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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Ion-Pair Reorganization Regulates Reactivity in Photoredox Catalysts

Cyclometalated and polypyridyl complexes of d6 metals are promising photoredox catalysts, using light to drive reactions with high kinetic or thermodynamic barriers via the generation of reactive radical intermediates. However, while tuning of their redox potentials, absorption energy, excited-state lifetime and quantum yield are well-known criteria for modifying activity, other factors could be important. Here we show that dynamic ion-pair reorganization controls the reactivity of a photoredox catalyst, [Ir[dF(CF3)ppy]2(dtbpy)]X. Time-resolved dielectric-loss experiments show how counter-ion identity influences excited-state charge distribution, evincing large differences in both the ground- and excited-state dipole moment depending on whether X is a small associating anion (PF6-) that forms a contact-ion pair versus a large one that either dissociates or forms a solvent-separated pair (BArF4-). These differences correlate with the reactivity of the photocatalyst toward both reductive and oxidative electron transfer, amounting to a 4-fold change in selectivity toward oxidation versus reduction. These results suggest that ion pairing could be an underappreciated factor that modulates reactivity in ionic photoredox catalysts.

catalysis↗
NASA NTRS1976

Psychological and physiological correlates of stress: Performance on a cooperative task

The relationship of personality dimensions to performance was investigated. The personality measure used to select subjects, the Barratt impulsiveness scale, is hypothesized to be related to a style of behavior which should affect the trend of choices which various subjects will make. Personality dimensions were specifically examined during performance of a cooperative task, the Prisoner's Dilemma.

Roessler, R.↗
DOE OSTI2023

Switchgrass sward establishment selection is consistent across multiple environments and fertilization levels

Strong selection can occur during switchgrass sward establishment. Differences in establishment selection due to environment or management could provide information on genotype-by-environment variation and could influence strategies for breeding perennial grasses. Leaf samples were collected before sward establishment and from 3-year-old swards for two breeding groups (lowland and hybrid) at three locations. Within two locations, samples were collected from paired fertilized (112 kg N ha –1 ) and unfertilized plots. Allele frequencies from pooled DNA samples were studied through multivariate analysis of variance, genomewide trait predictions (heading date and winter survivorship), and genomically estimated breeding values (GEBVs) for individual sward survival within an independent data set. This study found only minor variations in selection due to location or management. Predicted heading dates of the hybrid population had significant changes due to fertilization and location. There were strong correlations among sward establishment survival GEBVs between growing environments (hybrid r = 0.77; gulf r = 0.97). Interestingly, this study found a small number of genotypes that were over-represented in established swards across all growing environments. This study reinforces a prior report of selection during sward establishment and indicates that only a small degree of establishment selection is location-specific within these diverse growing conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Milestone Report:3.2.2.26 Appliances, HVAC & Water Heating R&D-Select Sorption Technology

The purpose of this report is to select a sorption technology based on recent work completed on characterizing working pairs for both absorption and adsorption technologies based on Global Warming Potential (GWP) of less than 100 (relative to carbon dioxide, 100-year atmospheric life span) and zero Ozone Depletion Potential (ODP). From a total of eighty-three potential working pairs (absorption technology), there were only two candidate working pairs for the absorption technology, and 8 potential working pairs for adsorption technology. After screening these ten potential candidates on the basis of sizes of the desorber, absorber/adsorber, evaporator, condenser, and rectifier (where applicable), the ORNL-Georgia Tech study concluded that best working pairs are NH3-H2O for the most compact system in terms of heat transfer equipment surface area, and NH3-LiNO3 and MeOH-[mmin][DMP] where efficiency is most important. Based on a single-stage absorption and adsorption modeling using the Engineering Equation Solver (EES), the performance of both sorption systems was evaluated from known heat transfer correlations, and thermos-physical properties. Based on these results, the technology chosen is absorption technology. The selected technology is absorption for the reasons cited in Section 4.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

