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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Initial Report of a Prospective Dosimetric and Clinical Feasibility Trial Demonstrates the Potential of Protons to Increase the Therapeutic Ratio in Breast Cancer Compared With Photons

Purpose: To compare dosimetric endpoints between proton therapy (PT) and conventional radiation and determine the feasibility of PT for regional nodal irradiation (RNI) in women with breast cancer. Methods and Materials: From 2012 to 2014, 18 women (stage IIA-IIIB) requiring RNI prospectively enrolled on a pilot study. Median age was 51.8 years (range, 42-73 years). The cohort included breast-conserving therapy (BCT) and mastectomy patients and right- and left-sided cancers. Treatment targets and organs at risk were delineated on computed tomography scans, and PT and conventional plans were developed. Toxicity was prospectively recorded using Common Terminology Criteria for Adverse Events version 4.0. A Wilcoxon signed-rank sum test compared the dose-volume parameters. The primary endpoint was a reduction in cardiac V5. Results: Median follow-up was 20 months (range, 2-31 months). For all patients, the PT plan better met the dosimetric goals and was used for treatment. Proton therapy alone was used for 10 patients (9 postmastectomy, 1 after BCT) and combined proton–photon in 8 (6 BCT, 2 postmastectomy with immediate expander reconstruction). Proton therapy improved coverage of level 2 axilla (P=.0005). Adequate coverage of internal mammary nodes was consistently achieved with PT (median D95, 50.3 Gy; range, 46.6-52.1 Gy) but not with conventional radiation therapy (median D95, 48.2 Gy; range, 40.8-55 Gy; P=.0005). Median cardiac V5 was 0.6% with PT and 16.3% with conventional radiation (P<.0001). Median ipsilateral lung V5 and V20 were improved with PT (median V5 35.3% vs 60.5% [P<.0001]; and median V20, 21.6% vs 35.5% [P<.0001]). Grade 3 dermatitis developed in 4 patients (22%), which was the only grade 3 toxicity. No grade 4+ toxicities developed. Conclusion: Proton therapy for RNI after mastectomy or BCT significantly improves cardiac dose, especially for left-sided patients, and lung V5 and V20 in all patients without excessive acute toxicity. Proton therapy simultaneously improves target coverage for the internal mammary nodes and level 2 axilla, which may positively impact long-term survival in breast cancer patients.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2016

1 H NMR metabolomics study of spleen from C57BL/6 mice exposed to gamma radiation

Due to the potential risk of accidental exposure to gamma radiation, it’s critical to identify the biomarkers of radiation exposed creatures. In the present study, NMR based metabolomics combined with multivariate data analysis to evaluate the metabolites changed in the C57BL/6 mouse spleen after 4 days whole body exposure to 3.0 Gy and 7.8 Gy gamma radiations. Principal component analysis (PCA) and orthogonal projection to latent structures analysis (OPLS) are employed for classification and identification potential biomarkers associated with gamma irradiation. Two different strategies for NMR spectral data reduction (i.e., spectral binning and spectral deconvolution) are combined with normalize to constant sum and unit weight before multivariate data analysis, respectively. The combination of spectral deconvolution and normalization to unit weight is the best way for identifying discriminatory metabolites between the irradiation and control groups. Normalized to the constant sum may achieve some pseudo biomarkers. PCA and OPLS results shown that the exposed groups can be well separated from the control group. Leucine, 2-aminobutyrate, valine, lactate, arginine, glutathione, 2-oxoglutarate, creatine, tyrosine, phenylalanine, π-methylhistidine, taurine, myoinositol, glycerol and uracil are significantly elevated while ADP is decreased significantly. As a result, these significantly changed metabolites are associated with multiple metabolic pathways and may be potential biomarkers in the spleen exposed to gamma irradiation.

1H NMR metabolomics↗
DOE OSTI2015

In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). In this paper, we have studied a common electrolyte, 1.0 M LiPF 6 /ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials where electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC 2 H 5 ) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. Finally, these findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.

