Galvanic Vestibular Reduction Modifies Perception of Coriolis Cross-Coupling and Delays Motion Sickness Onset
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G N Pradhan↗
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Photoenzymatic Csp 3 –Csp 3 bond formation via enzyme-templated radical–radical coupling
Cross-couplings are essential reactions in modern chemical synthesis, enabling the rapid construction of complex molecules from simple precursors. Transition metal catalysts are prized for these transformations because their reactivity and selectivity can be tuned via judicious selection of the metal and ligand. Although enzymes offer analogous opportunities for tuning via protein engineering, their application to cross-coupling remains limited, as nature relies on alternative paradigms for building molecular complexity. Here, we report the cross-coupling of alkyl halides and benzylic carboxylic acids using an engineered flavin-dependent lactate monooxygenase—a photoenzyme. The enzyme achieves this feat by exploiting the redox versatility of the flavin cofactor. Stoichiometric experiments, ultrafast spectroscopy, and computational studies support a mechanism in which photoexcited flavin quinone initiates the reaction via oxidative decarboxylation to generate a benzylic radical. The resulting flavin semiquinone can reduce the alkyl halide to form a second organic radical within the protein active site, which rapidly engages in C(sp 3 )–C(sp 3 ) bond formation. A variant was engineered to control the stereochemical outcome of this radical–radical coupling event, highlighting the ability of the protein to alter the energetic barrier for a mechanistic step that is traditionally understood to be near barrierless. This work demonstrates that the scope for nonnative reaction mechanisms in biocatalysis far exceeds previously established bounds and has potential to solve a variety of reactivity challenges in cross-coupling chemistry.
biocatalysis↗
Comparison of Hirs' equation of Moody's equation for determining rotordynamic coefficients of annular pressure seals
The rotordynamic coefficients of an incompressible-flow annular pressure seal were determined using a bulk-flow model in conjunction with two different friction factor relationships. The first, Hirs' equation, assumes the friction factor is a function of Reynolds number only. The second, Moody's equation, approximates Moody's diagram and assumes the friction factor is a function of both Reynolds number and relative roughness. For each value of relative roughness, Hirs' constants were determined so that both equations gave the same magnitude and slope of the friction factor. For smooth seals, both relationships give the same results. For rough seals (e/2 H sub 0 = 0.05) Moody's equation predicts 44% greater direct stiffness, 35% greater cross-coupled stiffness, 19% smaller cross-coupled damping, 59% smaller cross-coupled inertia, and nominally the same direct damping and direct inertia.
Nelson, Clayton C.↗
Comparison of Hirs' equation with Moody's equation for determining rotordynamic coefficients of annular pressure seals
The rotordynamic coefficients of an incompressible-flow annular pressure seal were determined using a bulk-flow model in conjunction with two different friction factor relationships. The first, Hirs' equation, assumes the friction factor is a function of Reynolds number only. The second, Moody's equation, approximates Moody's diagram and assumes the friction factor is a function of both Reynolds number and relative roughness. For each value of relative roughness, Hirs' constants were determined so that both equations gave the same magnitude and slope of the friction factor. For smooth seals, both relationships give the same results. For rough seals, Moody's equation predicts 44 percent greater direct stiffness, 35 percent greater cross-coupled stiffness, 19 percent smaller cross-coupled damping, 59 percent smaller cross-coupled inertia, and nominally the same direct damping and direct inertia.
Nelson, C. C.↗
Theoretical approach to obtaining dynamic characteristics of noncontacting spiral-grooved seals
The dynamic characteristics of spiral-grooved seals are theoretically obtained by using the Navier-Stokes equation. First, with the inertia term of the fluid considered, the flow and pressure in the steady state are obtained for the directions parallel to and perpendicular to the groove. Next, the dynamic character is obtained by analyzing the steady state and by analyzing the labyrinth seal. As a result, the following conclusions were drawn: (1) As the land width becomes shorter or the helix angle decreases, the cross-coupling stiffness, direct and cross-coupling damping, and add mass coefficients decrease; (2) As the axial Reynolds number increases, the stiffness and damping coefficients increase. But the add mass coefficient is not influenced by the axial Reynolds number; (3) The rotational Reynolds number influences greatly the direct and cross-coupling stiffness and direct damping coefficients; and (4) As the journal rotating frequency increases, the leakage flow decreases. Therefore zero net leakage flow is possible at a particular rotating frequency.