A Pentavalent HIV-1 Subtype C Vaccine Containing Computationally Selected gp120 Strains Improves the Breadth of V1V2 Region Responses

Background: HIV-1 envelope (Env) variable loops 1 and 2 (V1V2) directed non-neutralizing antibodies were a correlate of decreased transmission risk in the RV144 vaccine trial. Thus, the elicitation and breadth of antibody responses against the V1V2 of HIV-1 Env are important considerations for HIV-1 vaccine candidates. The V1V2 region’s highly variable nature and the extensive diversity of subtype C HIV-1 Envelopes (Envs) make the V1V2 response breadth a high priority for HIV-1 vaccine regimens aiming for V1V2-mediated protection in Southern Africa. Here, we determined whether the breadth of the anti-V1V2 vaccine response can be broadened by including HIV-1 Env strains computationally designed to enhance the coverage of subtype C V1V2 sequence diversity. Methods: Three subtype C Env strains were selected to maximize antibody binding coverage while complementing subtype C vaccine gp120s that were given in human clinical trials in South Africa, as well as to improve epitope accessibility. Humoral immunogenicity of a novel trivalent gp120 vaccine immunogen, a bivalent gp120 boost already in clinical trials (1086C and TV1), and a pentavalent (all five gp120s combined) were evaluated in a preclinical immunization study in guinea pigs. The pentavalent combination was further evaluated with alum versus glucopyranosyl lipid adjuvants formulated in squalene-in-water emulsion (GLA-SE) adjuvants in non-human primates. The breadth of the anti-V1V2 response was assessed using an array of cross-subtype variable loops 1&2 (V1V2) scaffold proteins and linear V2 peptides. Results: The breadth of the IgG response against V1V2 antigens of the trivalent and pentavalent groups was comparable, and both were greater than the breadth of the bivalent group. Linear epitope mapping showed that two linear epitopes in V2 were targeted by the vaccinated animals: the V2 hotspot focused at 169K that potentially correlated with decreased HIV-1 risk in RV144 and the V2.2 site (179LDV/I181) that is part of the integrin α4β7 binding site. The bivalent vaccine elicited a significantly higher magnitude of binding to the V2 hotspot compared to the trivalent vaccine whereas the trivalent vaccine elicited significantly higher binding to the V2.2 epitope compared to the bivalent vaccine, while the pentavalent recognized both regions. Conclusions: These results demonstrate that the three new computationally selected subtype C Envs successfully complemented 1086C and TV1 for broader V1V2 antibody responses, and, in concert with adjuvants that stimulate V1V2 responses, can be considered as part of a rationale immunogen design to improve V1V2 IgG coverage in future vaccine trials in South Africa.

Immunology↗
DOE OSTI2016

SU-F-R-33: Can CT and CBCT Be Used Simultaneously for Radiomics Analysis

Purpose: To investigate whether CBCT and CT can be used in radiomics analysis simultaneously. To establish a batch correction method for radiomics in two similar image modalities. Methods: Four sites including rectum, bladder, femoral head and lung were considered as region of interest (ROI) in this study. For each site, 10 treatment planning CT images were collected. And 10 CBCT images which came from same site of same patient were acquired at first radiotherapy fraction. 253 radiomics features, which were selected by our test-retest study at rectum cancer CT (ICC>0.8), were calculated for both CBCT and CT images in MATLAB. Simple scaling (z-score) and nonlinear correction methods were applied to the CBCT radiomics features. The Pearson Correlation Coefficient was calculated to analyze the correlation between radiomics features of CT and CBCT images before and after correction. Cluster analysis of mixed data (for each site, 5 CT and 5 CBCT data are randomly selected) was implemented to validate the feasibility to merge radiomics data from CBCT and CT. The consistency of clustering result and site grouping was verified by a chi-square test for different datasets respectively. Results: For simple scaling, 234 of the 253 features have correlation coefficient ρ>0.8 among which 154 features haveρ>0.9 . For radiomics data after nonlinear correction, 240 of the 253 features have ρ>0.8 among which 220 features have ρ>0.9. Cluster analysis of mixed data shows that data of four sites was almost precisely separated for simple scaling(p=1.29 * 10{sup −7}, χ{sup 2} test) and nonlinear correction (p=5.98 * 10{sup −7}, χ{sup 2} test), which is similar to the cluster result of CT data (p=4.52 * 10{sup −8}, χ{sup 2} test). Conclusion: Radiomics data from CBCT can be merged with those from CT by simple scaling or nonlinear correction for radiomics analysis.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Thermodynamics of Metal Carbonates and Bicarbonates and Their Hydrates for Mg, Ca, Fe, and Cd Relevant to Mineral Energetics