25 ENERGY STORAGE↗
DOE OSTI2020

An investigation of Newton-Sketch and subsampled Newton methods

Sketching, a dimensionality reduction technique, has received much attention in the statistics community. In this paper, we study sketching in the context of Newton's method for solving finite-sum optimization problems in which the number of variables and data points are both large. In this work, we study two forms of sketching that perform dimensionality reduction in data space: Hessian subsampling and randomized Hadamard transformations. Each has its own advantages, and their relative tradeoffs have not been investigated in the optimization literature. Additionally, our study focuses on practical versions of the two methods in which the resulting linear systems of equations are solved approximately, at every iteration, using an iterative solver. The advantages of using the conjugate gradient method vs. a stochastic gradient iteration are revealed through a set of numerical experiments, and a complexity analysis of the Hessian subsampling method is presented.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity

Here, the cyclability of silicon anodes in lithium ion batteries (LIBs) is affected by the reduction of the electrolyte on the anode surface to produce a coating layer termed the solid electrolyte interphase (SEI). One of the key steps for a major improvement of LIBs is unraveling the SEI’s structure-related diffusion properties as charge and discharge rates of LIBs are diffusion-limited. To this end, we have combined two surface sensitive techniques, sum frequency generation (SFG) vibrational spectroscopy, and X-ray reflectivity (XRR), to explore the first monolayer and to probe the first several layers of electrolyte, respectively, for solutions consisting of 1 M lithium perchlorate (LiClO 4 ) salt dissolved in ethylene carbonate (EC) or fluoroethylene carbonate (FEC) and their mixtures (EC/FEC 7:3 and 1:1 wt %) on silicon and sapphire surfaces. Our results suggest that the addition of FEC to EC solution causes the first monolayer to rearrange itself more perpendicular to the anode surface, while subsequent layers are less affected and tend to maintain their, on average, surface-parallel arrangements. This fundamental understanding of the near-surface orientation of the electrolyte molecules can aid operational strategies for designing high-performance LIBs.

36 MATERIALS SCIENCE↗
NASA NTRS1994

Scaling, elasticity, and CLPT

The first few viewgraphs describe the general solution properties of linear elasticity theory which are given by the following two statements: (1) for stress B.C. on S(sub sigma) and zero displacement B.C. on S(sub u) the altered displacements u(sub i)(*) and the actual stresses tau(sub ij) are elastically dependent on Poisson's ratio nu alone: thus the actual displacements are given by u(sub i) = mu(exp -1)u(sub i)(*); and (2) for zero stress B.C. on S(sub sigma) and displacement B.C. on S(sub u) the actual displacements u(sub i) and the altered stresses tau(sub ij)(*) are elastically dependent on Poisson's ratio nu alone: thus the actual stresses are given by tau(sub ij) = E tau(sub ij)(*). The remaining viewgraphs describe the minimum parameter formulation of the general classical laminate theory plate problem as follows: The general CLT plate problem is expressed as a 3 x 3 system of differential equations in the displacements u, v, and w. The eighteen (six each) A(sub ij), B(sub ij), and D(sub ij) system coefficients are ply-weighted sums of the transformed reduced stiffnesses (bar-Q(sub ij))(sub k); the (bar-Q(sub ij))(sub k) in turn depend on six reduced stiffnesses (Q(sub ij))(sub k) and the material and geometry properties of the k(sup th) layer. This paper develops a method for redefining the system coefficients, the displacement components (u,v,w), and the position components (x,y) such that a minimum parameter formulation is possible. The pivotal steps in this method are (1) the reduction of (bar-Q(sub ij))(sub k) dependencies to just two constants Q(*) = (Q(12) + 2Q(66))/(Q(11)Q(22))(exp 1/2) and F(*) - (Q(22)/Q(11))(exp 1/2) in terms of ply-independent reference values Q(sub ij); (2) the reduction of the remaining portions of the A, B, and D coefficients to nondimensional ply-weighted sums (with 0 to 1 ranges) that are independent of Q(*) and F(*); and (3) the introduction of simple coordinate stretchings for u, v, w and x,y such that the process is neatly completed.

