Kinetically-Controlled Ni-Catalyzed Direct Carboxylation of Unactivated Secondary Alkyl Bromides without Chain Walking.

Herein, we report the direct carboxylation of unactivated secondary alkyl bromides enabled by the merger of photoredox and nickel catalysis, a previously inaccessible endeavor in the carboxylation arena. Site-selectivity is dictated by a kinetically controlled insertion of CO2 at the initial C(sp3)-Br site by the rapid formation of Ni(I)-alkyl species, thus avoiding undesired ß-hydride elimination and chain-walking processes. Preliminary mechanistic experiments reveal the subtleties of stereoelectronic effects for guiding the reactivity and site-selectivity.

Spring arrival of the common cuckoo at breeding grounds is strongly determined by environmental conditions in tropical Africa.

Failure to adapt migration timing to changes in environmental conditions along migration routes and at breeding locations can result in mismatches across trophic levels, as occurs between the brood parasitic common cuckoo Cuculus canorus and its hosts. Using satellite tracking data from 87 male cuckoos across 11 years, we evaluate why the cuckoo has not advanced its arrival to the UK. Across years, breeding ground arrival was primarily determined by timing of departure from stopover in West Africa before northward crossing of the Sahara. Together with high population synchrony and low apparent endogenous control of this event, this suggests that a seasonal ecological constraint operating here limits overall variation in breeding grounds arrival, although this event was itself influenced by carry-over from timing of arrival into tropical Africa. Between-year variation within individuals was, in contrast, mostly determined by northward migration through Europe, probably due to weather conditions. We find evidence of increased mortality risk for (a) early birds following migration periods positively impacting breeding grounds arrival, and (b) late birds, possibly suffering energy limitation, after departure from the breeding grounds. These results help identify areas where demands of responding to global change can potentially be alleviated by improving stopover quality.

Ni-Catalyzed Carboxylation of Aziridines en Route to ß-Amino Acids.

A Ni-catalyzed reductive carboxylation of N-substituted aziridines with CO2 at atmospheric pressure is disclosed. The protocol is characterized by its mild conditions, experimental ease, and exquisite chemo- and regioselectivity pattern, thus unlocking a new catalytic blueprint to access ß-amino acids, important building blocks with considerable potential as peptidomimetics.

Reaction of Nitrogen-Radicals with Organometallics Under Ni-Catalysis: N-Arylations and Amino-Functionalization Cascades.

Herein, we report a strategy for the generation of nitrogen-radicals by ground-state single electron transfer with organyl-NiI species. Depending on the philicity of the N-radical, two types of processes have been developed. In the case of nucleophilic aminyl radicals direct N-arylation with aryl organozinc, organoboron, and organosilicon reagents was achieved. In the case of electrophilic amidyl radicals, cascade processes involving intramolecular cyclization, followed by reaction with both aryl and alkyl organometallics have been developed. The N-cyclization-alkylation cascade introduces a novel retrosynthetic disconnection for the assembly of substituted lactams and pyrrolidines with its potential demonstrated in the short total synthesis of four venom alkaloids.

Hydroxylamine Derivatives as Nitrogen-Radical Precursors in Visible-Light Photochemistry.

In recent years, hydroxylamines derivatives have been exploited as nitrogen-radical precursors in visible-light photochemistry. Their ability to serve as electrophores in redox chemistry has propelled the development of many novel transformations. Fundamental mechanistic aspects as well as the importance in the preparation of nitrogen-containing molecules will be highlighted.

Photoredox Imino Functionalizations of Olefins.

Shown herein is that polyfunctionalized nitrogen heterocycles can be easily prepared by a visible-light-mediated radical cascade process. This divergent strategy features the oxidative generation of iminyl radicals and subsequent cyclization/radical trapping, which allows the effective construction of highly functionalized heterocycles. The reactions proceed efficiently at room temperature, utilize an organic photocatalyst, use simple and readily available materials, and generate, in a single step, valuable building blocks that would be difficult to prepare by other methods.

Visible-Light-Mediated Synthesis of Amidyl Radicals: Transition-Metal-Free Hydroamination and N-Arylation Reactions.

The development of photoredox reactions of aryloxy-amides for the generation of amidyl radicals and their use in hydroamination-cyclization and N-arylation reactions is reported. Owing to the ease of single-electron-transfer reduction of the aryloxy-amides, the organic dye eosin Y was used as the photoredox catalyst, which results in fully transition-metal-free processes. These transformations exhibit a broad scope, are tolerant to several important functionalities, and have been used in the late-stage modification of complex and high-value N-containing molecules.

