Synthesis of macrocyclic diacyl/dialkyl glycerols containing disulfide tether and studies of their effects upon incorporation in DPPC membranes. Implications in the design of phospholipase A(2) modulators

A general method for the preparation of novel disulfide-tethered macrocyclic diacylglycerols (DAGs) has been described. Overall synthesis involved stepwise protection, acylation, and deprotection to yield the bis(omega-bromoacyl) glycerols. In the crucial macrocyclization step, a unique reagent, benzyltriethylammonium tetrathiomolybdate (BTAT), has been used to convert individual bis(omega-bromoacyl) glycerols to their respective macrocyclic disulfides. DAG 6, which had ether linkages between hydrocarbon chains and the glycerol backbone, was also synthesized from an appropriate precursor using a similar protocol. One of the DAGs (DAG 5) had a carbon-carbon tether instead of a disulfide one and was synthesized using modified Glaser coupling. Preparation of alpha-disulfide-tethered DAG (DAG 4) required an alternative method, as treatment of the bisbromo precursor with BTAT gave a mixture of several compounds from which separation of the target molecule was cumbersome. To avoid this problem, the bisbromide was converted to its corresponding dithiocyanate, which on further treatment with BTAT yielded the desired DAG (DAG 4) in good yield. Upon treatment with the reducing agent dithiothreitol (DTT), the DAGs that contain a disulfide tether could be quantitatively converted to their "open-chain" thiol analogues. These macrocyclic DAGs and their reduced "open-chain" analogues have been incorporated in DPPC vesicles to study their effect on model membranes. Upon incorporation of DAG 1 in DPPC vesicles, formation of new isotropic phases was observed by P-31 NMR, These isotropic phases disappeared completely on opening the macrocyclic ring by a reducing agent. The thermotropic properties of DPPC bilayers having DAGs (1-6) incorporated at various concentrations were studied by differential scanning calorimetry. Incorporation of DAGs in general reduced the cooperativity unit (CU) of the vesicles. Similar experiments with reduced "open-chain" DAGs incorporated in a DPPC bilayer indicated a recovery of CU with respect to their macrocyclic "disulfide" counterparts. The effect of inclusion of these DAGs on the activity of phospholipase A(2) (PLA(2)) was studied in vitro. Incorporation of DAC 1 in DPPC membranes potentiated both bee venom and cobra venom PLA(2) activities.

Hill Instability Analysis Of Tlp Tether Subjected To Combined Platform Surge And Heave Motions

This paper presents the Hill instability analysis of Tension Leg Platform (TLP) tether it, deep sea. The 2-D nonlinear beam model which is Undergoing Coupled axial and transverse vibrations, is applied. The governing equations are reduced to nonlinear Hill equation by use of the Galerkin's method and the modes superposition principle. The Hill instability charted Lip to large parameters is obtained. An important parameter M is defined and can he expressed as the functions of tether length, the platform surge and heave motion amplitudes. Some example studies are performed for various environmental conditions. The results demonstrate that the nonlinear coupling between the axial and transverse vibrations has a significant effect on the response of structure.. It needs to be considered for the accurate dynamic analysis of long TLP tether subjected to the combined platform surge and heave motions.

Nonlinear Dynamic Responses of the Tensioned Tether under Parametric Excitations

The nonlinear dynamic responses of the tensioned tether subjected to combined surge and heave motions of floating platform are investigated using 2-D nonlinear beam model. It is shown that if the transverse-axial coupling of nonlinear beam model and the combined surge-heave motions of platform are considered, the governing equation is not Mathieu equation any more, it becomes nonlinear Hill equation. The Hill stability chart is obtained by using the Hill's infinite determinant and harmonic balance method. A parameter M, which is the function of tether length, the surge and heave amplitude of platform, is defined. The Hill stability chart is obviously different from Mathieu stability chart which is the specific case as M=0. Some case studies are performed by employing linear and nonlinear beam model respectively. It can be found that the results differences between nonlinear and linear model are apparent.