Brunelle, Eugene J.↗
DOE OSTI2020

Algorithms for Efficient Reproducible Floating Point Summation

We define “reproducibility” as getting bitwise identical results from multiple runs of the same program, perhaps with different hardware resources or other changes that should not affect the answer. Many users depend on reproducibility for debugging or correctness. However, dynamic scheduling of parallel computing resources, combined with nonassociative floating point addition, makes reproducibility challenging even for summation, or operations like the BLAS. We describe a “reproducible accumulator” data structure (the “binned number”) and associated algorithms to reproducibly sum binary floating point numbers, independent of summation order. We use a subset of the IEEE Floating Point Standard 754-2008 and bitwise operations on the standard representations in memory. Our approach requires only one read-only pass over the data, and one reduction in parallel, using a 6-word reproducible accumulator (more words can be used for higher accuracy), enabling standard tiling optimization techniques. Summing n words with a 6-word reproducible accumulator requires approximately 9 n floating point operations (arithmetic, comparison, and absolute value) and approximately 3 n bitwise operations. The final error bound with a 6-word reproducible accumulator and our default settings can be up to 2 29 times smaller than the error bound for conventional (recursive) summation on ill-conditioned double-precision inputs.

Computer Science↗
DOE OSTI2024

Nonlinear susceptibilities for weakly turbulent magnetized plasma: Electrostatic approximation

The plasma weak turbulence theory is a perturbative nonlinear theory, which has been proven to be quite valid in a number of applications. However, the standard weak turbulence theory found in the literature is fully developed for highly idealized unmagnetized plasmas. As many plasmas found in nature and laboratory are immersed in a background static magnetic field, it is necessary to extend the existing discussions to include the effects of ambient magnetic field. Such a task is quite formidable, however, which has prevented fundamental and significant progresses in the subject matter. The central difficulty lies in the formulation of the complete nonlinear response functions for magnetized plasmas. The present paper derives the nonlinear susceptibilities for weakly turbulent magnetized plasmas up to the third order nonlinearity, but in doing so, a substantial reduction in mathematical complexity is achieved by the use of Bessel function addition theorem (or sum rule). The present paper also constructs the weak turbulence wave kinetic equation in a formal sense. For the sake of simplicity, however, the present paper assumes the electrostatic interaction among plasma particles. Fully electromagnetic generalization is a subject of a subsequent paper.

Physics↗
DOE OSTI2018

On the Goldbach Conjecture

This note confirms Goldbach’s Conjecture from 1742. This is, every even integer greater than two is the sum of two prime numbers. An analysis of the nature of multiplication as description length reduction for addition precedes a contraposition that it is impossible to subtract any prime from a given even integer without the result ever being prime.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2015

Efficient calculation of integrals in mixed ramp-Gaussian basis sets

Algorithms for the efficient calculation of two-electron integrals in the newly developed mixed ramp-Gaussian basis sets are presented, alongside a Fortran90 implementation of these algorithms, RAMPITUP. These new basis sets have significant potential to (1) give some speed-up (estimated at up to 20% for large molecules in fully optimised code) to general-purpose Hartree-Fock (HF) and density functional theory quantum chemistry calculations, replacing all-Gaussian basis sets, and (2) give very large speed-ups for calculations of core-dependent properties, such as electron density at the nucleus, NMR parameters, relativistic corrections, and total energies, replacing the current use of Slater basis functions or very large specialised all-Gaussian basis sets for these purposes. This initial implementation already demonstrates roughly 10% speed-ups in HF/R-31G calculations compared to HF/6-31G calculations for large linear molecules, demonstrating the promise of this methodology, particularly for the second application. As well as the reduction in the total primitive number in R-31G compared to 6-31G, this timing advantage can be attributed to the significant reduction in the number of mathematically complex intermediate integrals after modelling each ramp-Gaussian basis-function-pair as a sum of ramps on a single atomic centre.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanoparticle-Induced Disorder at Complex Liquid–Liquid Interfaces: Effects of Curvature and Compositional Synergy on Functional Surfaces

The self-assembly of surfactant monolayers at interfaces plays a sweeping role in tasks ranging from household cleaning to the regulation of the respiratory system. The synergy between different nanoscale species at an interface can yield assemblies with exceptional properties, which enhance or modulate their function. However, understanding the mechanisms underlying coassembly, as well as the effects of intermolecular interactions at an interface, remains an emerging and challenging field of study. Herein, we study the interactions of gold nanoparticles striped with hydrophobic and hydrophilic ligands with phospholipids at a liquid–liquid interface and the resulting surface-bound complexes. We show that these nanoparticles, which are themselves minimally surface active, have a direct concentration-dependent effect on the rapid reduction of tension for assembling phospholipids at the interface, implying molecular coassembly. Through the use of sum frequency generation vibrational spectroscopy, we reveal that nanoparticles impart structural disorder to the lipid molecular layers, which is related to the increased volumes that amphiphiles can sample at the curved surface of a particle. The results strongly suggest that hydrophobic and electrostatic attractions imparted by nanoparticle functionalization drive lipid–nanoparticle complex assembly at the interface, which synergistically aids lipid adsorption even when lipids and nanoparticles approach the interface from opposite phases. The use of tensiometric and spectroscopic analyses reveals a physical picture of the system at the nanoscale, allowing for a quantitative analysis of the intermolecular behavior that can be extended to other systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Round-off error in long-term orbital integrations using multistep methods

