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At least 55 records · Page 3

Polyimidazoles via aromatic nucleophilic displacement

Polyimidazoles (PI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethyl acetamide, sulfolane, N-methylpyrrolidinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl) imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxphenyl) imidazole monomer. This synthetic route has provided high molecular weight PI of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

Connell, John W.↗

Distributed intelligence for ground/space systems

DI is short for Distributed Intelligence for Ground/Space Systems and the DI Study is one in a series of ESA projects concerned with the development of new concepts and architectures for future autonomous spacecraft systems. The kick-off of DI was in January 1994 and the planned duration is three years. The background of DI is the desire to design future ground/space systems with a higher degree of autonomy than seen in today's missions. The aim of introducing autonomy in spacecraft systems is to: (1) lift the role of the spacecraft operators from routine work and basic troubleshooting to supervision; (2) ease access to and increase availability of spacecraft resources; (3) carry out basic mission planning for users; (4) enable missions which have not yet been feasible due to eg. propagation delays, insufficient ground station coverage etc.; and (5) possibly reduce mission cost. The study serves to identify the feasibility of using state-of-the-art technologies in the area of planning, scheduling, fault detection using model-based diagnosis and knowledge processing to obtain a higher level of autonomy in ground/space systems.

Aarup, Mads↗

Dissociative Ionization of Pyridine by Electron Impact

In order to understand the damage of biomolecules by electrons, a process important in radiation damage, we undertake a study of the dissociative ionization (DI) of pyridine (C5H5N) from the low-lying ionization channels. The methodology used is the same as in the benzene study. While no experimental DI data are available, we compare the dissociation products from our calculations with the dissociative photoionization measurements of Tixier et al. using dipole (e, e(+) ion) coincidence spectroscopy. Comparisons with the DI of benzene is also made so as to understand the difference in DI between a heterocyclic and an aromatic molecule.

Dateo, Christopher↗

Isocyanate Cross-Linked Silica: Structurally Strong Aerogels

Molecular-level synergism between the silica nanoparticles of pre-formed monoliths and molecular cross-linkers inverts the relative host-guest roles in glass-polymer composites, leading to new strong low-density materials. Attempts to load gels with variable amounts of polyurethane precursors such as di-ISO and diol end-capped polybutylene adipate followed by heat treatment, washing, and supercritical drying led to opaque materials, somewhat stronger than silica but still quite brittle and much inferior to the materials described above. Direct mixing of a diisocyanate and an alcohol-free sol has been attempted recently by Yim et al. Reportedly, that procedure leads to week-long gelation times and requires an at least equally long aging period. In our attempt to add various amounts of di-ISO in a base-catalyzed sol in PC, we also noticed a week-long gelation time. The resulting aerogels were translucent but no less brittle than native silica. According to more recent studies, if propylene carbonate is replaced with acetone, it leads not only to shorter processing times, but also to much stronger gels that can tolerate loads in excess of 40 kg in the arrangement presented. We attribute that behavior to the lower viscosity of acetone, that allows faster diffusion of the di-ISO solution within the pores before di-ISO has time to react with the surface of silica. Further studies are underway to vary the chemical identity of the diisocyanate, as well as the composition and density of silica.

Leventis, Nicholas↗

Luminous Binary Supersoft X-Ray Sources

We have made remarkable progress in the study of luminous supersoft X-ray sources during the past year. We have begun to discover a population of ultraluminous SSSs (e.g., in NGC 300 [Kong & Di Stefano 20031 as well as in Ml0l [Di Stefano & Kong 2003]), which may be accreting intermediate-mass (50-100 solar mass) black holes. This work follows from an algorithm we have developed (Di Stefano & Kong 2003) to identify SSSs in external galaxies, selecting them from among each galaxy s total population of X-ray sources. We have applied the algorithm to approximately one dozen galaxies and will make it public after it has been published in its entirety. Through our own application of the algorithm, we have discovered SSSs in every galaxy, mapping their spatial distribution, to obtain important clues to their fundamental natures. We have discovered that there is a large population of X-ray sources which are slightly hotter (100-250 eV) than standard SSSs. Some of these may be accreting BHs with masses between roughly 50 anf 100 solar masses. To explore this possibility, we are working on theoretical models for the formation and evolution of such systems (Di Stefano 2003).