The heats of formation of carbonate, bicarbonate and bicarbonate/hydroxide metal complexes and hydrated versions these complexes of Mg 2+ , Ca 2+ , Fe 2+ , and Cd 2+ are predicted from atomization energies using correlated molecular orbital theory at the CCSD(T) level extrapolated to the complete basis set limit following the Feller-Peterson-Dixon (FPD) approach. Using the calculated gas phase values and the available experimental solid state values, the cohesive energies of selected minerals were calculated. The gas phase decomposition energies into MO, CO 2 and H 2 O follow the order Mg ~ Ca > Cd ~ Fe, and correlate with the hardness of the metal +2 ions. Gas phase hydration energies show that the order is Mg > Fe > Ca ~ Cd. There are a number of bulk hydrated Mg and Ca complexes that occur as minerals but there are few if any for Fe and Cd, suggesting that a number of factors are important in determining the stability of the bulk mineral hydrates. The FPD heats of formation were used to benchmark a range of density functional theory exchange-correlation functionals, including those commonly used in solid state mineral calculations. None of the functionals provided chemical accuracy agreement (± 1 kcal/mol) with the FPD results The best functionals are ωB97X and ωB97X-D with mean average unsigned errors of 10 kcal/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Comparison of solar hard X-ray and UV line and continuum bursts with high time resolution

The close temporal correlation between the ultraviolet line emission from OV (lambda 1371A) and hard X-rays above 30 keV has been previously established from a comparison of data sets from the Ultraviolet Spectrometer and Polarimeter (UVSP) and Hard X-Ray Burst Spectrometer (HXRBS) instruments on Solar Maximum Mission (SMM). Corresponding features were found to be coincident to within 1 s. Following the SMM repair, similar measurements were made for a flare occurring on May 20, 1984, at 0259 UT, this time with UVSP observing in the continuum near 1600A with much higher time resolution (75ms). The simultaneity of several features in this flare were established to better than 0.1 s, thus reinforcing the close relationship between hard X-ray and UV emission. Following the repair of the UVSP wavelength drive, similar measurements were repeated for a flare occurring at 0148 UT on April 24, 1985. This event was observed simultaneously in the OV line, the UV continuum and in hard X-rays by the same SMM instruments. Temporal comparisons of the three data sets show that, for a few selected features, simultaneity of the hard X-ray and UV emissions does exist. However, cross-correlation analyses of the entire data sets indicate that there is a trend for the fastest OV emission features to be delayed with respect to the hard X-rays by approx. 260 ms. On the other hand the fast OV and UV continuum features are simultaneous to within the instrumental uncertainty. The combined results have established the close relationship of the impulsive phase hard X-ray and UV continuum and OV line emissions. They lend support to the argument that both the hard X-ray and UV radiations originate low in the solar atmosphere.