Iwatsubo, Takuzo↗
Bulky Phosphine Ligands Promote Palladium-Catalyzed Protodeboronation
The Suzuki-Miyaura cross-coupling reaction is plagued by protodeboronation, an undesirable side reaction with water that consumes the boronic acid derivatives required for the cross-coupling reaction. Meticulous mechanistic studies have previously established protodeboronation to be highly sensitive to the nature of the boronic reagent and reaction conditions. Particularly, the presence of bases, which are essential for the Suzuki-Miyaura coupling, is known to catalyze protodeboronation. However, protodeboronation catalyzed by palladium-phosphine complexes, the benchmark catalyst system for Suzuki-Miyaura cross-coupling, has been understudied compared to its base-catalyzed counterpart. Here, we demonstrate, using automated high-throughput experimentation, comprehensive computational mechanistic analyses and kinetic modeling, that protodeboronation is accelerated by palladium(II) complexes bound to bulky phosphine ligands. While sterically hindered ligands are typically used to facilitate difficult cross-couplings, these ligands can instead paradoxically impede cross-coupling product formation, requiring careful and judicious consideration when choosing ligands for Suzuki-Miyaura cross-couplings.
Ser, Cher Tian [University of Toronto, ON (Canada)↗
A four-axis hand controller for helicopter flight control
A proof-of-concept hand controller for controlling lateral and longitudinal cyclic pitch, collective pitch and tail rotor thrust was developed. The purpose of the work was to address problems of operator fatigue, poor proprioceptive feedback and cross-coupling of axes associated with many four-axis controller designs. The present design is an attempt to reduce cross-coupling to a level that can be controlled with breakout force, rather than to eliminate it entirely. The cascaded design placed lateral and longitudinal cyclic in their normal configuration. Tail rotor thrust was placed atop the cyclic controller. A left/right twisting motion with the wrist made the control input. The axis of rotation was canted outboard (clockwise) to minimize cross-coupling with the cyclic pitch axis. The collective control was a twist grip, like a motorcycle throttle. Measurement of the amount of cross-coupling involved in pure, single-axis inputs showed cross coupling under 10 percent of full deflection for all axes. This small amount of cross-coupling could be further reduced with better damping and force gradient control. Fatigue was not found to be a problem, and proprioceptive feedback was adequate for all flight tasks executed.
Demaio, Joe↗
Effect of structural compliance-induced cross- axis coupling on the stability of a two-axis thrust vector attitude control system.
Structural compliance induced cross axis coupling effect on gimballing system stability of rocket engine two-axis attitude TVC system
GIMBALLED CONTROL↗
On aerodynamic coupling between lateral and longitudinal degrees of freedom
An oscillatory technique for routine measurement of all the direct, cross and cross-coupling moment derivatives due to pitching and yawing has been developed and a series of comprehensive results at Mach numbers 0.7 and 0.25 and at angles of attack up to 40 deg has been obtained in a large wind tunnel. It was found that some of the dynamic cross-coupling derivatives, that at low angles of attack were all zero, at higher angles of attack could reach values that rendered the pertinent cross-coupling terms in the equations of motion comparable in magnitude to the well-established damping terms. Large nonlinear variations with angle of attack were observed in many of the measured derivatives including the important damping-in-pitch and damping-in-yaw derivatives. It was concluded that it may be desirable to include some dynamic cross-coupling derivatives, and the functional variation with angle of attack of many derivatives, in the equations of motion, and to consider all these equations simultaneously, rather than in separate longitudinal and lateral groups.