Oliversen, Ronald J.↗

Kinematic Characteristics of the Posture Corrective Responses After 6 Hours Exposure to Support Withdrawal Environment

Posture disorders are an inevitable consequence of exposure to microgravity . However, the role of different sensorimotor and sensory factors on postural function at different stages of the exposure to microgravity still remains unknown. The results obtained in a 6 hr dry immersion (DI) study where chest pushes served as a pre- and post-immersion perturbation, and DI was used as an analog of microgravity suggest that in addition to vestibular contributions, postural control may be related to a reduction of support loading and consequent decline of the tone of anti-gravitational muscles. Analysis of postural video data in response to chest pushes obtained before and after DI indicate that the structure of corrective responses was modified so that postural perturbations from threshold to moderate pushes showed a significant rise in the amplitude of ankle and knee angular displacement. With push intensity near the submaximal level, equilibrium was maintained by the elimination of excessive degrees of freedom; as manifested by the restriction of the hip joints mobility when coupled with a reduction of the knee and ankle displacement. These results suggest that DI increases the sensitivity of the posture control system by making posture control more rigid reflecting a change of the weight bearing receptors.

Sayenko D.↗

Polyimidazoles via aromatic nucleophilic displacement

Polyimidazoles (Pl) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethylacetamide, sulfolane, N-methylpyrroldinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperature under nitrogen. The di(hydroxyphenyl)imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl)imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxyphenyl)imidazole monomer. This synthetic route has provided high molecular weight Pl of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

Connell, John W.↗

Does the Hall Effect Solve the Flux Pileup Saturation Problem?

It is well known that magnetic flux pileup can significantly speed up the rate of magnetic reconnection in high Lundquist number resistive MHD,allowing reconnection to proceed at a rate which is insensitive to the plasma resistivity over a wide range of Lundquist number. Hence, pileup is a possible solution to the Sweet-Parker time scale problem. Unfortunately, pileup tends to saturate above a critical value of the Lundquist number, S_c, where the value ofS_c depends on initial and boundary conditions, with Sweet-Parker scaling returning above S_c. It has been argued (see Dorelli and Bim [2003] and Dorelli [2003]) that the Hall effect can allow flux pileup to saturate (when the scale of the current sheet approaches ion inertial scale, di) before the reconnection rate begins to stall. However, the resulting saturated reconnection rate, while insensitive to the plasma resistivity, was found to depend strongly on the di. In this presentation, we revisit the problem of magnetic island coalescence (which is a well known example of flux pileup reconnection), addressing the dependence of the maximum coalescence rate on the ratio of di in the "large island" limit in which the following inequality is always satisfied: l_eta di lambda, where I_eta is the resistive diffusion length and lambda is the island wavelength.

Dorelli, John C.↗

Physics-Based Methods of Failure Analysis and Diagnostics in Human Space Flight

The Integrated Health Management (IHM) for the future aerospace systems requires to interface models of multiple subsystems in an efficient and accurate information environment at the earlier stages of system design. The complexity of modern aeronautic and aircraft systems (including e.g. the power distribution, flight control, solid and liquid motors) dictates employment of hybrid models and high-level reasoners for analysing mixed continuous and discrete information flow involving multiple modes of operation in uncertain environments, unknown state variables, heterogeneous software and hardware components. To provide the information link between key design/performance parameters and high-level reasoners we rely on development of multi-physics performance models, distributed sensors networks, and fault diagnostic and prognostic (FD&P) technologies in close collaboration with system designers. The main challenges of our research are related to the in-flight assessment of the structural stability, engine performance, and trajectory control. The main goal is to develop an intelligent IHM that not only enhances components and system reliability, but also provides a post-flight feedback helping to optimize design of the next generation of aerospace systems. Our efforts are concentrated on several directions of the research. One of the key components of our strategy is an innovative approach to the diagnostics/prognostics based on the real time dynamical inference (DI) technologies extended to encompass hybrid systems with hidden state trajectories. The major investments are into the multiphysics performance modelling that provides an access of the FD&P technologies to the main performance parameters of e.g. solid and liquid rocket motors and composite materials of the nozzle and case. Some of the recent results of our research are discussed in this chapter. We begin by introducing the problem of dynamical inference of stochastic nonlinear models and reviewing earlier results. Next, we present our analytical approach to the solution of this problem based on the path integral formulation. The resulting algorithm does not require an extensive global search for the model parameters, provides optimal compensation for the effects of dynamical noise, and is robust for a broad range of dynamical models. In the following Section the strengths of the algorithm are illustrated illustrated by inferring the parameters of the stochastic Lorenz system and comparing the results with those of earlier research. Next, we discuss a number of recent results in application to the development of the IHM for aerospace system. Firstly, we apply dynamical inference approach to a solution of classical three tank problems with mixed unknown continuous and binary parameters. The problem is considered in the context of ground support system for filling fuel tanks of liquid rocket motors. It is shown that the DI algorithm is well suited for successful solution of a hybrid version of this benchmark problem even in the presence of additional periodic and stochastic perturbation of unknown strength. Secondly, we illustrate our approach by its application to an analysis of the nozzle fault in a solid rocket motor (SRM). The internal ballistics of the SRM is modelled as a set of one-dimensional partial differential equations coupled to the dynamics of the propellant regression. In this example we are specifically focussed on the inference of discrete and continuous parameters of the nozzle blocking fault and on the possibility of an application of the DI algorithm to reducing the probability of "misses" of an on-board FD&P for SRM. In the next section re-contact problem caused by first stage/upper stage separation failure is discussed. The reaction forces imposed on the nozzle of the upper stage during the re-contact and their connection to the nozzle damage and to the thrust vector control (TVC) signal are obtained. It is shown that transient impact induced torquean be modelled as a response of an effective damped oscillator. A possible application of the DI algorithm to the inference of damage parameters and predicting fault dynamics ahead of time using the actuator signal is discussed. Finally, we formulate Bayesian inferential framework for development of the IHM system for in-flight structural health monitoring (SHM) of composite materials. We consider the signal generated by piezoelectric actuator mounted on composite structure generating elastic waves in it. The signal received by the sensor is than compared with the baseline signal. The possibility of damage inference is discussed in the context of development of the SHM.

