Carbonates and intermediate-depth seismicity: Stable and unstable shear in altered subducting plates and overlying mantle.

A model for intermediate-depth earthquakes of subduction zones is evaluated based on shear localization, shear heating, and runaway creep within thin carbonate layers in an altered downgoing oceanic plate and the overlying mantle wedge. Thermal shear instabilities in carbonate lenses add to potential mechanisms for intermediate-depth seismicity, which are based on serpentine dehydration and embrittlement of altered slabs or viscous shear instabilities in narrow fine-grained olivine shear zones. Peridotites in subducting plates and the overlying mantle wedge may be altered by reactions with CO2-bearing fluids sourced from seawater or the deep mantle, to form carbonate minerals, in addition to hydrous silicates. Effective viscosities of magnesian carbonates are higher than those for antigorite serpentine and they are markedly lower than those for H2O-saturated olivine. However, magnesian carbonates may extend to greater mantle depths than hydrous silicates at temperatures and pressures of subduction zones. Strain rates within altered downgoing mantle peridotites may be localized within carbonated layers following slab dehydration. A simple model of shear heating and temperature-sensitive creep of carbonate horizons, based on experimentally determined creep laws, predicts conditions of stable and unstable shear with strain rates up to 10/s, comparable to seismic velocities of frictional fault surfaces. Applied to intermediate-depth earthquakes of the Tonga subduction zone and the double Wadati-Benioff zone of NE Japan, this mechanism provides an alternative to the generation of earthquakes by dehydration embrittlement, beyond the stability of antigorite serpentine in subduction zones.

Asmic Isocyanide [3 + 2] Cascade to Dihydrooxazoles and Dihydroimidazoles.

The versatile isocyanide building block Asmic, anisylsulfanylmethylisocyanide, reacts with aldehydes and ketones in a BF3·OEt2-mediated condensation to afford thioimidoyl-substituted 2,5-dihydrooxazoles. The condensation is distinguished from related base and transition-metal-catalyzed [3 + 2] processes in proceeding via the condensation of aldehydes and ketones with 2 equiv of an isocyanide followed by a molecular rearrangement that installs four new bonds. BF3·OEt2 mediates an analogous condensation of Asmic with imines to generate N-substituted dihydroimidazoles. Mechanistically, BF3·OEt2 activates the isocyanide to facilitate deprotonation evolving to a zwitterion that traps π-electrophiles in a formal [3 + 2] process. A second deprotonation-condensation with Asmic initiates a structural rearrangement involving a sulfanyl elimination-addition transposition sequence. The resulting dihydrooxazoles and dihydroimidazoles contain a thioimidate that serves as a diversification point for further elaboration.

Mesoionic pyrido[1,2-a]pyrimidinones: Discovery of triflumezopyrim as a potent hopper insecticide1.

A novel class of mesoionic pyrido[1,2-a]pyrimidinones has been discovered with exceptional insecticidal activity controlling a number of insect species. In this communication, we report the part of the optimization program which led to the discovery of triflumezopyrim as a highly potent insecticide controlling various hopper species. Our efforts in discovery, synthesis, structure-activity relationship elucidation, and biological activity evaluation are also presented.

Mesoionic pyrido[1,2-a]pyrimidinones: Discovery of dicloromezotiaz as a lepidoptera insecticide acting on nicotinic acetylcholine receptors1,2.

A novel class of mesoionic pyrido[1,2-a]pyrimidinones has been discovered with exceptional insecticidal activity controlling a number of insect species. In this communication, we report the part of the optimization program that led to the identification of dicloromezotiaz as a potent insecticide to control a broad range of lepidoptera. Our efforts in discovery, synthesis, structure-activity relationship elucidation, and biological activity evaluation are also presented.

Mesoionic pyrido[1,2-a]pyrimidinones: A novel class of insecticides inhibiting nicotinic acetylcholine receptors.

A novel class of mesoionic pyrido[1,2-a]pyrimidinones has been discovered with exceptional insecticidal activity controlling a number of insect species, particularly hemiptera and lepidoptera. Mode-of-action studies showed that they act on nicotinic acetylcholine receptors (nAChRs) primarily as inhibitors. Here we report the discovery, evolution, and preparation of this class of chemistry. Our efforts in structure-activity relationship elucidation and biological activity evaluation are also presented.

4-Azolylphenyl isoxazoline insecticides acting at the GABA gated chloride channel.

Isoxazoline insecticides have been shown to be potent blockers of insect GABA receptors with excellent activity on a broad pest range, including Lepidoptera and Hemiptera. Herein we report on the synthesis, biological activity and mode-of-action for a class of 4-heterocyclic aryl isoxazoline insecticides.

Stereoselective Synthesis of (E)- and (Z)-Isocyanoalkenes.

(E)- and (Z)-isocyanoalkenes were selectively synthesized via the sequential cross coupling of vinyl iodides with formamide, followed by dehydration. The optimal catalyst, generated in situ from CuII and trans-N,N'-dimethyl-1,2-cyclohexanediamine, rapidly coupled (E)- or (Z)-vinyl iodides with formamide, which minimized the isomerization of the resultant vinyl formamide. The method efficiently provided a range of acyclic, carbocyclic, and heterocyclic isocyanoalkenes; the versatility is illustrated with the selective, stereodivergent syntheses of the diastereomeric isocyanoalkene antibiotics, B371 and E-B371.

A Sectioning, Coring, and Image Processing Guide for High-Throughput Cortical Bone Sample Procurement and Analysis for Synchrotron Micro-CT.