Orlik-Rueckemann, K. J.↗
Ultrafast population and structural dynamics of a Ni-bipyridine photoredox catalyst reveal a significant deactivation pathway
The ultrafast excited state pathways and dynamics of NiII-bipyridine complexes influence the yield of photochemical processes involved in their catalytic cross-coupling reactions. Here we present ultrafast Ni K x-ray emission spectroscopy (XES) and x-ray solution scattering (XSS) of a NiII-bipyridine aryl halide complex, [Ni(t-Bubpy)(o-tol)Br], to quantify the excited state population dynamics and structural changes of the pre-catalyst. Due to the local spin-sensitivity of XES, the population dynamics of metal-to-ligand charge transfer (MLCT) and metal-centered (MC) excited states is established. A rapid ground state recovery pathway is newly identified, representing a significant deactivation pathway during photocatalysis. Furthermore, the pseudotetrahedral structure of the long-lived MC excited state is unambiguously identified and refined by XSS. The results advance our understanding of the ultrafast relaxation mechanisms that impact the photocatalytic mechanism and yield for NiII-bipyridine aryl halide cross-coupling catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Directional abnormalities of vestibular and optokinetic responses in cerebellar disease
Directional abnormalities of vestibular and optokinetic responses in patients with cerebellar degeneration are reported. Three-axis magnetic search-coil recordings of the eye and head were performed in eight cerebellar patients. Among these patients, examples of directional cross-coupling were found during (1) high-frequency, high-acceleration head thrusts; (2) constant-velocity chair rotations with the head fixed; (3) constant-velocity optokinetic stimulation; and (4) following repetitive head shaking. Cross-coupling during horizontal head thrusts consisted of an inappropriate upward eye-velocity component. In some patients, sustained constant-velocity yaw-axis chair rotations produced a mixed horizontal-torsional nystagmus and/or an increase in the baseline vertical slow-phase velocity. Following horizontal head shaking, some patients showed an increase in the slow-phase velocity of their downbeat nystagmus. These various forms of cross-coupling did not necessarily occur to the same degree in a given patient; this suggests that different mechanisms may be responsible. It is suggested that cross-coupling during head thrusts may reflect a loss of calibration of brainstem connections involved in the direct vestibular pathways, perhaps due to dysfunction of the flocculus. Cross-coupling during constant-velocity rotations and following head shaking may result from a misorientation of the angular eye-velocity vector in the velocity-storage system. Finally, responses to horizontal optokinetic stimulation included an inappropriate torsional component in some patients. This suggests that the underlying organization of horizontal optokinetic tracking is in labyrinthine coordinates. The findings are also consistent with prior animal-lesion studies that have shown a role for the vestibulocerebellum in the control of the direction of the VOR.
NASA Discipline Neuroscience↗
Susceptibility of the squirrel monkey to different motion conditions
The exact stimulus eliciting vomiting in animal studies of motion sickness is difficult to specify because the vestibular stimulation produced by many motion conditions is confounded by voluntary movements with animals. This is an important problem because experiments with animal models of motion sickness can provide useful information about antimotion sickness drugs or the role of neural mechanisms, only when animals are exposed to the same motion stimuli in each experimental session. A series of tests were conducted to determine the susceptibility of 15 adult squirrel monkeys to motion sickness in freely moving and restrained test conditions. Canal stimulation was varied by exposing the monkey in freely moving conditions to varying degrees of angular velocity (60, 90, 120, 150 deg/sec), and in restrained conditions to one angular velocity (150 deg/sec) and to cross-coupling effects of whole-body roll movements during rotation. Otolith stimulation was investigated by using sinusoidal vertical linear acceleration during free movement conditions, and off-vertical rotation and earth-horizontal (BBQ) rotation while restrained. The percentage of freely moving animal vomiting during vertical axis rotation was 27, 93, 86, and 92 for the angular velocities of 60, 90, 120, and 150 deg/sec respectively. None of the monkeys vomited during vertical axis rotation or cross-coupled rotation when restrained. Otolith stimulation appears to be a less provocative stimulus for the squirrel monkey as the percentage of animals vomiting were 13, 0, and 7 for the conditions of free movement during oscillation, restraint during off-vertical, and BBQ rotation respectively. Motion sickness to the point of vomiting occurred regularly only in conditions where self-motion was possible. Such effects could occur because voluntary movement during motion augments vestibular effects by producing self-inflicted cross-coupling, but the failure to elicit vomiting with experimenter-coupling cross-coupling argues against this interpretation. Alternatively, these results might imply that feedback from movement control mechanisms may play an important role in sensory conflict as suggested by Oman's sensory-motor conflict theory.
