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At least 91 records · Page 5

Kinetics of template-directed pyrophosphate-linked dideoxyguanylate synthesis as a function of 2-MeImpdG and poly(C) concentration: insights into the mechanism

Aqueous solutions of deoxyguanosine 5'-monophosphate 2-methylimidazolide, 2-MeImpdG, yield primarily deoxyguanosine 5'-monophosphate, 5'dGMP, and pyrophosphate-linked dideoxyguanylate, dG5'ppdG, abbreviated G2p (see Chart 1). The initial rate of G2p formation, d[G2p]/dt in M h-1, determined at 23 degrees C, pH 7.8, 1.0 M NaCl and 0.2 M Mg2+ by timed high-performance liquid chromatography (HPLC) analysis, exhibits a second-order dependence on 2-MeImpdG concentration, [G]o, indicating a bimolecular mechanism of dimerization in the range 0.02 M < or = [G]o < or = 0.09 M. In the presence of polycytidylate, poly(C), G2p synthesis is accelerated and oligodeoxyguanylate products are formed by incorporation of 2-MeImpdG molecules. The kinetics of G2p formation as a function of both monomer and polymer concentration, expressed in C equivalents, were also determined under the above conditions and exhibited a complex behavior. Specifically, at a constant [poly(C)], values of d[G2p]/dt typically increased with [G]o with a parabolic upward curvature. At a constant [G]o, values of d[G2p]/dt increase with [poly(C)], but level off at the higher poly(C) concentrations. As [G]o increases this saturation occurs at a higher poly(C) concentration, a result opposite to expectation for a simple complexation of two reacting monomers with the catalyst prior to reaction. Nevertheless, these results are shown to be quantitatively consistent with a template-directed (TD) mechanism of dimerization where poly(C) acts as the template to bind 2-MeImpdG in a cooperative manner and lead, for the first time, to the formulation of principles that govern template-directed chemistry. Analysis of the kinetic data via a proposed TD cooperative model provides association constants for the affinity between polymer and monomer and the intrinsic reactivity of 2-MeImpdG toward pyrophosphate synthesis. To the best of our knowledge, poly(C)/2-MeImpdG is the first system that could serve as a textbook example of a TD reaction under conditions such that the template is fully saturated by monomers and under conditions that it is not.

NASA Discipline Exobiology↗

The NuSTAR Extragalactic Surveys: The Number Counts Of Active Galactic Nuclei And The Resolved Fraction Of The Cosmic X-ray Background

We present the 3-8 kiloelectronvolts and 8-24 kiloelectronvolts number counts of active galactic nuclei (AGNs) identified in the Nuclear Spectroscopic Telescope Array (NuSTAR) extragalactic surveys. NuSTAR has now resolved 33 percent -39 percent of the X-ray background in the 8-24 kiloelectronvolts band, directly identifying AGNs with obscuring columns up to approximately 10 (exp 25) per square centimeter. In the softer 3-8 kiloelectronvolts band the number counts are in general agreement with those measured by XMM-Newton and Chandra over the flux range 5 times 10 (exp -15) less than or approximately equal to S (3-8 kiloelectronvolts) divided by ergs per second per square centimeter less than or approximately equal to 10 (exp -12) probed by NuSTAR. In the hard 8-24 kiloelectronvolts band NuSTAR probes fluxes over the range 2 times 10 (exp -14) less than or approximately equal to S (8-24 kiloelectronvolts) divided by ergs per second per square centimeter less than or approximately equal to 10 (exp -12), a factor approximately 100 times fainter than previous measurements. The 8-24 kiloelectronvolts number counts match predictions from AGN population synthesis models, directly confirming the existence of a population of obscured and/or hard X-ray sources inferred from the shape of the integrated cosmic X-ray background. The measured NuSTAR counts lie significantly above simple extrapolation with a Euclidian slope to low flux of the Swift/BAT15-55 kiloelectronvolts number counts measured at higher fluxes (S (15-55 kiloelectronvolts) less than or approximately equal to 10 (exp -11) ergs per second per square centimeter), reflecting the evolution of the AGN population between the Swift/BAT local (redshift is less than 0.1) sample and NuSTAR's redshift approximately equal to 1 sample. CXB (Cosmic X-ray Background) synthesis models, which account for AGN evolution, lie above the Swift/BAT measurements, suggesting that they do not fully capture the evolution of obscured AGNs at low redshifts

nucle↗

Computer-aided linear-circuit design.

Usually computer-aided design (CAD) refers to programs that analyze circuits conceived by the circuit designer. Among the services such programs should perform are direct network synthesis, analysis, optimization of network parameters, formatting, storage of miscellaneous data, and related calculations. The program should be embedded in a general-purpose conversational language such as BASIC, JOSS, or APL. Such a program is MARTHA, a general-purpose linear-circuit analyzer embedded in APL.