Techniques for reducing roundoff error are compared by testing them on high-order Stormer and summetric multistep methods. The best technique for most applications is to write the equation in summed, function-evaluation form and to store the coefficients as rational numbers. A larger error reduction can be achieved by writing the equation in backward-difference form and performing some of the additions in extended precision, but this entails a larger central processing unit (cpu) cost.

Quinlan, Gerald D.↗
NASA NTRS2011

Reconciling LCROSS and Orbital Neutron Water Abundance Estimates in Cabeus Crater

The Lunar Prospector Neutron Spectrometer (LPNS) first revealed Cabeus crater (84.9 deg S, 35.5degW) as having the highest inferred hydrogen on the Moon. Because of the broad LPNS footprint (approximately 40 km FWHM), the apparent peak water-equivalent hydrogen (WEH) concentration is only approximately 0.25 wt%, but could be much higher in smaller areas than the spectrometer footprint. Earlier image reconstruction work suggested that areas within permanent shadow have abundances approximately 1 wt% WEH. However, the LCROSS impact yielded total water estimates, ice plus vapor, of between 3 and 10 wt%. The large disagreement between LCROSS and apparent orbital values imply that either the ice is buried, by perhaps as much as 50 to 100 cm; or the ice distribution within Cabeus is spatially inhomogeneous, or both. Modeling reveals that the areal extent of a "shallow permafrost zone" is far greater than the area of permanent shadow. Ice can be virtually stable for billions of years within a few tens of centimeters of the surface in these areas. However, the LCROSS impact took place in an area of permanent shadow. If stably-trapped volatiles can be found in locales that receive occasional, oblique sunlight, landed missions may target these sites and eventual resource exploitation may be done more easily. Are orbital neutron data consistent with areally-extensive, volatile-rich cold traps? Orbital epithermal neutron data over the northern half of Cabeus (near the LCROSS impact site) are consistent with 0.2 wt% WEH or less in the "permafrost zone" near the crater. On the other hand, pixon reconstructions that confine the hydrogen enhancements to permanent shadow result in higher abundance estimates -- around 1 wt% if homogeneously mixed. But if the PSR abundance is increased to 10 wt%, consistent with the sum of all H-bearing compounds seen by LCROSS, a much larger-than-observed reduction in neutron count rate would be seen from orbit. It is likely that volatiles are inhomogeneously distributed, due to both impact processes and emplacement history. Two possibilities may bring consistency to the orbital and LCROSS measurements. Inhomogeneous lateral distribution: Consider the extreme case of a bimodal distribution within the crater -- dry and wet. In this case the epithermal leakage flux seen from orbit is a mixture of two different values, weighted according to fractional areas. Two possible outcomes, depending on whether the inferred leakage flux for the PSR or "permafrost" areas are considered. In the first case, approximately 40% of the PSR may be "wet", the remainder dry (and LCROSS was slightly lucky). However, if the whole area of permafrost is considered, then as little as 20% of the area will be as "wet" as the LCROSS results (and LCROSS was quite lucky). Inhomogeneous depth distribution: The leakage flux of thermal and epithermal neutrons depends on depth of burial of an icy layer beneath dry ferroan anorthosite soil (FAn). For the Cabeus PSR, the pixon reconstruction values for the epithermal flux allows a range of abundance and burial depth, while that of the thermal+epi detector constrains this range. (Uncertainties in iron abundance in the FAn can have significant impact on thermal neutron leakage flux estimates.) Between 20% and 40% of the Cabeus floor may be "wet", or alternatively a 5-10 wt% "wet" layer exists between 50 and 100 cm beneath a layer of dry regolith within the PSR. But volatile abundances of 5 wt% or more, distributed uniformly and homogeneously throughout the Cabeus PSR do not agree with orbital measurements

