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At least 37 records · Page 2

Generalizing Reversible Triplet–Triplet Energy Transfer as a Strategy to Increase Excited-State Lifetime in Copper(I) Charge-Transfer Chromophores

In this work, we generalize reversible triplet–triplet energy transfer (TTET) as a strategy to achieve long (μs range) excited-state lifetimes in copper(I) photosensitizers of the general formula Cu(RNacNac)(CN-Ar) (RNacNac is a substituted β-diketiminate and CN-Ar is an aryl isocyanide). Six new complexes are presented where the isocyanide is substituted with a triplet–acceptor moiety─anthracene, naphthalene, or phenanthrene. In-depth photophysical analysis reveals that energetic matching of the charge-transfer ( 3 CT) and acceptor-localized 3 (π→π*) states is key to achieving long triplet excited-state lifetimes via reversible TTET. With 2-isocyanoanthracene as the acceptor ligand, 3 CT and 3(π→π*) are not energetically proximate, and irreversible quenching of 3 CT occurs. With a small 0.1–0.2 eV gap between the two triplet states, luminescence originates from the 3 CT state with a moderate excited-state lifetime of 250 or 283 ns observed. As key to the success of this approach, we demonstrate that altering the N-substituent on the RNacNac ligand modulates the energy of the 3 CT state, giving three complexes where the 3 CT and 3 (π→π*) energies are perfectly matched and the excited-state lifetimes are much longer, spanning 1.9–2.7 μs. As such, the key lesson of this work is that long triplet-state lifetimes in these compounds can be achieved by proper “mixing and matching” of the RNacNac ligand, which influences the 3 CT energy, and the triplet acceptor group which dictates the energy of the 3 (π→π*) state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Data for Photoenzymatic Stereoablative Enantioconvergence of γ-chiral Oximes via Hydrogen Atom Transfer

Producing enantioenriched molecules from racemic mixtures is essential for manufacturing. Traditional methods such as resolution, deracemization and enantioconvergent catalysis primarily involve separating or converting enantiomers without altering their structures, or functionalization of stereocentres at or proximal to functional groups. However, there are challenges in enantioselectively forging C–H bonds that are remote from functional groups via hydrogen atom transfer (HAT) with these methods. Here we introduce a strategy for the photoenzymatic stereoablative enantioconvergence of γ-chiral oximes using repurposed flavin-dependent ene-reductases. A photoinduced single-electron reduction of the γ-chiral oxime by an ene-reductase generates an iminyl radical, which then undergoes stereoablative 1,5-HAT at the γ-stereocentre. Subsequent chiral reconstruction through enzymatic HAT and spontaneous imine hydrolysis yields the γ-chiral ketone with high enantioselectivity. This work provides a robust method for remote stereoablative enantioconvergent HAT and broadens the synthetic utility of photobiocatalysis.

Bioproducts

Calculation of turbulent boundary layers with heat transfer and pressure gradient utilizing a compressibility transformation. Part 2: Constant property turbulent boundary layer flow with simultaneous mass transfer and pressure gradient

An analysis of the incompressible turbulent boundary layer, developing under the combined effects of mass transfer and pressure gradient, is presented in this paper. A strip-integral method is employed whereby two of the three governing equations are obtained by integrating the combined momentum and continuity equation to 50 percent and 100 percent, respectively, of the boundary-layer height. The latter equation is the usual momentum-integral equation; the former equation requires specification of shear. Accordingly, Clauser's equilibrium eddy-viscosity law is assumed valid at this point. The third and final equation is obtained by specifying that Stevenson's velocity profiles apply throughout the domain of interest, from which a skin-friction law can be derived. Comparisons of the numerical results with the experiments of McQuaid, which include combined effects of variable pressure gradient and mass transfer, show good agreement.

Boccio, J.

Heat transfer with very high free-stream turbulence and heat transfer with streamwise vortices

Two experimental programs related to augmentation of heat transfer by complex flow characteristics are reviewed. The first program deals with very high turbulence (up to 63 percent) which was shown to result in Stanton numbers as much as five times the expected values. Results from a number of trials show that fixing the free stream velocity, x-Reynolds number, turbulence intensity and integral length scale does not fix the Stanton number. Two such cases were found in which the Stanton number of one was 40 percent larger than the other. Mean velocity and mean temperature profiles are presented, as well as profiles of turbulence intensity within the boundary layer. The second program deals with vortices originating at bluff bodies and traveling downstream embedded in the wall boundary layer. Velocity vector maps from the boundary layers and distributions of Stanton number on the wall are presented for three types of bodies: square, cylindrical and teardrop. The heat transfer and velocity maps do not show evidence of the expected horseshoe vortices but, instead, show a strong common flow up vortex pair. The fluid mechanic mechanism responsible for this secondary flow field has not yet been identified.

Moffat, Robert J.

Heat transfer from high-temperature surfaces to fluids II : correlation of heat-transfer and friction data for air flowing in inconel tube with rounded entrance

A heat transfer investigation, which was an extension of a previously reported NACA investigation, was conducted with air flowing through an electrically heated inconel tube with a rounded entrance,an inside diameter of 0.402 inch, and a length of 24 inches over a range of conditions, which included Reynolds numbers up to 500,000, average surface temperatures up to 2050 degrees R, and heat-flux densities up to 150,000 Btu per hour per square foot. Conventional methods of correlating heat-transfer data wherein properties of the air were evaluated at the average bulk, film, and surface temperatures resulted in reductions of Nusselt number of about 38, 46, and 53 percent, respectively, for an increase in surface temperature from 605 degrees to 2050 degrees R at constant Reynolds number. A modified correlation method in which the properties of air were based on the surface temperature and the Reynolds number was modified by substituting the product of the density at the inside tube wall and the bulk velocity for the conventional mass flow per unit cross-sectional area, resulted in a satisfactory correlation of the data for the extended ranges of conditions investigated.