Orwig, L. E.↗
DOE OSTI2022

Understanding the Reactivity, Selectivity, and Deactivation of Frustrated Lewis Pairs for Semihydrogenation of Acetylene

A good catalyst for semihydrogenation of alkynes must preclude both over-hydrogenation of alkene to alkane and isomerization to the other alkene isomer. In addition, it should balance the trade-off between selectivity and activity. In 2013, the Repo and Pápai groups reported a frustrated Lewis pair (FLP) (1-NMe 2 -2-B(C 6 F 5 ) 2 -C 6 H 4 ), 1, which is a metal-free catalyst and for the first time shows excellent reactivity for the hydrogenation of internal alkynes. However, it is unreactive for terminal alkynes. In this work, we have designed 13 FLPs, a–m, based on 1 by varying the Lewis base site with N and P and the Lewis acid site with B, Al, Ga, and In and replacing pentafluorophenyl with 1,3,5-trifluorophenyl, phenyl, or trifluoromethyl. We apply density functional theory to study the activity, selectivity, and deactivation of FLP 1-m for acetylene semihydrogenation. The catalytic cycle consists of three steps: (1) alkyne insertion, (2) H 2 heterolysis, and (3) intramolecular protonation. We found the activity does not change much by the modification of bulky ligands, while it decreases with the direct replacement of LA and LB sites. The overall activity depends on steps 1 and 3, which are, respectively, positively and negatively linear correlated with the charge of the Lewis acid site. Most of the FLPs in this work show comparable or better selectivity for semihydrogenation of acetylene than 1. FLP deactivation is due to the strong binding of acetylene and the elimination of electron-withdrawing bulky ligands at the preactivated catalyst rather than at activated catalysts. Furthermore, taking the selectivity and stability of FLPs into account, we predict d and k are potentially active for terminal alkynes.

02 PETROLEUM↗
DOE OSTI2016

Inter‐Fullerene Electronic Coupling Controls the Efficiency of Photoinduced Charge Generation in Organic Bulk Heterojunctions

Photoinduced charge generation (PCG) dynamics are notoriously difficult to correlate with specific molecular properties in device relevant polymer:fullerene organic photovoltaic blend films due to the highly complex nature of the solid state blend morphology. Here, this study uses six judiciously selected trifluoromethylfullerenes blended with the prototypical polymer poly(3‐hexylthiophene) and measure the PCG dynamics in 50 fs–500 ns time scales with time‐resolved microwave conductivity and femtosecond transient absorption spectroscopy. The isomeric purity and thorough chemical characterization of the fullerenes used in this study allow for a detailed correlation between molecular properties, driving force, local intermolecular electronic coupling and, ultimately, the efficiency of PCG yield. The findings show that the molecular design of the fullerene not only determines inter‐fullerene electronic coupling, but also influences the decay dynamics of free holes in the donor phase even when the polymer microstructure remains unchanged.

Larson, Bryon W.↗
DOE OSTI2023

Elucidating the Effect of Ion Exchange Protocol on the Copper Exchange Efficacy, Copper Siting, and SCR activity in Cu-SSZ-13

The influence of the copper ion exchange protocol on SCR activity of SSZ-13 is quantified. Using the same parent SSZ-13 zeolite, four exchange protocols are used to assess how exchange protocol impacts metal uptake and SCR activity. Large differences in the SCR activity, nearly 30 percentage points at 160 °C at constant copper content, are observed for different exchange protocols implying that different exchange protocols lead to different copper species. Hydrogen temperature programmed reduction on selected samples and infrared spectroscopy of CO binding corroborates this conclusion as the reactivity at 160 °C correlates with the intensity of the IR band at 2162 cm -1 . DFT-based calculations show that such an IR assignment is consistent with CO adsorbed on a Cu(I) cation within an eight-membered ring. This work shows that SCR activity can be influenced by the ion exchange process even when different protocols lead to the same metal loading. Perhaps most interesting, a protocol used to generate Cu-MOR for methane to methanol studies led to the most active catalyst both on a unit mass or unit mole copper basis. This points to a yet not recognized means to tailor catalyst activity as the open literature is silent on this issue.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Prediction of correlation energies using variational subspace valence bond