Elphic, Richard↗
DOE OSTI2015

Emissions of nitrogen oxides from US urban areas: estimation from Ozone Monitoring Instrument retrievals for 2005–2014

Satellite remote sensing of tropospheric nitrogen dioxide (NO 2 ) can provide valuable information for estimating surface nitrogen oxides (NO x ) emissions. Using an exponentially modified Gaussian (EMG) method and taking into account the effect of wind on observed NO 2 distributions, we estimate 3-year moving-average emissions of summertime NO x from 35 US (United States) urban areas directly from NO 2 retrievals of the Ozone Monitoring Instrument (OMI) during 2005–2014. Following conclusions of previous studies that the EMG method provides robust and accurate emission estimates under strong-wind conditions, we derive top-down NO x emissions from each urban area by applying the EMG method to OMI data with wind speeds greater than 3–5 m s -1 . Meanwhile, we find that OMI NO 2 observations under weak-wind conditions (i.e., < 3 m s &minus;1 ) are qualitatively better correlated to the surface NO x source strength in comparison to all-wind OMI maps; therefore, we use them to calculate the satellite-observed NO 2 burdens of urban areas and compare with NO x emission estimates. The EMG results show that OMI-derived NO x emissions are highly correlated ( R > 0.93) with weak-wind OMI NO 2 burdens as well as with bottom-up NO x emission estimates over 35 urban areas, implying a linear response of the OMI observations to surface emissions under weak-wind conditions. The simultaneous EMG-obtained effective NO 2 lifetimes (~ 3.5 ± 1.3 h), however, are biased low in comparison to the summertime NO 2 chemical lifetimes. In general, isolated urban areas with NO x emission intensities greater than ~ 2 Mg h -1 produce statistically significant weak-wind signals in 3-year average OMI data. From 2005 to 2014, we estimate that total OMI-derived NO x emissions over all selected US urban areas decreased by 49 %, consistent with reductions of 43, 47, 49, and 44 % in the total bottom-up NO x emissions, the sum of weak-wind OMI NO 2 columns, the total weak-wind OMI NO 2 burdens, and the averaged NO 2 concentrations, respectively, reflecting the success of NO x control programs for both mobile sources and power plants. The decrease rates of these NO x -related quantities are found to be faster (i.e., -6.8 to -9.3 % yr &minus;1 ) before 2010 and slower (i.e., -3.4 to -4.9 % yr &minus;1 ) after 2010. For individual urban areas, we calculate the R values of pair-wise trends among the OMI-derived and bottom-up NO x emissions, the weak-wind OMI NO 2 burdens, and ground-based NO 2 measurements, and high correlations are found for all urban areas (median R = 0.8), particularly large ones ( R up to 0.97). The results of the current work indicate that using the EMG method and considering the wind effect, the OMI data allow for the estimation of NO x emissions from urban areas and the direct constraint of emission trends with reasonable accuracy.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Emissions of nitrogen oxides from US urban areas: estimation from Ozone Monitoring Instrument retrievals for 2005-2014

Satellite remote sensing of tropospheric nitrogen dioxide (NO 2 ) can provide valuable information for estimating surface nitrogen oxides (NO x ) emissions. Using an exponentially-modified Gaussian (EMG) method and taking into account the effect of wind on observed NO 2 distributions, we estimate three-year moving-average emissions of summertime NO x from 35 US urban areas directly from NO 2 retrievals of the Ozone Monitoring Instrument (OMI) during 2005–2014. Following the conclusions of previous studies that the EMG method provides robust and accurate emission estimates under strong-wind conditions, we derive top-down NO x emissions from each urban area by applying the EMG method to OMI data with wind speeds greater than 3–5 m s -1 . Meanwhile, we find that OMI NO 2 observations under weak-wind conditions (i.e., < 3 m s -1 ) are qualitatively better correlated with the surface NO x source strength in comparison to all-wind OMI maps; and therefore we use them to calculate the satellite-observed NO 2 burdens of urban areas and compare with NO x emission estimates. The EMG results show that OMI-derived NO x emissions are highly correlated ( R > 0.93) with weak-wind OMI NO 2 burdens as well as bottom-up NO x emission estimates over 35 urban areas, implying a linear response of the OMI observations to surface emissions under weak-wind conditions. The simultaneous, EMG-obtained, effective NO 2 lifetimes (~3.5 ± 1.3 h), however, are biased low in comparison to the summertime NO 2 chemical lifetimes. In general, isolated urban areas with NO x emission intensities greater than ~ 2 Mg h -1 produce statistically significant weak-wind signals in three-year average OMI data. From 2005 to 2014, we estimate that total OMI-derived NO x emissions over all selected US urban areas decreased by 49%, consistent with reductions of 43, 47, 49, and 44% in the total bottom-up NO x emissions, the sum of weak-wind OMI NO 2 columns, the total weak-wind OMI NO 2 burdens, and the averaged NO 2 concentrations, respectively, reflecting the success of NO x control programs for both mobile sources and power plants. The decrease rates of these NO x -related quantities are found to be faster (i.e., -6.8 to -9.3% yr -1 ) before 2010 and slower (i.e., -3.4 to -4.9% yr -1 ) after 2010. For individual urban areas, we calculate the R values of pair-wise trends among the OMI-derived and bottom-up NO x emissions, the weak-wind OMI NO 2 burdens, and ground-based NO 2 measurements; and high correlations are found for all urban areas (median R = 0.8), particularly large ones ( R up to 0.97). The results of the current work indicate that using the EMG method and considering the wind effect, the OMI data allow for the estimation of NO x emissions from urban areas and the direct constraint of emission trends with reasonable accuracy.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Heterogenized Molecular Catalysts: Vibrational Sum-Frequency Spectroscopic, Electrochemical, and Theoretical Investigations

