Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules.

The chemiluminescent reactions of the group 3 metals Sc and Y with F2, Cl2, Br2, ClF, ICl (Sc), IBr (Y), and SF6 and La with F2, SF6, Cl2, and ClF have been studied at low pressures (6 × 10-6 to 4 × 10-4 Torr) using a beam-gas arrangement and extended to the 10-3 Torr multiple collision pressure range. Contrary to previous reports, the observed chemiluminescent spectra are primarily attributed to emission from the metal monohalides. Extensive pressure and temperature dependence studies and high-level correlated molecular orbital theory calculations of the bond dissociation energies support this conclusion and the attribution of the chemiluminescence. Evidence for the "selective" production of a monohalide excited electronic state is obtained for several of the Sc and Y reactions. All reactions producing the metal monofluorides are first order with respect to the oxidant, while reactions producing the monochlorides and monobromides are found to be "faster than first order" with respect to the oxidant. This difference is associated with the metal halide bond dissociation energies and the metal halide product internal density of states. Analysis of the temperature dependence for six representative reactions indicates that the "selective" excited-state formation of the metal monohalides proceeds via a direct mechanism with negligible activation energy. We compare and contrast the present results with previous experiments and interpretations which have assigned the selective emission from these systems to the group 3 dihalides produced in a two-step reaction sequence analogous to an electron jump process. The current results suggest a distinctly different interpretation of the observed processes in these systems. The observed selectivity observed in these studies is remarkable given the significant number of known and potential excited states in the scandium and yttrium halides as well as their different electronic configurations.

Excited Electronic State Cross Sections for Group 3 Halide and Oxide Production: Evaluating Relative Excited-State Quantum Yields.

The cross sections for excited-state formation from the reactions of the group 3 metals, Sc, Y, and La, with F2 and NO2, are evaluated from experimental data. Detailed calibrations indicate that the cross sections for MF formation greatly exceed those for MO formation. The experimentally determined cross sections are compared to upper bounds for total reactive cross sections. Based on this comparison, the ratios of excited state to ground state product formation (quantum yield) are evaluated. The reactions of Sc and Y with F2, which produce excited states selectively, may represent candidates to create a population inversion for use in a chemical laser.

Quantitative analysis of vascular heterogeneity in breast lesions using contrast-enhanced 3-D harmonic and subharmonic ultrasound imaging.

Ability to visualize breast lesion vascularity and quantify the vascular heterogeneity using contrast-enhanced 3-D harmonic (HI) and subharmonic (SHI) ultrasound imaging was investigated in a clinical population. Patients (n = 134) identified with breast lesions on mammography were scanned using power Doppler imaging, contrast-enhanced 3-D HI, and 3-D SHI on a modified Logiq 9 scanner (GE Healthcare). A region of interest corresponding to ultrasound contrast agent flow was identified in 4D View (GE Medical Systems) and mapped to raw slice data to generate a map of time-intensity curves for the lesion volume. Time points corresponding to baseline, peak intensity, and washout of ultrasound contrast agent were identified and used to generate and compare vascular heterogeneity plots for malignant and benign lesions. Vascularity was observed with power Doppler imaging in 84 lesions (63 benign and 21 malignant). The 3-D HI showed flow in 8 lesions (5 benign and 3 malignant), whereas 3-D SHI visualized flow in 68 lesions (49 benign and 19 malignant). Analysis of vascular heterogeneity in the 3-D SHI volumes found benign lesions having a significant difference in vascularity between central and peripheral sections (1.71 ± 0.96 vs. 1.13 ± 0.79 dB, p < 0.001, respectively), whereas malignant lesions showed no difference (1.66 ± 1.39 vs. 1.24 ± 1.14 dB, p = 0.24), indicative of more vascular coverage. These preliminary results suggest quantitative evaluation of vascular heterogeneity in breast lesions using contrast-enhanced 3-D SHI is feasible and able to detect variations in vascularity between central and peripheral sections for benign and malignant lesions.

Chronic liver disease: noninvasive subharmonic aided pressure estimation of hepatic venous pressure gradient.