Smelyanskiy, Vadim N.↗

Property Differencing for Incremental Checking

This paper introduces iProperty, a novel approach that facilitates incremental checking of programs based on a property di erencing technique. Speci cally, iProperty aims to reduce the cost of checking properties as they are initially developed and as they co-evolve with the program. The key novelty of iProperty is to compute the di erences between the new and old versions of expected properties to reduce the number and size of the properties that need to be checked during the initial development of the properties. Furthermore, property di erencing is used in synergy with program behavior di erencing techniques to optimize common regression scenarios, such as detecting regression errors or checking feature additions for conformance to new expected properties. Experimental results in the context of symbolic execution of Java programs annotated with properties written as assertions show the e ectiveness of iProperty in utilizing change information to enable more ecient checking.

Yang, Guowei↗

Poly(N-arylenbenzimidazoles) via aromatic nucleophilic displacement

Novel poly(N-arylenebenzimidazole)s (PNABIs) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl N-arylenebenzimidazole) monomers are synthesized by reacting phenyl 4-hydroxybenzoate with bis(2-aminoanilino) arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyl N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

Connell, John W.↗

Thermal Rearrangements of Polybutadienes with Different Vinyl Contents

A study was made of the loss of double bonds in equibinary (1,4-1,2) polybutadiene (EB) and in polybutadienes with 30% 1,2, 70% 1,4 (FI), and 10% 1,2, 90% 1,4 (DI) double-bond content, when heated in vacuum under nonpyrolitic conditions (temperature range 220-280 C). These polymers were found to undergo second-order loss of 1,2 unsaturation with similar activation energies (E(sub a) = 34.0 +/- 3 kcal/mole), by analogy to the previously reported thermally induced loss of double bonds in 1,2-polybutadiene (VB) (E(sub a) = 33.6 +/- 3 kcal/mole). Moreover, EB and Fl exhibited also second-order loss of 1,4 unsaturation, with E(sub a) ca. 36 and 40 kcal/mole, respectively, while DI showed negligible loss of 1,4 unsaturation below 260 C, in common with cis-1,4-polybutadiene (CB) (with 2% 1,2 double bonds) examined earlier. The loss of 1,2 double bonds in the various polybutadienes with different vinyl contents is accompanied by substantial methyl production, ranging from about one methyl group formed for every 4-5 vinyl units lost in VB, to one methyl for every two vinyls lost in EB,and to almost one methyl for each vinyl lost in DI or CB. Mechanisms are proposed for the thermally induced loss of 1,2 and 1,4 unsaturation in various polybutadienes and for the accompanying methyl production.

Golub, Morton A.↗

Reentry Vehicle Flight Controls Design Guidelines: Dynamic Inversion

This report addresses issues in developing a flight control design for vehicles operating across a broad flight regime and with highly nonlinear physical descriptions of motion. Specifically it addresses the need for reentry vehicles that could operate through reentry from space to controlled touchdown on Earth. The latter part of controlled descent is achieved by parachute or paraglider - or by all automatic or a human-controlled landing similar to that of the Orbiter. Since this report addresses the specific needs of human-carrying (not necessarily piloted) reentry vehicles, it deals with highly nonlinear equations of motion, and then-generated control systems must be robust across a very wide range of physics. Thus, this report deals almost exclusively with some form of dynamic inversion (DI). Two vital aspects of control theory - noninteracting control laws and the transformation of nonlinear systems into equivalent linear systems - are embodied in DI. Though there is no doubt that the mathematical tools and underlying theory are widely available, there are open issues as to the practicality of using DI as the only or primary design approach for reentry articles. This report provides a set of guidelines that can be used to determine the practical usefulness of the technique.