Visible-Light-Mediated Generation of Nitrogen-Centered Radicals: Metal-Free Hydroimination and Iminohydroxylation Cyclization Reactions.

The formation and use of iminyl radicals in novel and divergent hydroimination and iminohydroxylation cyclization reactions has been accomplished through the design of a new class of reactive O-aryl oximes. Owing to their low reduction potentials, the inexpensive organic dye eosin Y could be used as the photocatalyst of the organocatalytic hydroimination reaction. Furthermore, reaction conditions for a unique iminohydroxylation were identified; visible-light-mediated electron transfer from novel electron donor-acceptor complexes of the oximes and Et3N was proposed as a key step of this process.

Estimating the distribution of reedbed in Britain demonstrates challenges of remotely sensing rare land cover types at large spatial scales.

Common Reed Phragmites australis, globally one of the mostly widely distributed wetland plants, is important for biodiversity and for humans. However, like most wetland plant communities, reedbed has rarely been mapped at large geographical scales, restricting the information available to study reed's range dynamics or inform its management. Using Sentinel-2 data and machine learning, we aimed to produce the first published remotely-sensed reedbed map of Britain; however, accuracy as assessed by field validation was relatively low (AUC = 0.671), with many false positives (commission error of 93.4%). A similar workflow carried out in Google Earth Engine, using nearly an order of magnitude more images, gave a lower commission error but a disproportionately higher omission error. Using the known commission and omission error, we estimate that in 2015-2017 ~ 7800 ha of Britain was reedbed. Our study highlights the enduring barriers to accurate land cover classification at large spatial scales. Even with a 'big data' approach, reflectance error and ecological factors such as confusion land cover types and geographical variation in temporal reflectance function will probably continue to limit the size of area for which land cover can be classified accurately, therefore limiting the utility of remote sensing for ecologists.

Balance of activity during a critical period tunes a developing network.

Developing neural circuits are influenced by activity and are especially sensitive to changes in activity during critical periods (CPs) of development. Changes occurring during a CP often become 'locked in' so that they affect the mature network. Indeed, several neurodevelopmental disorders have been linked to excessive activity during such periods. It is, therefore, important to identify those aspects of neural circuit development that are influenced by neural activity during a CP. In this study, we take advantage of the genetic tractability of Drosophila to show that activity perturbation during an embryonic CP permanently alters properties of the locomotor circuit. Specific changes we identify include increased synchronicity of motoneuron activity and greater strengthening of excitatory over inhibitory synaptic drive to motoneurons. These changes are sufficient to reduce network robustness, evidenced by increased sensitivity to induced seizure. We also show that we can rescue these changes when increased activity is mitigated by inhibition provided by mechanosensory neurons. Similarly, we demonstrate a dose-dependent relationship between inhibition experienced during the CP and the extent to which it is possible to rescue the hyperexcitable phenotype characteristic of the parabss mutation. This suggests that developing circuits must be exposed to a properly balanced sum of excitation and inhibition during the CP to achieve normal mature network function. Our results, therefore, provide novel insight into how activity during a CP shapes specific elements of a circuit, and how activity during this period is integrated to tune neural circuits to the environment in which they will likely function.

Flight heights obtained from GPS versus altimeters influence estimates of collision risk with offshore wind turbines in Lesser Black-backed Gulls Larus fuscus.

The risk posed by offshore wind farms to seabirds through collisions with turbine blades is greatly influenced by species-specific flight behaviour. Bird-borne telemetry devices may provide improved measurement of aspects of bird behaviour, notably individual and behaviour specific flight heights. However, use of data from devices that use the GPS or barometric altimeters in the gathering of flight height data is nevertheless constrained by a current lack of understanding of the error and calibration of these methods. Uncertainty remains regarding the degree to which errors associated with these methods can affect recorded flight heights, which may in turn have a significant influence on estimates of collision risk produced by Collision Risk Models (CRMs), which incorporate flight height distribution as an input. Using GPS/barometric altimeter tagged Lesser Black-backed Gulls Larus fuscus from two breeding colonies in the UK, we examine comparative flight heights produced by these devices, and their associated errors. We present a novel method of calibrating barometric altimeters using behaviour characterised from GPS data and open-source modelled atmospheric pressure. We examine the magnitude of difference between offshore flight heights produced from GPS and altimeters, comparing these measurements across sampling schedules, colonies, and years. We found flight heights produced from altimeter data to be significantly, although not consistently, higher than those produced from GPS data. This relationship was sustained across differing sampling schedules of five minutes and of 10 s, and between study colonies. We found the magnitude of difference between GPS and altimeter derived flight heights to also vary between individuals, potentially related to the robustness of calibration factors used. Collision estimates for theoretical wind farms were consequently significantly higher when using flight height distributions generated from barometric altimeters. Improving confidence in telemetry-obtained flight height distributions, which may then be applied to CRMs, requires sources of errors in these measurements to be identified. Our study improves knowledge of the calibration processes for flight height measurements based on telemetry data, with the aim of increasing confidence in their use in future assessments of collision risk and reducing the uncertainty over predicted mortality associated with wind farms.