In the variational subspace valence bond (VSVB) [G. D. Fletcher, J. Chem. Phys. 142, 134112 (2015)] method, the electronic orbitals comprising the wave function correspond to chemically meaningful objects, such as bonds, lone pairs, atomic cores, and so on. Selected regions of a molecule (for example, a single chemical bond, as opposed to all the bonds) can be modeled with different levels of basis set and possible methods for modeling correlation from the other regions. The interactions between the components of a molecule (say, a bond and a neighboring orbital) can then be studied in detail for their impact on a chemical phenomenon while avoiding the expense of necessarily applying the higher levels and methods to the entire molecule. Here, this work presents the theoretical basis for modeling correlation effects between specific electron pairs by incorporating terms in the inter-electronic coordinates (“r 12 ”) into VSVB. The approach is validated with calculations on small systems using single-reference wave functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Engineering two-dimensional superconductivity and Rashba spin–orbit coupling in LaAlO 3 /SrTiO 3 quantum wells by selective orbital occupancy

We find the discovery of two-dimensional electron gases (2DEGs) at oxide interfaces—involving electrons in narrow d-bands—has broken new ground, enabling the access to correlated states that are unreachable in conventional semiconductors based on s- and p- electrons. There is a growing consensus that emerging properties at these novel quantum wells—such as 2D superconductivity and magnetism—are intimately connected to specific orbital symmetries in the 2DEG sub-band structure. Here we show that crystal orientation allows selective orbital occupancy, disclosing unprecedented ways to tailor the 2DEG properties. By carrying out electrostatic gating experiments in LaAlO 3 /SrTiO 3 wells of different crystal orientations, we show that the spatial extension and anisotropy of the 2D superconductivity and the Rashba spin–orbit field can be largely modulated by controlling the 2DEG sub-band filling. Such an orientational tuning expands the possibilities for electronic engineering of 2DEGs at LaAI0 3 /SrTio 3 interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Plasmon-Driven Ammonia Decomposition on Pd(111): Hole Transfer’s Role in Changing Rate-Limiting Steps

Here, ammonia (NH 3 ) has the potential to be a hydrogen carrier because it can be transported and stored with ease, but only if it also can be decomposed easily when needed. Understanding how to control the frequently rate-limiting N–H bond breaking and N–N bond forming on catalytic surfaces may help design efficient means for NH 3 decomposition. Yuan et al. recently demonstrated photocatalytically selective N–H bond breaking in NH 3 on plasmon-driven aluminum–palladium (Al–Pd) antenna–reactor heterostructures. Using embedded correlated wavefunction (ECW) theory, we predict that the rate-determining step (RDS) for NH 3 decomposition on Pd(111) via thermocatalysis (dissociating the first N–H bond, *NH 3 → *NH 2 + *H, in the ground state, where * means adsorbed) differs from that via photocatalysis (dissociating the second N–H bond, *NH 2 → *NH + *H, in the excited state). This result is consistent with the measured catalytic efficiency and selectivity of NH 3 -deuterium (D 2 ) exchange reactions (an indirect way to measure N–H bond breaking) on Al–Pd heterodimers. We also determine the origin of the observed selectivity of thermocatalysis and photocatalysis on Pd(111) toward doubly deuterated (NHD 2 ) and monodeuterated (NH 2 D) products, respectively, and explore viability of the full NH 3 decomposition path, also via ECW theory. Additionally, we predict that the associative desorption of *N as N 2 from Pd(111) is extremely difficult in thermocatalysis at least at low surface coverages; metal-to-adsorbate hole transfer in photocatalysis stabilizes the transition state for the first N–H bond dissociation, shifting the RDS to the second N–H bond breaking. Furthermore, the redistribution of electrons around *N upon excitation reduces the electron density in the Pd–N bonds, which may lower the barrier for N 2 associative desorption in photocatalysis. Thus, light-induced, plasmon-mediated, excited-state hole transfer may provide an efficient mechanism to accelerate NH 3 decomposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Strong Clustering of Lyman Break Galaxies around Luminous Quasars at Z ∼ 4

