Dioxygen Reduction by a Pd(0)–Hydroquinone Diphosphine Complex

A novel p-terphenyl diphosphine ligand was synthesized with a noninnocent hydroquinone moiety as the central arene (1-H). Pseudo-tetrahedral 4-coordinate Ni^0 and Pd^0–quinone (2 and 3, respectively) complexes proved accessible by metalating 1-H with the corresponding M(OAc)_2 precursors. O_2 does not react with the Pd^0–quinone species (3) and protonation occurs at the quinone moiety indicating that the coordinated oxidized quinonoid moiety prevents reactivity at the metal. A 2-coordinate Pd^0–hydroquinone complex (4-H) was prepared using a one-pot metalation with Pd^(II) followed by reduction. The reduced quinonoid moiety in 4-H shows metal-coupled reactivity with small molecules. 4-H was capable of reducing a variety of substrates including dioxygen, nitric oxide, nitrous oxide, 1-azido adamantane, trimethylamine n-oxide, and 1,4-benzoquinone quantitatively producing 3 as the Pd-containing reaction product. Mechanistic investigations of dioxygen reduction revealed that the reaction proceeds through a η^2-peroxo intermediate (Int1) at low temperatures followed by subsequent ligand oxidation at higher temperatures in a reaction that consumed half an equivalent of O_2 and produced water as a final oxygenic byproduct. Control compounds with methyl protected phenolic moieties (4-Me), displaying a Ag^I center incapable of O_2 binding (7-H) or a cationic Pd–H motif (6-H) allowed for the independent examination of potential reaction pathways. The reaction of 4-Me with dioxygen at low temperature produces a species (8-Me) analogous to Int1 demonstrating that initial dioxygen activation is an inner sphere Pd-based process where the hydroquinone moiety only subsequently participates in the reduction of O_2, at higher temperatures, by H^+/e^– transfers

Detection of bearing failure in mechanical devices using neural networks

We present a novel time-domain method for the detection of faulty bearings that has direct applicability to monitoring the health of the turbo pumps on the Space Shuttle Main Engine. A feed-forward neural network was trained to detect modelled roller bearing faults on the basis of the periodicity of impact pulse trains. The network's performance was dependent upon the number of pulses in the network's input window and the signal-to-noise ratio of the input signal. To test the model's validity, we fit the model's parameters to an actual vibration signal generated by a faulty roller element bearing and applied the network trained on this model to detect faults in actual vibration data. When this network was tested on the actual vibration data, it correctly identified the vibration signal as a fault condition 76 percent of the time

Bistatic LIDAR experiment proposed for the shuttle/tethered satellite system missions

A new experiment concept has been proposed for the shuttle/tethered satellite system missions, which can provide high resolution, global density mappings of certain ionospheric species. The technique utilizes bistatic LIDAR to take advantage of the unique dual platform configuration offered by these missions. A tuned, shuttle-based laser is used to excite a column of the atmosphere adjacent to the tethered satellite, while triangulating photometic detectors on the satellite are employed to measure the fluorescence from sections of the column. The fluorescent intensity at the detectors is increased about six decades over both ground-based and monostatic shuttle-based LIDAR sounding of the same region. In addition, the orbital motion of the Shuttle provides for quasi-global mapping unattainable with ground-based observations. Since this technique provides such vastly improved resolution on a synoptic scale, many important middle atmospheric studies, heretofore untenable, may soon be addressed

Trinuclear Nickel Complexes with Metal–Arene Interactions Supported by Tris- and Bis(phosphinoaryl)benzene Frameworks

Triphosphine and diphosphine ligands with backbones designed to facilitate metal–arene interactions were employed to support multinuclear Ni complexes. Di- and trinuclear metal complexes supported by a triphosphine containing a triarylbenzene linker display diverse metal–arene binding modes. Multinuclear Ni halide complexes were isolated with strongly interacting metal centers bound to opposite faces of the coordinated arene. Upon reaction of the trinickel diiodide complex 2 with disodium tetracarbonylferrate, a cofacial triangulo nickel(0) complex, 4, was isolated. The Ni^(0)_(3) cluster motif can also be supported by a para-terphenyl diphosphine, where a terminal carbon monoxide ligand replaces the third phosphine donor. All multinuclear complexes feature strong metal–arene interactions, demonstrating the use of an arene as a versatile ligand design element for small clusters

Scaling properties of cavity-enhanced atom cooling

We extend an earlier semiclassical model to describe the dissipative motion of N atoms coupled to M modes inside a coherently driven high-finesse cavity. The description includes momentum diffusion via spontaneous emission and cavity decay. Simple analytical formulas for the steady-state temperature and the cooling time for a single atom are derived and show surprisingly good agreement with direct stochastic simulations of the semiclassical equations for N atoms with properly scaled parameters. A thorough comparison with standard free-space Doppler cooling is performed and yields a lower temperature and a cooling time enhancement by a factor of M times the square of the ratio of the atom-field coupling constant to the cavity decay rate. Finally it is shown that laser cooling with negligible spontaneous emission should indeed be possible, especially for relatively light particles in a strongly coupled field configuration.Comment: 7 pages, 5 figure

Control of posture with FES systems

One of the major obstacles in restoration of functional FES supported standing in paraplegia is the lack of knowledge of a suitable control strategy. The main issue is how to integrate the purposeful actions of the non-paralysed upper body when interacting with the environment while standing, and the actions of the artificial FES control system supporting the paralyzed lower extremities. In this paper we provide a review of our approach to solving this question, which focuses on three inter-related areas: investigations of the basic mechanisms of functional postural responses in neurologically intact subjects; re-training of the residual sensory-motor activities of the upper body in paralyzed individuals; and development of closed-loop FES control systems for support of the paralyzed joints

Trapping and cooling single atoms with far-off resonance intracavity doughnut modes

We investigate cooling and trapping of single atoms inside an optical cavity using a quasi-resonant field and a far-off resonant mode of the Laguerre-Gauss type. The far-off resonant doughnut mode provides an efficient trapping in the case when it shifts the atomic internal ground and excited state in the same way, which is particularly useful for quantum information applications of cavity quantum electrodynamics (QED) systems. Long trapping times can be achieved, as shown by full 3-D simulations of the quasi-classical motion inside the resonator.Comment: 18 pages, 18 figures, RevTe

Cavity cooling of a single atom

All conventional methods to laser-cool atoms rely on repeated cycles of optical pumping and spontaneous emission of a photon by the atom. Spontaneous emission in a random direction is the dissipative mechanism required to remove entropy from the atom. However, alternative cooling methods have been proposed for a single atom strongly coupled to a high-finesse cavity; the role of spontaneous emission is replaced by the escape of a photon from the cavity. Application of such cooling schemes would improve the performance of atom cavity systems for quantum information processing. Furthermore, as cavity cooling does not rely on spontaneous emission, it can be applied to systems that cannot be laser-cooled by conventional methods; these include molecules (which do not have a closed transition) and collective excitations of Bose condensates, which are destroyed by randomly directed recoil kicks. Here we demonstrate cavity cooling of single rubidium atoms stored in an intracavity dipole trap. The cooling mechanism results in extended storage times and improved localization of atoms. We estimate that the observed cooling rate is at least five times larger than that produced by free-space cooling methods, for comparable excitation of the atom