Nonlinear Dynamic Responses of Tension Leg Platform with Slack-Taut Tether

The slack-taut state of tether is a particular Averse circumstance, which may influence the normal operation stale of tension leg platform (TLP). The dynamic responses of TLP with slack-taut tether are studied with consideration of several nonlinear factors introduced by large amplitude motions. The time histories of stresses of tethers of a typical TLP in slack-taut state are given. In addition, the sensitivities of slack to stiffness and mass are investigated by varying file stiffness of tether and mass of TLP. It is found that slack is sensitive to the mass of TLP. The critical culled surfaces (over which indicates the slack) for the increase of mass are obtained.

Quantification of the benefits of a streamlined tether for a high-altitude-tethered balloon

A high-altitude tethered balloon (HATB) reaching a height of 20 km has numerous applications including communications, meteorological monitoring, surveillance and, for the current paper, geoengineering. The HATB configuration consists of a 20 km tether rising up from the ground through the troposphere, where the wind-regime can be turbulent and include high-wind velocities due to the jet-stream, up into the more stable stratosphere where the tether would be attached to a spherical balloon. This paper evaluates wind-excited vibration of a HATB and will investigate the advantages of using a streamlined instead of a circular tether profile. Streamlining the tether reduces drag but introduces stability problems and complicates the numerical modelling. Consequently, prior to a thorough investigation of the stability issues due to fluid-structure interaction, a 3D nonlinear lumped-mass HATB model is used to quantify the benefit of a streamlined tether. The benefit is quantified by comparing the system specifications - such as balloon size and the tension in the tether - required to meet certain design requirements driven by the Stratospheric Particle Injection for Climate Engineering (SPICE) project. The SPICE project is investigating the feasibility of climate engineering using a HATB.

Alkene-arene meta photocycloadditions with a four-carbon-atom tether: efficient approach toward the polycyclic ring systems of aphidicolin and stemodinone

At the end of its tether! The fusion of a six-membered ring onto the four-carbon-atom tether of substrate 1 provides an efficient approach toward the polycyclic ring systems of the natural products aphidicolin and stemodinone. The reaction represents a unique example of a preference for product formation from an endo exciplex in an intramolecular system (exo:endo 2:3=1.0:1.2).

Artificial auroral effects from a bare conducting tether

An electrically floating metallic bare tether in a low Earth orbit would be highly negative with respect to the ambient plasma over most of its length, and would be bombarded by ambient ions.This would liberates secondary electrons which after acceleration through the same voltage, would form a magnetically guided two-sided planar e beam,and result in auroral effects(ionization and light emission)upon impacto on the atmospheric E layer, at about 120-140 km altitude.This papere examines in a preliminary way the feasibility of using this effecet as an uppeart atmospheric probe. Ionization rate can reach up to 10 3 cm 3 S -1 if a tape, instead of a wire, is used as tether. Contrary to standard e beams,the beam from the tether is free of spacecrafct charging and plasma interaction problems and its energy flux varies across the crosss ection,w hich is quite large;this would make possible continuous observation from the satellite, with high resolution both spectral and vertical, of the induced optical emissions. Ground observation might be possible at latitudes around 40ø , for night, magnetically quiet conditions.

Bare-tether cathodic contact through thermoionic emission by low work-function materials

A new material, C12A7 : electride, which might present a work function as low as 0.6 eV and moderately high temperature stability, was recently proposed as coating for floating bare tethers. Arising from heating under space operation, current is emitted by thermionic emission along a thus coated cathodic segment. A preliminary study on the space-charge-limited (SCL) double layer in front of the cathodic segment is presented using Langmuir’s SCL electron current between cylindrical electrodes and orbital-motion-limited ion-collection sheath. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects and the transition from SCL to full Richardson-Dushman emission included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission leads to a short cathodic section and may eliminate the need for an active cathodic device and its corresponding gas feed requirements and power subsystem, which results in a truly “propellant-less” tether system for such basic applications as de-orbiting low earth orbit satellites.