R A Fox↗
Illuminating the Role of Alcohol Substrate in Nickel Photoredox Catalysis via Ground State and Transient Absorption Spectroscopy
Direct excitation of nickel photocatalysts has gained popularity over the last several years following the successful activation of nickel by Ir and Ru photosensitizers. The ability to pair these photosensitizers with Ni catalysts facilitates the formation of crucial chemical bonds under relatively mild conditions. However, there are still gaps in our understanding of what influences the performance of these Ni photocatalysts. Previous work from our group identified a nickel photocatalyst supported by a tridentate pyridinophane ligand that undergoes wavelength-dependent cross-coupling reactivity. Herein, we report detailed studies of the wavelength dependence of the C–O cross-coupling reactivity, illustrating that the catalytic activity has an optimal wavelength, and excitation on both the blue and red sides of this optimal wavelength leads to a reduction in product yield. We also reveal a crucial catalyst-alcohol preirradiation interaction that drastically alters the catalyst’s optical properties. Furthermore, we investigate both wavelength dependency and alcohol dependency via optical transient absorption spectroscopy and reveal a substrate binding process responsible for the observed wavelength-dependent cross-coupling catalysis.
alcohol↗
SSME Long-life Bearings
Hybrid hydrostatic/ball bearings for LH2 and LO2 service in turbopumps were studied as a means of improving speed and life capabilities. Four hybrid bearing configurations were designed with emphasis on achieving maximum stiffness and damping. Parallel load bearings were tested at steady-state and transient conditions with LH2 (externally fed) and LN2 (internally fed). The hydrostatic elements were tested with Freon 113 for empirical determination of dynamic characteristics. Tests using an eccentric journal for loading showed the externally and internally fed hydrostatic bearings to have significant separated coefficients of direct stiffness and damping. For the internally fed bearing, the strongly speed-dependent cross-coupling stiffness arising from fluid swirl, along with significant cross-coupling damping, resulted in low net effective stiffness and damping. The test method used can produce separated coefficients with a sufficiently elliptic journal orbit; otherwise, only net effective coefficients combining direct and cross-coupling terms can be determined. Testing with nonsynchronous excitation is recommended to avoid this restriction. Investigation of hard materials, including ceramics, is recommended as a means of eliminating the need for the rolling bearing for startup and shutdown support. The testing was performed in 1984 (LH2), 1985 (LN2) and 1985-86 (Freon).
