Computing magnetic anisotropy constants of single molecule magnets

We present here a theoretical approach to compute the molecular magnetic anisotropy parameters, D (M) and E (M) for single molecule magnets in any given spin eigenstate of exchange spin Hamiltonian. We first describe a hybrid constant M (S) valence bond (VB) technique of solving spin Hamiltonians employing full spatial and spin symmetry adaptation and we illustrate this technique by solving the exchange Hamiltonian of the Cu6Fe8 system. Treating the anisotropy Hamiltonian as perturbation, we compute the D (M)and E(M) values for various eigenstates of the exchange Hamiltonian. Since, the dipolar contribution to the magnetic anisotropy is negligibly small, we calculate the molecular anisotropy from the single-ion anisotropies of the metal centers. We have studied the variation of D (M) and E(M) by rotating the single-ion anisotropies in the case of Mn12Ac and Fe-8 SMMs in ground and few low-lying excited states of the exchange Hamiltonian. In both the systems, we find that the molecular anisotropy changes drastically when the single-ion anisotropies are rotated. While in Mn12Ac SMM D (M) values depend strongly on the spin of the eigenstate, it is almost independent of the spin of the eigenstate in Fe-8 SMM. We also find that the D (M)value is almost insensitive to the orientation of the anisotropy of the core Mn(IV) ions. The dependence of D (M) on the energy gap between the ground and the excited states in both the systems has also been studied by using different sets of exchange constants.

Comparison of the Radar and Seeker Modes of Pursuer Guidance

This paper compares closed-loop performance of seeker-based and radar-based estimators for surface-to-air interception through 6-degree-of-freedom simulation using proportional navigation guidance.Ground radar measurements are evader range, azimuth and elevation angles contaminated by Gaussian noise. Onboard seeker measurements are pursuer-evader relative range, range rate also contaminated by Gaussian noise. The gimbal angles and line-of-sight rates in the gimbal frame,contaminated by time-correlated non-Gaussian noise with realistic numerical values are also available as measurements. In both the applications, extended Kalman filter with Gaussian noise assumption are used for state estimation. For a typical engagement, it is found that,based on Monte Carlo studies, seeker estimator outperforms radar estimator in terms of autopilot demand and reduces the miss distance.Thus, a seeker estimator with white Gaussian assumption is found to be adequate to handle the measurements even in the presence of non-Gaussian correlated noise. This paper uses realistic numerical values of all noise parameters.

Observation of Peierls transition in nanowires (diameter similar to 130 nm) of the charge transfer molecule TTF-TCNQ synthesized by electric-field-directed growth

We report the growth of nanowires of the charge transfer complex tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) with diameters as low as 130 nm and show that such nanowires can show Peierls transitions at low temperatures. The wires of sub-micron length were grown between two prefabricated electrodes (with sub-micron gap) by vapor phase growth from a single source by applying an electric field between the electrodes during the growth process. The nanowires so grown show a charge transfer ratio similar to 0.57, which is close to that seen in bulk crystals. Below the transition the transport is strongly nonlinear and can be interpreted as originating from de-pinning of CDW that forms at the Peierls transition.

A Nonlinear Approach for Re-entry Guidance of Reusable Launch Vehicles Using Model Predictive Static Programming

A nonlinear suboptimal guidance scheme is developed for the reentry phase of the reusable launch vehicles. A recently developed methodology, named as model predictive static programming (MPSP), is implemented which combines the philosophies of nonlinear model predictive control theory and approximate dynamic programming. This technique provides a finite time nonlinear suboptimal guidance law which leads to a rapid solution of the guidance history update. It does not have to suffer from computational difficulties and can be implemented online. The system dynamics is propagated through the flight corridor to the end of the reentry phase considering energy as independent variable and angle of attack as the active control variable. All the terminal constraints are satisfied. Among the path constraints, the normal load is found to be very constrictive. Hence, an extra effort has been made to keep the normal load within a specified limit and monitoring its sensitivity to the perturbation.

Capturability analysis of a geometric guidance law in relative velocity space

In this paper, a relative velocity approach is used to analyze the capturability of a geometric guidance law. Point mass models are assumed for both the missile and the target. The speeds of the missile and target are assumed to remain constant throughout the engagement. Lateral acceleration, obtained from the guidance law, is applied to change the path of the missile. The kinematic equations for engagements in the horizontal plane are derived in the relative velocity space. Some analytical results for the capture region are obtained for non-maneuvering and maneuvering targets. For non-maneuvering targets it is enough for the navigation gain to be a constant to intercept the target, while for maneuvering targets a time varying navigation gain is needed for interception. These results are then verified through numerical simulations.

Promoting and providing expert guidance in work-intensive clinical settings

This paper discusses how expert guidance can be best provided in work intensive clinical settings. The adequacy for supporting learning in the clinical practicum for health care disciplines is often complicated by the intensive work practices in healthcare settings. Often, clinicians' work is so intense that the scope for providing close guidance for students is quite restricted. The case advanced here draws on a range of empirical work to propose how clinician-student interactions might be optimized through the provision of a clinical ccn guided learning such as demonstrating and role-modeling. These roles can contribute in essential ways to the development of learning environments where clinicians have the opportunity to facilitate the learning of others as part of their workload, and without being burdened by the requirements of teaching and assessment processes. It differs from other approaches because although clinicians partner students and provide feedback to them, clinicians are not expected to formally assess or award a grade for student performance. Assessment and remedial action, when required, is undertaken by the role of a designated clinical supervisor qualified to perform such activities. © 2010 Springer Science+Business Media B.V.