In the standard picture of structure formation, the first massive galaxies are expected to form at the highest peaks of the density field, which constitute the cores of massive proto-clusters. Luminous quasars (QSOs) at z ∼ 4 are the most strongly clustered population known, and should thus reside in massive dark matter halos surrounded by large overdensities of galaxies, implying a strong QSO–galaxy cross-correlation function. We observed six z ∼ 4 QSO fields with VLT/FORS, exploiting a novel set of narrow-band filters custom designed to select Lyman Break Galaxies (LBGs) in a thin redshift slice of Δz∼0.3, mitigating the projection effects that have limited the sensitivity of previous searches for galaxies around z≳4 QSOs. We find that LBGs are strongly clustered around QSOs, and present the first measurement of the QSO–LBG cross-correlation function at z ∼ 4, on scales of 0.1≲R≲9 h{sup −1} Mpc (comoving). Assuming a power-law form for the cross-correlation function ξ=(r/r{sub 0}{sup QG}){sup γ}, we measure r{sub 0}{sup QG}=8.83{sub −1.51}{sup +1.39} h{sup −1} Mpc for a fixed slope of γ=2.0. This result is in agreement with the expected cross-correlation length deduced from measurements of the QSO and LBG auto-correlation function, and assuming a deterministic bias model. We also measure a strong auto-correlation of LBGs in our QSO fields, finding r{sub 0}{sup GG}=21.59{sub −1.69}{sup +1.72} h{sup −1} Mpc for a fixed slope of γ=1.5, which is ∼4 times larger than the LBG auto-correlation length in blank fields, providing further evidence that QSOs reside in overdensities of LBGs. Our results qualitatively support a picture where luminous QSOs inhabit exceptionally massive (M{sub halo}>10{sup 12} M{sub ⊙}) dark matter halos at z ∼ 4.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Quantum Solvers for Plane-Wave Hamiltonians: Abridging Virtual Spaces Through the Optimization of Pairwise Correlations

For many-body methods such as MCSCF and CASSCF, in which the number of one-electron orbitals is optimized and independent of the basis set used, there are no problems with using plane-wave basis sets. However, for methods currently used in quantum computing such as select configuration interaction (CI) and coupled cluster (CC) methods, it is necessary to have a virtual space that is able to capture a significant amount of electron-electron correlation in the system. The virtual orbitals in a pseudopotential plane-wave Hartree–Fock calculation, because of Coulomb repulsion, are often scattering states that interact very weakly with the filled orbitals. As a result, very little correlation energy is captured from them. The use of virtual spaces derived from the one-electron operators has also been tried, and while some correlations are captured, the amount is quite low. To overcome these limitations, we have been developing new classes of algorithms to define virtual spaces by optimizing orbitals from small pairwise CI Hamiltonians, which we term as correlation optimized virtual orbitals with the abbreviation COVOs. With these procedures, we have been able to derive virtual spaces, containing only a few orbitals, which are able to capture a significant amount of correlation. The focus in this manuscript is on using these derived basis sets to target full CI (FCI) quality results for H2 on near-term quantum computers. However, the initial results for this approach were promising. We were able to obtain good agreement with FCI/cc-pVTZ results for this system with just 4 virtual orbitals, using both FCI and quantum simulations. The quality of the results using COVOs suggests that it may be possible to use them in other many-body approaches, including coupled cluster and Møller–Plesset perturbation theories, and open up the door to many-body calculations for pseudopotential plane-wave basis set methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Method to Regioselectively Iodine-Tag Free-Phenolic Aromatic End-Groups in Lignin for 1 H– 13 C-HSQC NMR Analysis