Ito, Daigoro↗

A Deuterium NMR Study of Bent-Core Liquid Crystals: Synthesis and Characterization of Deuterium-Labeled Oxadiazole-Containing Liquid Crystals - 1

We have synthesized two deuterated boomerang-shaped liquid crystals based on 2,5-bis(4-hydroxyphenyl)-1,3,4-oxadiazole (ODBP). Deuterium was introduced in the rigid 2,5-diphenyl-1,3,4-oxadiazole core and in the aromatic ring of the terminal 4-dodecyloxyphenyl moiety using standard acid catalyzed deuterium exchange conditions. Both compounds, ([4,4'(1,3,4-oxadiazole-2,5-diyl-d4)] di-4-dodecyloxybenzoate: ODBP-d4-Ph-O-C12) and ([4,4'(1,3,4-oxadiazole-2,5-diyl)] di-4-dodecyloxy-benzoate-d4; ODBP-Ph-d4-O-C12) were investigated by nuclear magnetic resonance, optical microscopy and differential scanning calorimetry. The optical textures and thermal behavior of both compounds were found to be identical to the non-deuterated analog [4,4(1,3,4-oxadiazole-2,5-diyl)] di-4-dodecyloxybenzoate (ODBP-Ph-O-C12) which we reported earlier. These compounds exhibit behavior indicative of a biaxial nematic liquid crystal phase, which we hope to confirm using deuterium NMR spectroscopy in the next phase of this study.

Dingemans, Theo J.↗

Molecular Data for a Biochemical Model of DNA Radiation Damage: Electron Impact Ionization and Dissociative Ionization of DNA Bases and Sugar-Phosphate Backbone

As part of the database for building up a biochemical model of DNA radiation damage, electron impact ionization cross sections of sugar-phosphate backbone and DNA bases have been calculated using the improved binary-encounter dipole (iBED) model. It is found that the total ionization cross sections of C3'- and C5'-deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 10%. Of the four DNA bases, the ionization cross section of guanine is the largest, then in decreasing order, adenine, thymine, and cytosine. The order is in accordance with the known propensity of oxidation of the bases by ionizing radiation. Dissociative ionization (DI), a process that both ionizes and dissociates a molecule, is investigated for cytosine. The DI cross section for the formation of H and (cytosine-Hl)(+), with the cytosine ion losing H at the 1 position, is also reported. The threshold of this process is calculated to be 17.1 eV. Detailed analysis of ionization products such as in DI is important to trace the sequential steps in the biochemical process of DNA damage.

Dateo, Christopher E.↗

Structural specificity of mucosal-cell transport and metabolism of peptide drugs: implication for oral peptide drug delivery

The brush border membrane of intestinal mucosal cells contains a peptide carrier system with rather broad substrate specificity and various endo- and exopeptidase activities. Small peptide (di-/tripeptide)-type drugs with or without an N-terminal alpha-amino group, including beta-lactam antibiotics and angiotensin-converting enzyme (ACE) inhibitors, are transported by the peptide transporter. Polypeptide drugs are hydrolyzed by brush border membrane proteolytic enzymes to di-/tripeptides and amino acids. Therefore, while the intestinal brush border membrane has a carrier system facilitating the absorption of di-/tripeptide drugs, it is a major barrier limiting oral availability of polypeptide drugs. In this paper, the specificity of peptide transport and metabolism in the intestinal brush border membrane is reviewed.

Review, Tutorial↗

Poly(N-arylenebenzimidazole)s via aromatic nucleophilic displacement

Novel poly(N-arylenebenzimidazole)s (PNABls) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl-N-arylenebenzimidazole) monomers are synthesized by reacting phenyl-4-hydroxybenzoate with bis(2-aminoanilino)arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyI-N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

Connell, John W.↗

X-38 Application of Dynamic Inversion Flight Control

This paper summarizes the application of a nonlinear dynamic inversion (DI) flight control system (FCS) to an autonomous flight test vehicle in NASA's X-38 Project, a predecessor to the International Space Station (ISS) Crew Return Vehicle (CRV). Honeywell's Multi-Application Control-H (MACH) is a parameterized FCS design architecture including both model-based DI rate-compensation and classical P+I command-tracking. MACH was adopted by X-38 in order to shorten the design cycle time for different vehicle shapes and flight envelopes and evolving aerodynamic databases. Specific design issues and analysis results are presented for the application of MACH to the 3rd free flight (FF3) of X-38 Vehicle 132 (V132). This B-52 drop test, occurring on March 30, 2000, represents the first flight test of MACH and one of the first few known applications of DI in the primary FCS of an autonomous flight test vehicle.

Wacker, Roger↗