Lowdermilk, Warren H

Orbit transfer rocket engine technology program enhanced heat transfer combustor technology

In order to increase the performance of a high performance, advanced expander-cycle engine combustor, higher chamber pressures are required. In order to increase chamber pressure, more heat energy is required to be transferred to the combustor coolant circuit fluid which drives the turbomachinery. This requirement was fulfilled by increasing the area exposed to the hot-gas by using combustor ribs. A previous technology task conducted 2-d hot air and cold flow tests to determine an optimum rib height and configuration. In task C.5 a combustor calorimeter was fabricated with the optimum rib configuration, 0.040 in. high ribs, in order to determine their enhancing capability. A secondary objective was to determine the effects of mixture ratio changers on the enhancement during hot-fire testing. The program used the Rocketdyne Integrated Component Evaluator (ICE) reconfigured into a thrust chamber only mode. The test results were extrapolated to give a projected enhancement from the ribs for a 16 in. long cylindrical combustor at 15 Klb nominal thrust level. The hot-gas wall ribs resulted in a 58 percent increase in heat transfer. When projected to a full size 15K combustor, it becomes a 46 percent increase. The results of those tests, a comparison with previous 2-d results, the effects of mixture ratio and combustion gas flow on the ribs and the potential ramifications for expander cycle combustors are detailed.

Brown, William S.

Data Transfer Efficiency Over Satellite Circuits Using a Multi-Socket Extension to the File Transfer Protocol (FTP)

In several experiments using NASA's Advanced Communications Technology Satellite (ACTS), investigators have reported disappointing throughput using the transmission control protocol/Internet protocol (TCP/IP) protocol suite over 1.536Mbit/sec (T1) satellite circuits. A detailed analysis of file transfer protocol (FTP) file transfers reveals that both the TCP window size and the TCP 'slow starter' algorithm contribute to the observed limits in throughput. In this paper we summarize the experimental and and theoretical analysis of the throughput limit imposed by TCP on the satellite circuit. We then discuss in detail the implementation of a multi-socket FTP, XFTP client and server. XFTP has been tested using the ACTS system. Finally, we discuss a preliminary set of tests on a link with non-zero bit error rates. XFTP shows promising performance under these conditions, suggesting the possibility that a multi-socket application may be less effected by bit errors than a single, large-window TCP connection.

Allman, Mark

Heat-Transfer and Pressure Measurements from a Flight Test of the Third 1/18-Scale Model of the Titan Intercontinental Ballistic Missile up to a Mach Number of 3.86 and Reynolds Number per Foot of 23.5 x 10(exp 6) and a Comparison with Heat Transfer

Heat-transfer and pressure measurements were obtained from a flight test of a 1/18-scale model of the Titan intercontinental ballistic missile up to a Mach number of 3.86 and Reynolds number per foot of 23.5 x 10(exp 6) and are compared with the data of two previously tested 1/18-scale models. Boundary-layer transition was observed on the nose of the model. Van Driest's theory predicted heat-transfer coefficients reasonably well for the fully laminar flow but predictions made by Van Driest's theory for turbulent flow were considerably higher than the measurements when the skin was being heated. Comparison with the flight test of two similar models shows fair repeatability of the measurements for fully laminar or turbulent flow.

Graham, John B., Jr.

Radiative Transfer Modeling of a Large Pool Fire by Discrete Ordinates, Discrete Transfer, Ray Tracing, Monte Carlo and Moment Methods

Five computational methods for solution of the radiative transfer equation in an absorbing-emitting and non-scattering gray medium were compared on a 2 m JP-8 pool fire. The temperature and absorption coefficient fields were taken from a synthetic fire due to the lack of a complete set of experimental data for fires of this size. These quantities were generated by a code that has been shown to agree well with the limited quantity of relevant data in the literature. Reference solutions to the governing equation were determined using the Monte Carlo method and a ray tracing scheme with high angular resolution. Solutions using the discrete transfer method, the discrete ordinate method (DOM) with both S(sub 4) and LC(sub 11) quadratures, and moment model using the M(sub 1) closure were compared to the reference solutions in both isotropic and anisotropic regions of the computational domain. DOM LC(sub 11) is shown to be the more accurate than the commonly used S(sub 4) quadrature technique, especially in anisotropic regions of the fire domain. This represents the first study where the M(sub 1) method was applied to a combustion problem occurring in a complex three-dimensional geometry. The M(sub 1) results agree well with other solution techniques, which is encouraging for future applications to similar problems since it is computationally the least expensive solution technique. Moreover, M(sub 1) results are comparable to DOM S(sub 4).

Jensen, K. A.

Heat Transfer from High-Temperature Surfaces to Fluids III - Correlation of Heat-Transfer Data for Air Flowing in Silicon Carbide Tube with Rounded Entrance, Inside Diameter of 3/4 Inch, and Effective Length of 12 Inches

A heat-transfer investigation was conducted with air flowing through an electrically heated silicon carbide tube with a rounded entrance, an inside diameter of 3/4 inch, and effective heat-transfer length of 12 inches over a range of Reynolds numbers up to 300,000 and a range of average inside-tube-wall temperatures up to 2500 R. The highest corresponding local outside-tube-wall temperature was 3010 R.

Sams, Eldon W.