Bone is a dynamic and mechanically active tissue that changes in structure over the human lifespan. The products of the bone remodeling process have been studied substantially using traditional two-dimensional techniques. Recent advancements in X-ray imaging technology via desktop micro-computed tomography (µCT) and synchrotron radiation micro-computed tomography (SRµCT) have allowed for the acquisition of high-resolution three-dimensional (3D) scans of a larger field of view (FOV) than other 3D imaging techniques (e.g., SEM) providing a more complete picture of microscopic structures within human cortical bone. The specimen should be accurately centered within the FOV, however, to limit the appearance of streak artifacts known to impact data analysis. Previous studies have reported procurement of irregularly shaped rectilinear bone blocks that result in imaging artifacts due to uneven edges or image truncation. We have applied a geological sampling protocol (coring) to procure consistently sized cortical bone core specimens for SRµCT experiments from the anterior aspect of human femora. This coring method is efficient and minimally destructive to tissue. It creates uniform cylindrical samples that decrease imaging artifacts by nature of being isometric during rotation and providing a uniform path length for X-ray beams throughout scanning. Image processing of X-ray tomographic data of cored and irregularly shaped samples confirms the potential of the technique to improve visualization and analysis of cortical bone microarchitecture. A goal of this protocol is to deliver a reliable and repeatable method for the extraction of cortical bone cores that is adaptable for various types of high-resolution bone imaging experiments. An overarching goal of the work is to create a standardized cortical bone procurement for SRµCT that is affordable, consistent, and straightforward. This procedure may further be adapted by researchers in related fields who commonly evaluate hard composite materials such as in biological anthropology, geosciences, or material sciences.

Mesoionic insecticides: a novel class of insecticides that modulate nicotinic acetylcholine receptors.

BACKGROUND: As the world population grows towards 9 billion by 2050, it is projected that food production will need to increase by 60%. A critical part of this growth includes the safe and effective use of insecticides to reduce the estimated 20-49% loss of global crop yields owing to pests. The development of new insecticides will help to sustain this protection and overcome insecticide resistance. RESULTS: A novel class of mesoionic compounds has been discovered, with exceptional insecticidal activity on a range of Hemiptera and Lepidoptera. These compounds bind to the orthosteric site of the nicotinic acetylcholine receptor and result in a highly potent inhibitory action at the receptor with minimal agonism. The synthesis, biological activity, optimization and mode of action will be discussed. CONCLUSION: Triflumezopyrim insect control will provide a powerful tool for control of hopper species in rice throughout Asia. Dicloromezotiaz can provide a useful control tool for lepidopteran pests, with an underexploited mode of action among these pests. © 2016 Society of Chemical Industry.

Mode of action of triflumezopyrim: A novel mesoionic insecticide which inhibits the nicotinic acetylcholine receptor.

Triflumezopyrim, a newly commercialized molecule from DuPont Crop Protection, belongs to the novel class of mesoionic insecticides. This study characterizes the biochemical and physiological action of this novel insecticide. Using membranes from the aphid, Myzus persicae, triflumezopyrim was found to displace (3)H-imidacloprid with a Ki value of 43 nM with competitive binding results indicating that triflumezopyrim binds to the orthosteric site of the nicotinic acetylcholine receptor (nAChR). In voltage clamp studies using dissociated Periplaneta americana neurons, triflumezopyrim inhibits nAChR currents with an IC50 of 0.6 nM. Activation of nAChR currents was minimal and required concentrations ≥100 µM. Xenopus oocytes expressing chimeric nAChRs (Drosophila α2/chick ß2) showed similar inhibitory effects from triflumezopyrim. In P. americana neurons, co-application experiments with acetylcholine reveal the inhibitory action of triflumezopyrim to be rapid and prolonged in nature. Such physiological action is distinct from other insecticides in IRAC Group 4 in which the toxicological mode of action is attributed to nAChR agonism. Mesoionic insecticides act via inhibition of the orthosteric binding site of the nAChR despite previous beliefs that such action would translate to poor insect control. Triflumezopyrim is the first commercialized insecticide from this class and provides outstanding control of hoppers, including the brown planthopper, Nilaparvata lugens, which is already displaying strong resistance to neonicotinoids such as imidacloprid.

Axial temperature gradient and stress measurements in the deformation-DIA cell using alumina pistons.

The deformation-DIA apparatus (D-DIA) coupled with synchrotron X-rays allows investigating materials elastic and plastic properties at high pressure. Most D-DIA deformation cells use alumina pistons that can also be used for measurement of the differential stress in the compression column by in situ X-ray diffraction. Here, we quantify the axial temperature (T) gradient in the D-DIA deformation cell and better constrain stress measurements in its compression column by studying an alumina specimen compressed and deformed at pressure P in the range 3.9-5.5 GPa and nominal temperature To = 1673 K. The axial T gradient, obtained from alumina equation of state, is ∼155 K∕mm at the centre of the cell and does not vary significantly during deformation to 20% specimen strain. This T gradient, if not taken into account when measuring the experimental pressure in the alumina pistons, leads to significantly overestimating pressure. Unlike pressure, stress measurements in alumina are weakly sensitive to temperature. During deformation, the "true" differential stress in the compression column is evaluated at 596 ± 20 MPa using an elastoplastic self-consistent model, while raw uncertainties on experimental differential stresses reach 84 MPa. A comparison between the simulated and experimental data allows to conclude that, although dislocation glide in the basal plane is the primary slip system at run condition, with an estimated critical resolved shear stress (CRSS) of 120 MPa, prism plane slips and pyramidal plane slips also contribute significantly to the aggregate homogenous deformation and texture development, with CRSS on the order of 280 MPa.