Phenolic end-groups on lignin molecules are vital sites for continued lignification, their influence over lignin molecular properties, their ability to enhance lignin degradation, and their potential for derivatization to produce lignin materials. Here we use iodination to regioselectively tag, and HSQC-NMR to monitor, guaiacyl phenolic aromatic end-groups in lignins. Using dimeric lignin models, iodination at the 5-position of the phenolic ring was shown to be clean, and almost quantitative. Additionally, the 6-position C/H correlation peak shifted downfield in both carbon and proton dimensions in HSQC spectra. As phenolic aromatic rings could be selectively iodinated, and as their C6/H6 aromatic signals appear in a clear region of HSQC NMR spectra (different from the original position), we would have a new method for tagging and analyzing such phenolic aromatic rings in lignins if the method could be applied to the polymer. The new tagging approach was therefore applied to a synthetic guaiacyl lignin polymer (DHP) and a milled wood lignin (MWL) isolated from Japanese cedar ( Cryptomeria japonica ). The derivatization proceeded directly in the NMR tube, without needing isolation or purification, from which HSQC-NMR revealed that the diagnostic C6/H6 correlations matched one from the dimeric model compound. This phenolic unit tagging method adds a useful method to the lignin structural analysis toolbox, helping to gain a better understanding of lignin’s phenolic end-units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Rapid estimation of 4DCT motion-artifact severity based on 1D breathing-surrogate periodicity

Purpose: Motion artifacts are common in patient four-dimensional computed tomography (4DCT) images, leading to an ill-defined tumor volume with large variations for radiotherapy treatment and a poor foundation with low imaging fidelity for studying respiratory motion. The authors developed a method to estimate 4DCT image quality by establishing a correlation between the severity of motion artifacts in 4DCT images and the periodicity of the corresponding 1D respiratory waveform (1DRW) used for phase binning in 4DCT reconstruction. Methods: Discrete Fourier transformation (DFT) was applied to analyze 1DRW periodicity. The breathing periodicity index (BPI) was defined as the sum of the largest five Fourier coefficients, ranging from 0 to 1. Distortional motion artifacts (excluding blurring) of cine-scan 4DCT at the junctions of adjacent couch positions around the diaphragm were classified in three categories: incomplete, overlapping, and duplicate anatomies. To quantify these artifacts, discontinuity of the diaphragm at the junctions was measured in distance and averaged along six directions in three orthogonal views. Artifacts per junction (APJ) across the entire diaphragm were calculated in each breathing phase and phase-averaged APJ{sup ¯}, defined as motion-artifact severity (MAS), was obtained for each patient. To make MAS independent of patient-specific motion amplitude, two new MAS quantities were defined: MAS{sup D} is normalized to the maximum diaphragmatic displacement and MAS{sup V} is normalized to the mean diaphragmatic velocity (the breathing period was obtained from DFT analysis of 1DRW). Twenty-six patients’ free-breathing 4DCT images and corresponding 1DRW data were studied. Results: Higher APJ values were found around midventilation and full inhalation while the lowest APJ values were around full exhalation. The distribution of MAS is close to Poisson distribution with a mean of 2.2 mm. The BPI among the 26 patients was calculated with a value ranging from 0.25 to 0.93. The DFT calculation was within 3 s per 1DRW. Correlations were found between 1DRW periodicity and 4DCT artifact severity: −0.71 for MAS{sup D} and −0.73 for MAS{sup V}. A BPI greater than 0.85 in a 1DRW suggests minimal motion artifacts in the corresponding 4DCT images. Conclusions: The breathing periodicity index and motion-artifact severity index are introduced to assess the relationship between 1DRW and 4DCT. A correlation between 1DRW periodicity and 4DCT artifact severity has been established. The 1DRW periodicity provides a rapid means to estimate 4DCT image quality. The rapid 1DRW analysis and the correlative relationship can be applied prospectively to identify irregular breathers as candidates for breath coaching prior to 4DCT scan and retrospectively to select high-quality 4DCT images for clinical motion-management research.

60 APPLIED LIFE SCIENCES↗