Phantom investigation of 3D motion-dependent volume aliasing during CT simulation for radiation therapy planning

PURPOSE: To quantify volumetric and positional aliasing during non-gated fast- and slow-scan acquisition CT in the presence of 3D target motion. METHODS: Single-slice fast, single-slice slow, and multi-slice fast scan helical CTs were acquired of dynamic spherical targets (1 and 3.15 cm in diameter), embedded in an anthropomorphic phantom. 3D target motions typical of clinically observed tumor motion parameters were investigated. Motion excursions included ± 5, ± 10, and ± 15 mm displacements in the S-I direction synchronized with constant displacements of ± 5 and ± 2 mm in the A-P and lateral directions, respectively. For each target, scan technique, and motion excursion, eight different initial motion-to-scan phase relationships were investigated. RESULTS: An anticipated general trend of target volume overestimation was observed. The mean percentage overestimation of the true physical target volume typically increased with target motion amplitude and decreasing target diameter. Slow-scan percentage overestimations were larger, and better approximated the time-averaged motion envelope, as opposed to fast-scans. Motion induced centroid misrepresentation was greater in the S-I direction for fast-scan techniques, and transaxial direction for the slow-scan technique. Overestimation is fairly uniform for slice widths < 5 mm, beyond which there is gross overestimation. CONCLUSION: Non-gated CT imaging of targets describing clinically relevant, 3D motion results in aliased overestimation of the target volume and misrepresentation of centroid location, with little or no correlation between the physical target geometry and the CT-generated target geometry. Slow-scan techniques are a practical method for characterizing time-averaged target position. Fast-scan techniques provide a more reliable, albeit still distorted, target margin

Enhanced Fe-centered redox flexibility in Fe–Ti heterobimetallic complexes

Previously, we reported the synthesis of Ti[N(o-(NCH2P(iPr)2)C6H4)3] and the Fe–Ti complex, FeTi[N(o-(NCH2P(iPr)2)C6H4)3], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe–Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at −2.16 and −1.36 V (versus Fc/Fc+), respectively. Two isostructural redox members, [FeTiL]+ and [FeTiL]− (2ox and 2red, respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL]+ complex (1ox). The solid-state structures of the [FeTiL]+/0/– series feature short metal–metal bonds, ranging from 1.94–2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL]+,0,– series are primarily Fe-based and that the polarized Fe–Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%)

Reduction of CO\u3csub\u3e2\u3c/sub\u3e By a Masked Two-Coordinate Cobalt(I) Complex and Characterization of a Proposed Oxodicobalt(II) Intermediate

Fixation and chemical reduction of CO2 are important for utilization of this abundant resource, and understanding the detailed mechanism of C-O cleavage is needed for rational development of CO2 reduction methods. Here, we describe a detailed analysis of the mechanism of the reaction of a masked two-coordinate cobalt(i) complex, LtBuCo (where LtBu = 2,2,6,6-tetramethyl-3,5-bis[(2,6-diisopropylphenyl)imino]hept-4-yl), with CO2, which yields two products of C-O cleavage, the cobalt(i) monocarbonyl complex LtBuCo(CO) and the dicobalt(ii) carbonate complex (LtBuCo)2(μ-CO3). Kinetic studies and computations show that the κN,η6-arene isomer of LtBuCo rearranges to the κ2N,N′ binding mode prior to binding of CO2, which contrasts with the mechanism of binding of other substrates to LtBuCo. Density functional theory (DFT) studies show that the only low-energy pathways for cleavage of CO2 proceed through bimetallic mechanisms, and DFT and highly correlated domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) calculations reveal the cooperative effects of the two metal centers during facile C-O bond rupture. A plausible intermediate in the reaction of CO2 with LtBuCo is the oxodicobalt(II) complex LtBuCoOCoLtBu, which has been independently synthesized through the reaction of LtBuCo with N2O. The rapid reaction of LtBuCoOCoLtBu with CO2 to form the carbonate product indicates that the oxo species is kinetically competent to be an intermediate during CO2 cleavage by LtBuCo. LtBuCoOCoLtBu is a novel example of a thoroughly characterized molecular cobalt-oxo complex where the cobalt ions are clearly in the +2 oxidation state. Its nucleophilic reactivity is a consequence of high charge localization on the μ-oxo ligand between two antiferromagnetically coupled high-spin cobalt(ii) centers, as characterized by DFT and multireference complete active space self-consistent field (CASSCF) calculations