PURPOSE: To compare subharmonic aided pressure estimation (SHAPE) with pressure catheter-based measurements in human patients with chronic liver disease undergoing transjugular liver biopsy. MATERIALS AND METHODS: This HIPAA-compliant study had U.S. Food and Drug Administration and institutional review board approval, and written informed consent was obtained from all participants. Forty-five patients completed this study between December 2010 and December 2011. A clinical ultrasonography (US) scanner was modified to obtain SHAPE data. After transjugular liver biopsy with pressure measurements as part of the standard of care, 45 patients received an infusion of a microbubble US contrast agent and saline. During infusion, SHAPE data were collected from a portal and hepatic vein and were compared with invasive measurements. Correlations between data sets were determined by using the Pearson correlation coefficient, and statistical significance between groups was determined by using the Student t test. RESULTS: The 45 study patients included 27 men and 18 women (age range, 19-71 years; average age, 55.8 years). The SHAPE gradient between the portal and hepatic veins was in good overall agreement with the hepatic venous pressure gradient (HVPG) (R = 0.82). Patients at increased risk for variceal hemorrhage (HVPG ≥ 12 mm Hg) had a significantly higher mean subharmonic gradient than patients with lower HVPGs (1.93 dB ± 0.61 [standard deviation] vs -1.47 dB ± 0.29, P < .001), with a sensitivity of 100% and a specificity of 81%, indicating that SHAPE may be a useful tool for the diagnosis of clinically important portal hypertension. CONCLUSION: Preliminary results show SHAPE to be an accurate noninvasive technique for estimating portal hypertension.

Investigating the efficacy of subharmonic aided pressure estimation for portal vein pressures and portal hypertension monitoring.

The efficacy of using subharmonic emissions from Sonazoid microbubbles (GE Healthcare, Oslo, Norway) to track portal vein pressures and pressure changes was investigated in 14 canines using either slow- or high-flow models of portal hypertension (PH). A modified Logiq 9 scanner (GE Healthcare, Milwaukee, WI, USA) operating in subharmonic mode (f(transmit): 2.5 MHz, f(receive): 1.25 MHz) was used to collect radiofrequency data at 10-40% incident acoustic power levels with 2-4 transmit cycles (in triplicate) before and after inducing PH. A pressure catheter (Millar Instruments, Inc., Houston, TX, USA) provided reference portal vein pressures. At optimum insonification, subharmonic signal amplitude changes correlated with portal vein pressure changes; r ranged from -0.82 to -0.94 and from -0.70 to -0.73 for PH models considered separately or together, respectively. The subharmonic signal amplitudes correlated with absolute portal vein pressures (r: -0.71 to -0.79). Statistically significant differences between subharmonic amplitudes, before and after inducing PH, were noted (p ≤ 0.01). Portal vein pressures estimated using subharmonic aided pressure estimation did not reveal significant differences (p > 0.05) with respect to the pressures obtained using the Millar pressure catheter. Subharmonic-aided pressure estimation may be useful clinically for portal vein pressure monitoring.

Multi-modality 3D breast imaging with X-Ray tomosynthesis and automated ultrasound.

This study evaluated the utility of 3D automated ultrasound in conjunction with 3D digital X-Ray tomosynthesis for breast cancer detection and assessment, to better localize and characterize lesions in the breast. Tomosynthesis image volumes and automated ultrasound image volumes were acquired in the same geometry and in the same view for 27 patients. 3 MQSA certified radiologists independently reviewed the image volumes, visually correlating the images from the two modalities with in-house software. More sophisticated software was used on a smaller set of 10 cases, which enabled the radiologist to draw a 3D box around the suspicious lesion in one image set and isolate an anatomically correlated, similarly boxed region in the other modality image set. In the primary study, correlation was found to be moderately useful to the readers. In the additional study, using improved software, the median usefulness rating increased and confidence in localizing and identifying the suspicious mass increased in more than half the cases. As automated scanning and reading software techniques advance, superior results are expected.

Automated ultrasound scanning on a dual-modality breast imaging system: coverage and motion issues and solutions.

OBJECTIVE: We are developing an automated ultrasound imaging-mammography system wherein a digital mammography unit has been augmented with a motorized ultrasound transducer carriage above a special compression paddle. Challenges of this system are acquiring complete coverage of the breast and minimizing motion. We assessed these problems and investigated methods to increase coverage and stabilize the compressed breast. METHODS: Visual tracings of the breast-to-paddle contact area and breast periphery were made for 10 patients to estimate coverage area. Various motion artifacts were evaluated in 6 patients. Nine materials were tested for coupling the paddle to the breast. Fourteen substances were tested for coupling the transducer to the paddle in lateral-to-medial and medial-to-lateral views and filling the gap between the peripheral breast and paddle. In-house image registration software was used to register adjacent ultrasound sweeps. RESULTS: The average breast contact area was 56%. The average percentage of the peripheral air gap filled with ultrasound gel was 61%. Shallow patient breathing proved equivalent to breath holding, whereas speech and sudden breathing caused unacceptable artifacts. An adhesive spray that preserves image quality was found to be best for coupling the breast to the paddle and minimizing motion. A highly viscous ultrasound gel proved most effective for coupling the transducer to the paddle for lateral-to-medial and medial-to-lateral views and for edge fill-in. CONCLUSIONS: The challenges of automated ultrasound scanning in a multimodality breast imaging system have been addressed by developing methods to fill in peripheral gaps, minimize patient motion, and register and reconstruct multisweep ultrasound image volumes.