Butner, M. F.↗
Reconceptualizing the Ir III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor
Dual Ir III /L n Ni II metallaphotoredox catalyzed C(sp 3 )–C(sp 2 ) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir III * excited state (Ir III = [Ir(dF(CF 3 )ppy) 2 (dtbbpy)] + [PF 6 ] – ; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir III * and various LnNi II precatalysts and intermediates with k q ≥ 10 8 M –1 s –1 also drives catalysis. Specifically, the excited states of L n Ni II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir III *. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L n Ni II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir III , direct excitation of L n Ni II (Br) 2 also activates the precatalyst to form a L n Ni II (Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br – (k SET = 4.1 × 10 8 M –1 s –1 ) and for the subsequent electron transfer from reduced Ir III•– to L n Ni II (Br) 2 (k SET = 4.1 × 10 7 M –1 s –1 ) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L n Ni II (Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp 3 )–C(sp 2 ) cross-coupled product. Similarly, energy transfer rather than Ni II oxidation drives C(sp 2 )–OR reductive elimination, despite the strongly oxidizing ability of Ir III *. In total, these reactions demonstrate energy transfer processes from Ir III * to L n Ni II in metallaphotoredox catalysis that can unlock alternative reactive pathways.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Reconfigurable Control with Neural Network Augmentation for a Modified F-15 Aircraft
This paper describes the performance of a simplified dynamic inversion controller with neural network supplementation. This 6 DOF (Degree-of-Freedom) simulation study focuses on the results with and without adaptation of neural networks using a simulation of the NASA modified F-15 which has canards. One area of interest is the performance of a simulated surface failure while attempting to minimize the inertial cross coupling effect of a [B] matrix failure (a control derivative anomaly associated with a jammed or missing control surface). Another area of interest and presented is simulated aerodynamic failures ([A] matrix) such as a canard failure. The controller uses explicit models to produce desired angular rate commands. The dynamic inversion calculates the necessary surface commands to achieve the desired rates. The simplified dynamic inversion uses approximate short period and roll axis dynamics. Initial results indicated that the transient response for a [B] matrix failure using a Neural Network (NN) improved the control behavior when compared to not using a neural network for a given failure, However, further evaluation of the controller was comparable, with objections io the cross coupling effects (after changes were made to the controller). This paper describes the methods employed to reduce the cross coupling effect and maintain adequate tracking errors. The IA] matrix failure results show that control of the aircraft without adaptation is more difficult [leas damped) than with active neural networks, Simulation results show Neural Network augmentation of the controller improves performance in terms of backing error and cross coupling reduction and improved performance with aerodynamic-type failures.
Burken, John J.↗
Spatial orientation of the vestibular system
1. A simplified three-dimensional state space model of visual vestibular interaction was formulated. Matrix and dynamical system operators representing coupling from the semicircular canals and the visual system to the velocity storage integrator were incorporated into the model. 2. It was postulated that the system matrix for a tilted position was a composition of two linear transformations of the system matrix for the upright position. One transformation modifies the eigenvalues of the system matrix while another rotates the pitch and roll eigenvectors with the head, while maintaining the yaw axis eigenvector approximately spatially invariant. Using this representation, the response characteristics of the pitch, roll, and yaw eye velocity were obtained in terms of the eigenvalues and associated eigenvectors. 3. Using OKAN data obtained from monkeys and comparing to the model predictions, the eigenvalues and eigenvectors of the system matrix were identified as a function of tilt to the side or of tilt to the prone positions, using a modification of the Marquardt algorithm. The yaw eigenvector for right-side-down tilt and for downward pitch cross-coupling was approximately 30 degrees from the spatial vertical. For the prone position, the eigenvector was computed to be approximately 20 degrees relative to the spatial vertical. For both side-down and prone positions, oblique OKN induced along eigenvector directions generated OKAN which decayed to zero along a straight line with approximately a single time constant. This was verified by a spectral analysis of the residual sequence about the straight line fit to the decaying data. The residual sequence was associated with a narrow autocorrelation function and a wide power spectrum. 4. Parameters found using the Marquardt algorithm were incorporated into the model. Diagonal matrices in a head coordinate frame were introduced to represent the direct pathway and the coupling of the visual system to the integrator. Model simulations predicted the behavior of yaw and pitch OKN and OKAN when the animal was upright, as well as the cross-coupling in the tilted position. The trajectories in velocity space were also accurately simulated. 5. There were similarities between the monkey eigenvectors and human perception of the spatial vertical. For side-down tilts and downward eye velocity cross-coupling, there was only an Aubert (A) effect. For upward eye velocity cross-coupling there were both Muller (E) and Aubert (A) effects. The mean of the eigenvectors for upward and downward eye velocities overlay human 1 x g perceptual data.(ABSTRACT TRUNCATED AT 400 WORDS).
NASA Discipline Neuroscience↗
K-band Cross-Aperture Coupled Circularly Polarized Dual Frequency Microstrip Patch Antenna with Single Feed
The paper presents the design, modeling, simulation, and characterization of a K-band cross-aperture coupled CP microstrip patch antenna element with a single feed for dual frequency operation. The patch element can be used as a building block for a larger planar array for SATCOM (SATellite COMmunications).
Satellite Communications↗