The Freshman, vol. 4, no. 20

The Freshman was a weekly, student newsletter issued on Mondays throughout the academic year. The newsletter included calendar notices, coverage of campus social events, lectures, and athletic teams. The intent of the publication was to create unity, a sense of community, and class spirit among first year students. The Class of 1937 run of The Freshman featured original cover art by sketch artist Jack Frost (John Edward Frost, 1915-1997), who was born in Eastport, Maine. He attended the University of Maine for only a single academic year before moving to Massachusetts to work for the Boston Herald. Frost later became a columnist and illustrator for the Boston Post

The Freshman, vol. 4, no. 23

The Freshman was a weekly, student newsletter issued on Mondays throughout the academic year. The newsletter included calendar notices, coverage of campus social events, lectures, and athletic teams. The intent of the publication was to create unity, a sense of community, and class spirit among first year students. The Class of 1937 run of The Freshman featured original cover art by sketch artist Jack Frost (John Edward Frost, 1915-1997), who was born in Eastport, Maine. He attended the University of Maine for only a single academic year before moving to Massachusetts to work for the Boston Herald. Frost later became a columnist and illustrator for the Boston Post

The Freshman, vol. 4, no. 19

The Freshman was a weekly, student newsletter issued on Mondays throughout the academic year. The newsletter included calendar notices, coverage of campus social events, lectures, and athletic teams. The intent of the publication was to create unity, a sense of community, and class spirit among first year students. Rush wraps up as members of the Freshman class decide which frats to pledge. The Class of 1937 run of The Freshman featured original cover art by sketch artist Jack Frost (John Edward Frost, 1915-1997), who was born in Eastport, Maine. He attended the University of Maine for only a single academic year before moving to Massachusetts to work for the Boston Herald. Frost later became a columnist and illustrator for the Boston Post

The Freshman, vol. 4, no. 25

The Freshman was a weekly, student newsletter issued on Mondays throughout the academic year. The newsletter included calendar notices, coverage of campus social events, lectures, and athletic teams. The intent of the publication was to create unity, a sense of community, and class spirit among first year students. The Class of 1937 run of The Freshman featured original cover art by sketch artist Jack Frost (John Edward Frost, 1915-1997), who was born in Eastport, Maine. He attended the University of Maine for only a single academic year before moving to Massachusetts to work for the Boston Herald. Frost later became a columnist and illustrator for the Boston Post

The Freshman, vol. 4, no. 26

The Freshman was a weekly, student newsletter issued on Mondays throughout the academic year. The newsletter included calendar notices, coverage of campus social events, lectures, and athletic teams. The intent of the publication was to create unity, a sense of community, and class spirit among first year students

The Freshman, vol. 4, no. 24

The Freshman was a weekly, student newsletter issued on Mondays throughout the academic year. The newsletter included calendar notices, coverage of campus social events, lectures, and athletic teams. The intent of the publication was to create unity, a sense of community, and class spirit among first year students. The Class of 1937 run of The Freshman featured original cover art by sketch artist Jack Frost (John Edward Frost, 1915-1997), who was born in Eastport, Maine. He attended the University of Maine for only a single academic year before moving to Massachusetts to work for the Boston Herald. Frost later became a columnist and illustrator for the Boston Post

The Freshman, vol. 4, no. 26

The Freshman was a weekly, student newsletter issued on Mondays throughout the academic year. The newsletter included calendar notices, coverage of campus social events, lectures, and athletic teams. The intent of the publication was to create unity, a sense of community, and class spirit among first year students