Ni-catalyzed Reductive Deaminative Arylation at sp3 Carbon Centers.

A Ni-catalyzed reductive deaminative arylation at unactivated sp3 carbon centers is described. This operationally simple and user-friendly protocol exhibits excellent chemoselectivity profile and broad substrate scope, thus complementing existing metal-catalyzed cross-coupling reactions to forge sp3 C-C linkages. These virtues have been assessed in the context of late-stage functionalization, hence providing a strategic advantage to reliably generate structure diversity with amine-containing drugs.

The first calcium-catalysed Nazarov cyclisation.

The first calcium-catalysed Nazarov cyclisation is described. The Ca(NTf2)(PF6) complex is found to be a very active catalyst for 4π electrocyclisations. The remarkable catalytic activity of this complex is attributed to its increased Lewis acidity compared to other Ca complexes. Spectroscopic studies have provided an insight into the chelating interactions between the substrate and the Ca catalyst.

High-temperature (>500°c) wall thickness monitoring using dry-coupled ultrasonic waveguide transducers.

Conventional ultrasonic transducers cannot withstand high temperatures for two main reasons: the piezoelectric elements within them depolarize, and differential thermal expansion of the different materials within a transducer causes them to fail. In this paper, the design of a high-temperature ultrasonic thickness gauge that bypasses these problems is described. The system uses a waveguide to isolate the vulnerable transducer and piezoelectric elements from the high-temperature measurement zone. Use of thin and long waveguides of rectangular cross section allows large temperature gradients to be sustained over short distances without the need for additional cooling equipment. The main problems that had to be addressed were the transmission and reception of ultrasonic waves into and from the testpiece that the waveguides are coupled to, and optimization of the wave propagation along the waveguide itself. It was found that anti-plane shear loading performs best at transmitting and receiving from the surface of a component that is to be inspected. Therefore, a nondispersive guided wave mode in large-aspect-ratio rectangular strips was employed to transmit the anti-plane shear loading from the transducer to the measurement zone. Different joining methods to attach the waveguides to the component were investigated and experiments showed that clamping the waveguides to the component surface gave the best results. The thickness of different plate samples was consistently measured to within less than 0.1 mm. Performance at high temperatures was tested in a furnace at 730°C for 4 weeks without signal degradation. Thicknesses in the range of 3 to 25 mm could be monitored using Hanning windowed tonebursts with 2 MHz center frequency.

The application of synthetic focusing for imaging crack-like defects in pipelines using guided waves.

This paper deals with quantifying the performance of a technique for detection, location, and sizing of circumferential crack-like defects in pipelines using synthetically focused guided waves. The system employs a circumferential array of piezoelectric transducer elements. A torsional probing guided wave is excited using the array, which subsequently interacts with the reflecting features of the pipe, such as defects or weld caps. The recorded backscattered signals are synthetically focused to every point of interest in the pipe wall, to form an image of the reflecting features of the pipe. The defect image amplitude is used to estimate the defect depth, and the full width at half maximum of the defect image circumferential profile is used to estimate the circumferential extent of the defect. The imaging system is tested with data from finite element simulations and from laboratory experiments. It is found that reliable sizing of circumferential cracks in finite element simulations and experiments can be achieved if the circumferential extent of the defect is greater than 1.5 lambda(S), where lambda(S) is the shear wavelength at the frequency of inspection. This result is theoretically valid for any pipe size, any axial defect location, and any inspection frequency. Amplitude gains of around 18 dB over an unfocused system have been observed experimentally in an 8-inch pipe with a 9 dB SNR improvement.