Penfield, P.↗

Stereoselective aminoacylation of a dinucleoside monophosphate by the imidazolides of DL-alanine and N-(tert-butoxycarbonyl)-DL-alanine

The aminoacylation of diinosine monophosphate was studied experimentally. When the acylating agent was the imidazolide of N-(tert-butoxycarbonyl)-DL-alanine, a 40 percent enantiomeric excess of the isomer was incorporated at the 2' site and the positions of equilibrium for the reversible 2'-3' migration reaction differed for the D and L enantiomers. The reactivity of the nucleoside hydroxyl groups was found to decrease on the order 2'(3') less than internal 2' and less than 5', and the extent of the reaction was affected by the concentration of the imidazole buffer. Reaction of IpI with imidazolide of unprotected DL-alanine, by contrast, led to an excess of the D isomer at the internal 2' site. Finally, reaction with the N-carboxy anhydride of DL-alanine occurred without stereoselection. These results are found to be relevant to the study of the evolution of optical chemical activity and the origin of genetically directed protein synthesis.

Profy, A. T.↗

Preparation Of High-Temperature Reactive Oligomers

Very reactive materials form very-heat-stable polymers. Recent research directed toward synthesis of polyimides soluble in common organic solvents, melt-processable, and thermally curable without evolution of volatile by-products. Diels-Alder polymerization yields compounds that maintain integrities and toughnesses during long exposure times at high temperatures. High-temperature polymers synthesized by use of technique. Films and perhaps fibers fabricated from prepolymer in solution. Major potential at this stage of research limited to aerospace applications.

Ottenbrite, Raphael M.↗

Computer-aided design of flight control systems

A computer program is presented for facilitating the development and assessment of flight control systems, and application to a control design is discussed. The program is a computer-aided control-system design program based on direct digital synthesis of a proportional-integral-filter controller with scheduled linear-quadratic-Gaussian gains and command generator tracking of pilot inputs. The FlightCAD system concentrates on aircraft dynamics, flight-control systems, stability and performance, and has practical engineering applications.

Stengel, Robert F.↗

Low-latency digital frequency synthesizer using the residue number system

A low-latency frequency synthesizer using the Direct Digital Synthesis (DDS) technique has been designed. Called the Residue Assisted Frequency Synthesizer (RAFS), it exhibits frequency switching times which are reduced by more than 50 percent below previously published designs. The switching speed advantage is made possible by the use of the Residue Number System, which allows the pipeline lengths in the Phase Accumulator and other circuitry to be reduced significantly.

Chren, William A., Jr.↗

Whole-cell biocomputing

The ability to manipulate systems on the molecular scale naturally leads to speculation about the rational design of molecular-scale machines. Cells might be the ultimate molecular-scale machines and our ability to engineer them is relatively advanced when compared with our ability to control the synthesis and direct the assembly of man-made materials. Indeed, engineered whole cells deployed in biosensors can be considered one of the practical successes of molecular-scale devices. However, these devices explore only a small portion of cellular functionality. Individual cells or self-organized groups of cells perform extremely complex functions that include sensing, communication, navigation, cooperation and even fabrication of synthetic nanoscopic materials. In natural systems, these capabilities are controlled by complex genetic regulatory circuits, which are only partially understood and not readily accessible for use in engineered systems. Here, we focus on efforts to mimic the functionality of man-made information-processing systems within whole cells.

Non-NASA Center↗

FLUXNET-CH4 Synthesis Activity: Objectives, Observations, and Future Directions

This paper describes the formation of, and initial results for, a new FLUXNET coordination network for ecosystem-scale methane (CH4) measurements at 60 sites globally, organized by the Global Carbon Project in partnership with other initiatives and regional flux tower networks. The objectives of the effort are presented along with an overview of the coverage of eddy covariance (EC) CH4 flux measurements globally, initial results comparing CH4 fluxes across the sites, and future research directions and needs. Annual estimates of net CH4 fluxes across sites ranged from −0.2 ± 0.02 g C m(exp -2) yr(exp -1) for an upland forest site to 114.9 ± 13.4 g C m(exp -2) yr(exp -1) for an estuarine freshwater marsh, with fluxes exceeding 40 g C m(exp -2) yr(exp -1) at multiple sites. Average annual soil and air temperatures were found to be the strongest predictor of annual CH4 flux across wetland sites globally. Water table position was positively correlated with annual CH4 emissions, although only for wetland sites that were not consistently inundated throughout the year. The ratio of annual CH4 fluxes to ecosystem respiration increased significantly with mean site temperature. Uncertainties in annual CH4 estimates due to gap-filling and random errors were on average ±1.6 g C m(exp -2) yr(exp -1) at 95% confidence, with the relative error decreasing exponentially with increasing flux magnitude across sites. Through the analysis and synthesis of a growing EC CH4 flux database, the controls on ecosystem CH4 fluxes can be better understood, used to inform and validate Earth system models, and reconcile differences between land surface model- and atmospheric-based estimates of CH4 emissions.