Specific Small-Molecule Activator of Aurora Kinase A Induces Autophosphorylation in a Cell-Free System

Aurora kinases are essential for chromosomal segregation and cell division and thereby important for maintaining the proper genomic integrity. There are three classes of aurora kinases in humans: A, B, and C. Aurora kinase A is frequently overexpressed in various cancers. The link of the overexpression and tumorigenesis is yet to be understood. By employing virtual screening, we have found that anacardic acid, a pentadecane aliphatic chain containing hydroxylcarboxylic acid, from cashew nut shell liquid could be docked in Aurora kinases A and B. Remarkably, we found that anacardic acid could potently activate the Aurora kinase A mediated phosphorylation of histone H3, but at a similar concentration the activity of aurora kinase B remained unaffected in vitro. Mechanistically, anacardic acid induces the structural changes and also the autophosphorylation of the aurora kinase A to enhance the enzyme activity. This data thus indicate anacardic acid as the first small-molecule activator of Aurora kinase, which could be highly useful for probing the function of hyperactive (overexpressed) Aurora kinase A.

Stabilization of an All-Metal Antiaromatic Molecule (Al4Li4) Using BH and C as Caps

It has been reported by Pati et al. (J. Am. Chem. Soc. 2005, 127, 3496) that coordination with a transition metal can stabilize the “antiaromatic”, all-metal compound Al4Li4. Here, we report that it can also be stabilized by capping with a main group element like C and its isoelectronic species BH. Our calculations of binding energy, nuclear independent chemical shift, energy decomposition analysis, and molecular orbital analysis support the capping-induced stability, reduction of bond length alternation, and increase of aromaticity of these BH/C-capped Al4Li4 systems. The interaction between px and py orbitals of BH/C and the HOMO and LUMO of Al4Li4 is responsible for the stabilization. Our calculations suggest that capping can introduce fluxionality at room temperature.

Understanding the folding process of synthetic polymers by small-molecule folding agents

Two acceptor containing polyimides PDI and NDI carrying pyromellitic diimide units and 1,4,5,8-naphthalene tetracarboxy diimide units, respectively, along with hexa(oxyethylene) (EO6) segments as linkers, were prepared from the corresponding dianhydrides and diamines. These polyimides were made to fold by interaction with specifically designed folding agents containing a dialkoxynaphtha-lene (DAN) donor linked to a carboxylic acid group. The alkali-metal counter-ion of the donor carboxylic acid upon complexation with the EO6 segment brings the DAN unit in the right location to induce a charge-transfer complex formation with acceptor units in the polymer backbone. This two-point interaction between the folding agent and the polymer backbone leads to a folding of the polymer chain, which was readily monitored by NMR titrations. The effect of various parameters, such as structures of the folding agent and polymer, and the solvent composition, on the folding propensities of the polymer was studied.

Observation of a power-law memory kernel for fluctuations within a single protein molecule

The fluctuation of the distance between a fluorescein-tyrosine pair within a single protein complex was directly monitored in real time by photoinduced electron transfer and found to be a stationary, time-reversible, and non-Markovian Gaussian process. Within the generalized Langevin equation formalism, we experimentally determine the memory kernel K(t), which is proportional to the autocorrelation function of the random fluctuating force. K(t) is a power-law decay, t(-0.51 +/- 0.07) in a broad range of time scales (10(-3)-10 s). Such a long-time memory effect could have implications for protein functions.

Performance Analysis of Guidance Laws Based on Timescale Gap

An analytical treatment of performance analysis of guidance laws is possible only in simplistic scenarios. As the complexity of the guidance system increases, a search for analytical solutions becomes quite impractical. In this paper, a new performance measure, based upon the notion of a timescale gap that can be computed through numerical simulations, is developed for performance analysis of guidance laws. Finite time Lyapunov exponents are used to define the timescale gap. It is shown that the timescale gap can be used for quantification of the rate of convergence of trajectories to the collision course. Comparisonbetween several guidance laws, based on the timescale gap, is presented. Realistic simulations to study the effect of aerodynamicsand atmospheric variations on the timescale gap of these guidance laws are also presented.

Structure of the hydrogen-bonded water molecule in crystals

A correlation of the structural data on IS hydrates obtained by x-ray diffraction, neutron diffraction, and proton magnetic resonance reveals that when a water molecule is hydrogen bonded into a crystal structure and the angle subtended at the donor water oxygen by the acceptor atoms deviates from the vapor H-O-H angle, bent hydrogen bonds are formed in preference to distortion of the H-O-H angle. Theoretical justification for this result is obtained from energy considerations by calculating the energy of formation of bent hydrogen bonds on the basis of the Lippincott-Schroeder potential function model for the hydrogen bond and the energy of deformation of the H-O-H angle from spectroscopic force constants.

Time Scale Separated Nonlinear Partial Integrated Guidance and Control of Interceptors in the Terminal Phase

The paper proposes a time scale separated partial integrated guidance and control of an interceptor for engaging high speed targets in the terminal phase. In this two loop design, the outer loop is an optimal control formulation based on nonlinear model predictive spread control philosophies. It gives the commanded pitch and yaw rates whereas necessary roll-rate command is generated from a roll-stabilization loop. The inner loop tracks the outer loop commands using the dynamicinversion philosophy. However, unlike conventional designs, in both the loops the Six degree of freedom (Six-DOF) interceptor model is used directly. This intelligent manipulation preserves the inherent time scale separation property between the translational and rotational dynamics, and hence overcomes the deficiency of current IGC designs, while preserving its benefits. Six-DOF simulation studies have been carried out accounting for three dimensional engagement geometry. Different comparison studies were also conducted to measure the performance of the algorithm.