. Matching the mechanical properties of the catheter and the surrounding tissue may improve the catheter seal and reduce leakage. However, little data is available on the mechanical properties of colorectal tissue. Therefore, our group examined the mechanical properties of colorectal tissue obtained from both a common animal model and humans. Uniaxial tension tests were performed to determine the effects of location, orientation, and species (porcine and human) on bowel tissue tensile mechanical properties. Bowel tissue ultimate strength, elongation at failure, and elastic modulus were derived from these tests and statistically analyzed. Ultimate tensile strength (0.58 MPa, 0.87 MPa), elongation at failure (113.19%, 62.81%), and elastic modulus (1.83 MPa, 5.18 MPa) for porcine and human samples respectively exhibited significant differences based on species. Generally, human tissues were stronger and less compliant than their porcine counterparts. Furthermore, harvest site location and testing orientation significantly affected several mechanical properties in porcine derived tissues, but very few in human tissues. The data suggests that porcine colorectal tissue does not accurately model human colorectal tissue mechanical properties. Ultimately, the tensile properties reported herein may be used to help guide the design of next generation rectal catheters with tissue mimetic properties, as well as aid in the development of physical and computer based bowel models.

Since Breslow's initial report on the thiamine mode of action, the study of catalytic acyl carbanion processes has been an area of immense interest. With the advent of azolylidene catalysis, a plethora of reactivtiy has been harnessed, but the crucial nucleophilic intermediate proposed by Breslow had never been isolated or fully characterized. Herein, we report the isolation and full characterization of nitrogen analogues of the Breslow intermediate. Both stable and catalytically relevant, these species provide a model system for the study of acyl carbanion and homoenolate processes catalyzed by triazolylidene carbenes.

Acoustic Doppler profilers and associated software packages presently are being used to measure water velocity, channel bathymetry, and river discharge. The instruments have various configurations and frequencies; choice of the appropriate instrument depends on various factors including depth, width, and sediment load of the rivers being measured. The acoustic Doppler profilers are mounted on powerboats or small remote-controlled or tethered rafts or catamarans. Profilers enable users to make fast, accurate, and economical discharge measurements on large rivers and rivers with unsteady flow conditions because of flooding or irregular releases from reservoirs. This article describes the principles of operation, application of acoustic Doppler profilers to the measurement of velocity and discharge, and calibration and verification issues.

A [4+2] cycloaddition of α, β-unsaturated imines and isocyanates catalyzed by a phosphoramiditerhodium complex provides pyrimidinones in good yields and high enantioselectivities.

The catalytic asymmetric intermolecular Stetter reaction of heterocyclic aldehydes and nitroalkenes has been developed. We have identified a strong stereoelectronic effect on catalyst structure when a fluorine substituent is placed in the backbone. X-ray structure analysis provides evidence that hyperconjugative effects are responsible for a change in conformation in the azolium precatalyst. This new N-heterocyclic carbene precursor bearing fluorine substitution in the backbone results in significantly improved enantioselectivities across a range of substrates.

Pentafluorophenyl triazolium carbenes, widely used in NHC-catalysis, can decompose by several mechanisms. Under high concentration conditions, the azolium may undergo a pentafluorophenyl exchange by a proposed SNAr mechanism to give an inactive salt. In the presence of appropriate substrates, cyclization on the ortho-position of the arene can occur, also by SNAr. These adducts provide a potential pathway for catalyst decomposition and serve as a caveat to the development of new reactions and catalysts.

[1] This work presents a systematic analysis quantifying the role of the presence of turbulence fluctuations on uncertainties (random errors) of acoustic Doppler current profiler (ADCP) discharge measurements from moving platforms. Data sets of three-dimensional flow velocities with high temporal and spatial resolution were generated from direct numerical simulation (DNS) of turbulent open channel flow. Dimensionless functions relating parameters quantifying the uncertainty in discharge measurements due to flow turbulence (relative variance and relative maximum random error) to sampling configuration were developed from the DNS simulations and then validated with field-scale discharge measurements. The validated functions were used to evaluate the role of the presence of flow turbulence fluctuations on uncertainties in ADCP discharge measurements. The results of this work indicate that random errors due to the flow turbulence are significant when: (a) a low number of transects is used for a discharge measurement, and (b) measurements are made in shallow rivers using high boat velocity (short time for the boat to cross a flow turbulence structure).

The title reaction allows the synthesis of pyrimidinones such as (III) possessing a substitution pattern complementary to that of Biginelli adducts.

The discovery and development of the asymmetric rhodium-catalyzed [2+2+2] cycloaddition of alkenyl isocyanates and exogenous alkynes to form indolizinone and quinolizinone scaffolds is described. This methodology has been expanded to include substituted alkenes and dienes, a variety of sterically and electronically diverse alkynes, and carbodiimides in place of the isocyanate. Through X-ray analysis of Rh(cod)/phosphoramidite complexes, additives that modify the enantio-determining step, and other experimental data, a mechanism has been proposed that explains lactam, vinylogous amide, and pyridone products and the factors governing their formation. Finally, we have applied this methodology to the synthesis of (+)-lasubine-II and (-)-209D.

[1] In order to investigate the interactions between turbulence and suspended sediment transport in natural aqueous environments, we ideally require a technique that allows simultaneous measurement of fluid velocity and sediment concentration for the whole flow field. Here, we report on development of a methodology using the water column acoustic backscatter signal from a multibeam echo sounder to simultaneously quantify flow velocities and sediment concentrations. The application of this new technique is illustrated with reference to flow over the leeside of an alluvial sand dune, which allows, for the first time in a field study, quantitative visualization of large-scale, whole flow field, turbulent coherent flow structures associated with the dune leeside that are responsible for suspending bed sediment. This methodology holds great potential for use in a wide range of aqueous geophysical flows.

The catalytic asymmetric intermolecular Stetter reaction of heterocyclic aldehydes and nitroalkenes has been developed. We have identified a strong stereoelectronic effect on catalyst structure when a fluorine substituent is placed in the backbone. X-ray structure analysis provides evidence that hyperconjugative effects are responsible for a change in conformation in the azolium precatalyst. This new N-heterocyclic carbene precursor bearing fluorine substitution in the backbone results in significantly improved enantioselectivities across a range of substrates.

A highly regioselective rhodium-catalyzed intermolecular [2+2+2] cycloaddition of terminal alkynes with a variety of isocyanates to provide 2- and 4-pyridones has been developed. This reaction proceeds in good to excellent yields and overcomes the problem of dimerization and trimerization through the use of phosphoramidite ligands. A CO migration in the metallacycle is proposed to account for the formation of 4-pyridone.

Synthetic velocity profiles are used to determine guidelines for sampling discharge with acoustic Doppler current profilers (ADCPs). The analysis allows the effects of instrument characteristics, sampling parameters, and properties of the flow to be studied systematically. For mid-section measurements, the averaging time required for a single profile measurement always exceeded the 40 s usually recommended for velocity measurements, and it increased with increasing sample interval and increasing time scale of the large eddies. Similarly, simulations of transect measurements show that discharge error decreases as the number of large eddies sampled increases. The simulations allow sampling criteria that account for the physics of the flow to be developed.