Rhenium and manganese bipyridyl tricarbonyl complexes have attracted intense interest for their promising applications in photocatalytic and electrocatalytic CO 2 reduction in both homogeneous and heterogenized systems. To date, there have been extensive studies on immobilizing Re catalysts on solid surfaces for higher catalytic efficiency, reduced catalyst loading, and convenient product separation. However, in order for the heterogenized molecular catalysts to achieve the combination of the best aspects of homogeneous and heterogeneous catalysts, it is essential to understand the fundamental physicochemical properties of such heterogeneous systems, such as surface-bound structures of Re/Mn catalysts, substrate&ndash;adsorbate interactions, and photoinduced or electric-field-induced effects on Re/Mn catalysts. For example, the surface may act to (un)block substrates, (un)trap charges, (de)stabilize particular intermediates (and thus affect scaling relations), and shift potentials in different directions, just as protein environments do. The close collaboration between the Lian, Batista, and Kubiak groups has resulted in an integrated approach to investigate how the semiconductor or metal surface affects the properties of the attached catalyst. Synthetic strategies to achieve stable and controlled attachment of Re/Mn molecular catalysts have been developed. Steady-state, time-resolved, and electrochemical vibrational sum-frequency generation (SFG) spectroscopic studies have provided insight into the effects of interfacial structures, ultrafast vibrational energy relaxation, and electric field on the Re/Mn catalysts, respectively. Various computational methods utilizing density functional theory (DFT) have been developed and applied to determine the molecular orientation by direct comparison to spectroscopy, unravel vibrational energy relaxation mechanisms, and quantify the interfacial electric field strength of the Re/Mn catalyst systems. This Account starts with a discussion of the recent progress in determining the surface-bound structures of Re catalysts on semiconductor and Au surfaces by a combined vibrational SFG and DFT study. The effects of crystal facet, length of anchoring ligands, and doping of the semiconductor on the bound structures of Re catalysts and of the substrate itself are discussed. This is followed by a summary of the progress in understanding the vibrational relaxation (VR) dynamics of Re catalysts covalently adsorbed on semiconductor and metal surfaces. The VR processes of Re catalysts on TiO 2 films and TiO 2 single crystals and a Re catalyst tethered on Au, particularly the role of electron–hole pair (EHP)-induced coupling on the VR of the Re catalyst bound on Au, are discussed. The Account also summarizes recent studies in quantifying the electric field strength experienced by the catalytically active site of the Re/Mn catalyst bound on a Au electrode based on a combined electrochemical SFG and DFT study of the Stark tuning of the CO stretching modes of these catalysts. Finally, future research directions on surface-immobilized molecular catalyst systems are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Television noise-reduction device

System greatly improves signal-to-noise ratio with little or no loss in picture resolution. By storage of luminance component, which is summed with chrominance component, system performs mathematical integration of basically-repetitive television signals. Integration of signals over interval of their repetition causes little change in original signals and eliminates random noise.

Stamps, J. C.↗