Bare-tether sheath and current: comparison of asymptotic theory and kinetic simulations in stationary plasma

Analytical expressions for current to a cylindrical Langmuir probe at rest in unmagnetized plasma are compared with results from both steady-state Vlasov and particle-in-cell simulations. Probe bias potentials that are much greater than plasma temperature (assumed equal for ions and electrons), as of interest for bare conductive tethers, are considered. At a very high bias, both the electric potential and the attracted-species density exhibit complex radial profiles; in particular, the density exhibits a minimum well within the plasma sheath and a maximum closer to the probe. Excellent agreement is found between analytical and numerical results for values of the probe radiusR close to the maximum radius Rmax for orbital-motion-limited (OML) collection at a particular bias in the following number of profile features: the values and positions of density minimum and maximum, position of sheath boundary, and value of a radius characterizing the no-space-charge behavior of a potential near the high-bias probe. Good agreement between the theory and simulations is also found for parametric laws jointly covering the following three characteristic R ranges: sheath radius versus probe radius and bias for Rmax; density minimum versus probe bias for Rmax; and (weakly bias-dependent) current drop below the OML value versus the probe radius for R > Rmax.

Electrodynamic Tether at Jupiter I: Capture operation and constraints

Tethered spacecraft missions to the Jovian system suit the use of electrodynamic tethers because: 1) magnetic stresses are 100 times greater than at the Earth; 2) the stationary orbit is one-third the relative distance for Earth; and 3) moon Io is a nearby giant plasma source. The (bare) tether is a reinforced aluminum foil with tens of kilometer length L and a fraction of millimeter thickness h, which collects electrons as an efficient Langmuir probe and can tap Jupiter’s rotational energy for both propulsion and power. In this paper, the critical capture operation is explicitly formulated in terms of orbit geometry and established magnetic and thermal plasma models. The design parameters L and h and capture perijove radius rp face opposite criteria independent of tape width. Efficient capture requires a low rp and a high L 3/2/h ratio. However, combined bounds on tether bowing and tether tensile stress, arising from a spin made necessary by the low Jovian gravity gradient, require a high rp and a low L 5/2/h ratio. Bounds on tether temperature again require a high rp and a low L 3/8/(tether emissivity)1/4 ratio. Optimal design values are discussed.

Electrodynamic tether at Jupiter II:Fast moon tour after capture

An electrodynamic bare-tether mission to Jupiter,following the capture of a spacecraft (SC) into an equatorial highly elliptical orbit with perijove at about 1.3 times the Jovian radius, is discussed. Repeated applications of the propellantless Lorentz drag on a spinning tether, at the perijove vicinity, can progressively lower the apojove at constant perijove, for a tour of Galilean moons. Electrical energy is generated and stored as the SC moves from an orbit at 1 : 1 resonance with a moon, down to resonance with the next moon; switching tether current off, stored power is then used as the SC makes a number of flybys of each moon. Radiation dose is calculated throughout the mission,during capture, flybys and moves between moons. The tour mission is limited by both power needs and accumulated dose. The three-stage apojove lowering down to Ganymede, Io, and Europa resonances would total less than 14 weeks, while 4 Ganymede, 20 Europa, and 16 Io flybys would add up to 18 weeks, with the entire mission taking just over seven months and the accumulated radiation dose keeping under 3 Mrad (Si) at 10-mm Al shield thickness.

A proposed two-stage two-tether scientific mission at Jupiter

A two-stage mission to place a spacecraft (SC) below the Jovian radiation belts, using a spinning bare tether with plasma contactors at both ends to provide propulsion and power,is proposed. Capture by Lorentz drag on the tether, at the periapsis of a barely hyperbolic equatorial orbit, is followed by a sequence of orbits at near-constant periapsis, drag finally bringing the SC down to a circular orbit below the halo ring. Although increasing both tether heating and bowing, retrograde motion can substantially reduce accumulated dose as compared with prograde motion, at equal tether-to-SC mass ratio. In the second stage,the tether is cut to a segment one order of magnitude smaller, with a single plasma contactor, making the SC to slowly spiral inward over severalmonths while generating large onboard power, which would allow multiple scientific applications, including in situ study of Jovian grains, auroral sounding of upper atmosphere, and space- and time-resolved observations of surface and subsurface.

Low work-function coating for an entirely propellantless bare electrodynamic tether

We present the possibility of a low work-function material, calcium aluminate electride, being used for a coating on a bare electrodynamic tether system. Analyses suggest that the coating would eliminate the need for an active cathodic device like a hollow cathode and, consequently, eliminate the need for an expellant to the hollow cathode, thus resulting in an electrodynamic tether system that requires no consumables. Applications include on-orbit power generation and deorbiting debris from low Earth orbit in a simple and trouble-free manner.