Knox, Sara H.↗

Biomimetic, Self-Healing Nanocomposites for Aerospace Applications

This final report contains a summary of significant findings, and bibliographies of publications and patents resulting from the research. The findings are grouped as follows: A) Lustrin-Mimetic Self-Healing Polymer Networks; B) Nanostructure-Directing Catalysis of Synthesis of Electronically and Optoelectronically Active Metallo-oxanes and Organometallics; C) New Discovery that Molecular Stencils Control Directional Growth to Form Light-Weight Mineral Foams.

Morse, Daniel E.↗

High angle of attack control law development for a free-flight wind tunnel model using direct eigenstructure assignment

Flight-control laws are developed for a wind-tunnel aircraft model flying at a high angle of attack by using a synthesis technique called direct eigenstructure assignment. The method employs flight guidelines and control-power constraints to develop the control laws, and gain schedules and nonlinear feedback compensation provide a framework for considering the nonlinear nature of the attack angle. Linear and nonlinear evaluations show that the control laws are effective, a conclusion that is further confirmed by a scale model used for free-flight testing.

Wendel, Thomas R.↗

Aircraft noise synthesis system: Version 4 user instructions

A modified version of the Aircraft Noise Synthesis System with improved directivity and tonal content modeling has been developed. The synthesis system is used to provide test stimuli for studies of community annoyance to aircraft flyover noise. The computer-based system generates realistic, time-varying audio simulations of aircraft flyover noise at a specified observer location on the ground. The synthesis takes into account the time-varying aircraft position relative to the observer; specified reference spectra consisting of broadband, narrowband, and pure tone components; directivity patterns; Doppler shift; atmospheric effects; and ground effects. These parameters can be specified and controlled in such a way as to generate stimuli in which certain noise characteristics such as duration or tonal content are independently varied while the remaining characteristics such as broadband content are held constant. The modified version of the system provides improved modeling of noise directivity patterns and an increased number of pure tone components. User instructions for the modified version of the synthesis system are provided.

Mccurdy, David A.↗

Digital robust active control law synthesis for large order systems using constrained optimization

This paper presents a direct digital control law synthesis procedure for a large order, sampled data, linear feedback system using constrained optimization techniques to meet multiple design requirements. A linear quadratic Gaussian type cost function is minimized while satisfying a set of constraints on the design loads and responses. General expressions for gradients of the cost function and constraints, with respect to the digital control law design variables are derived analytically and computed by solving a set of discrete Liapunov equations. The designer can choose the structure of the control law and the design variables, hence a stable classical control law as well as an estimator-based full or reduced order control law can be used as an initial starting point. Selected design responses can be treated as constraints instead of lumping them into the cost function. This feature can be used to modify a control law, to meet individual root mean square response limitations as well as minimum single value restrictions. Low order, robust digital control laws were synthesized for gust load alleviation of a flexible remotely piloted drone aircraft.

Mukhopadhyay, Vivek↗

Synthesis of offset dual shaped subreflector antennas for control of Cassegrain aperture distributions

The method presented for antenna upgrading involves a redesign of only the subreflector portion of a Cassegrain antenna or the introduction of a subreflector feed system for a paraboloid. A pair of offset subreflectors are synthesized which will produce a controllable high gain amplitude distribution in the aperture of the large paraboloid. The synthesis method is based on the approximate formulation for an offset dual shaped high gain antenna first presented by Galindo-Israel and Mittra (1977). It is pointed out that in their approximate formulation, the geometrical optics energy was scattered from a subreflector and then from a second large reflector, which reflected a uniform phase distribution. In the offset dual shaped subreflector (DSS) antenna proposed here, the second reflection is from a smaller (sub) reflector, and it scatters a spherical wave that feeds a hyperboloid or feeds a large paraboloid directly. The DSS synthesis is tested on the 210-ft-diameter Cassegrain antenna at Goldstone, California.

Galindo-Israel, V.↗

A thin polymer insulator for Josephson tunneling applications

The progress made towards forming thin organic layers on superconductors and how these layers effect the transition temperature is discussed. The work was primarily directed towards 1) synthesis of the organics, 2) deposition of organics, and 3) setting up to make transition temperature measurements. The greatest effort was placed on synthesis, and most of the synthesis procedures are now perfected.

Wilmsen, C. W.↗