Photochemistry of Furyl- and Thienyldiazomethanes: Spectroscopic Characterization of Triplet 3-Thienylcarbene

Photolysis (λ \u3e 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N2 at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm–1, |E/hc| = 0.0554 cm–1; |D/hc| = 0.579 cm–1, |E/hc| = 0.0315 cm–1). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon—an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λmax = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C5H4S or C5H4O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively)

Areas of normal pulmonary parenchyma on HRCT exhibit increased FDG PET signal in IPF patients

Purpose: Patients with idiopathic pulmonary fibrosis (IPF) show increased PET signal at sites of morphological abnormality on high-resolution computed tomography (HRCT). The purpose of this investigation was to investigate the PET signal at sites of normal-appearing lung on HRCT in IPF. Methods: Consecutive IPF patients (22 men, 3 women) were prospectively recruited. The patients underwent 18F-FDG PET/HRCT. The pulmonary imaging findings in the IPF patients were compared to the findings in a control population. Pulmonary uptake of 18F-FDG (mean SUV) was quantified at sites of morphologically normal parenchyma on HRCT. SUVs were also corrected for tissue fraction (TF). The mean SUV in IPF patients was compared with that in 25 controls (patients with lymphoma in remission or suspected paraneoplastic syndrome with normal PET/CT appearances). Results: The pulmonary SUV (mean ± SD) uncorrected for TF in the controls was 0.48 ± 0.14 and 0.78 ± 0.24 taken from normal lung regions in IPF patients (p < 0.001). The TF-corrected mean SUV in the controls was 2.24 ± 0.29 and 3.24 ± 0.84 in IPF patients (p < 0.001). Conclusion: IPF patients have increased pulmonary uptake of 18F-FDG on PET in areas of lung with a normal morphological appearance on HRCT. This may have implications for determining disease mechanisms and treatment monitoring. © 2013 The Author(s)

Design of a low-dose, stationary, tomographic Molecular Breast Imaging system using 3D position sensitive CZT detectors

Molecular Breast Imaging (MBI) has been shown to have high sensitivity for lesion detection, particularly in patients with dense breasts where conventional mammography is limited. However, relatively high radiation dose and long imaging time are limiting factors. Most current MBI systems are based on planar imaging. Improved performance can be achieved using tomographic techniques, which normally involve detector motion. Our goal is to develop a low-dose stationary tomographic MBI system with similar or better performance in terms of lesion detection compared to planar MBI. The proposed system utilizes two opposing CZT detectors with high intrinsic resolution and depth of interaction (DOI) capability, combined with densely packed multi-pinhole collimators. This leads to improved efficiency and adequate angular sampling, but also to significant multiplexing (MX), which can result in artefacts. We have developed de-MX algorithms that take advantage of the DOI information. We have performed both analytic and Monte Carlo simulations to demonstrate the feasibility, optimize the design and investigate the expected performance of the proposed system. Lesion detectability was preserved with reduction of acquisition time (or radiation dose) by a factor of 2 compared to planar images at the lowest reported dose. The first prototype is under evaluation at Kromek

Integration of advanced 3D SPECT modelling for pinhole collimators into the open-source STIR framework

Single-photon emission computed tomography (SPECT) systems with pinhole collimators are becoming increasingly important in clinical and preclinical nuclear medicine investigations as they can provide a superior resolution-sensitivity trade-off compared to conventional parallel-hole and fanbeam collimators. Previously, open-source software did not exist for reconstructing tomographic images from pinhole-SPECT datasets. A 3D SPECT system matrix modelling library specific for pinhole collimators has recently been integrated into STIR—an open-source software package for tomographic image reconstruction. The pinhole-SPECT library enables corrections for attenuation and the spatially variant collimator–detector response by incorporating their effects into the system matrix. Attenuation correction can be calculated with a simple single line-of-response or a full model. The spatially variant collimator–detector response can be modelled with point spread function and depth of interaction corrections for increased system matrix accuracy. In addition, improvements to computational speed and memory requirements can be made with image masking. This work demonstrates the flexibility and accuracy of STIR’s support for pinhole-SPECT datasets using measured and simulated single-pinhole SPECT data from which reconstructed images were analysed quantitatively and qualitatively. The extension of the open-source STIR project with advanced pinhole-SPECT modelling will enable the research community to study the impact of pinhole collimators in several SPECT imaging scenarios and with different scanners

Systematic Evaluation of the Impact of Involuntary Motion in Whole Body Dynamic PET

Involuntary patient motion can happen in dynamic whole body (DWB) PET due to long scanning times, which may cause inaccurate quantification of tissue parameters. To quantify the impact on Patlak parameters, we simulated dynamic data using patient-derived motion fields, systematically introducing the motion at different passes of the dynamic scan, both inter and intra-frame. Estimated parameters are compared against the ground truth. Results show that errors can be large, even for small motion. Caution is advised when quantitatively evaluating DWB-PET images, if any motion has been detected

Towards accurate partial volume correction in (99m}^Tc oncology SPECT: perturbation for case-specific resolution estimation

BACKGROUND: Currently, there is no consensus on the optimal partial volume correction (PVC) algorithm for oncology imaging. Several existing PVC methods require knowledge of the reconstructed resolution, usually as the point spread function (PSF)-often assumed to be spatially invariant. However, this is not the case for SPECT imaging. This work aimed to assess the accuracy of SPECT quantification when PVC is applied using a case-specific PSF. METHODS: Simulations of SPECT [Formula: see text]Tc imaging were performed for a range of activity distributions, including those replicating typical clinical oncology studies. Gaussian PSFs in reconstructed images were estimated using perturbation with a small point source. Estimates of the PSF were made in situations which could be encountered in a patient study, including; different positions in the field of view, different lesion shapes, sizes and contrasts, noise-free and noisy data. Ground truth images were convolved with the perturbation-estimated PSF, and with a PSF reflecting the resolution at the centre of the field of view. Both were compared with reconstructed images and the root-mean-square error calculated to assess the accuracy of the estimated PSF. PVC was applied using Single Target Correction, incorporating the perturbation-estimated PSF. Corrected regional mean values were assessed for quantitative accuracy. RESULTS: Perturbation-estimated PSF values demonstrated dependence on the position in the Field of View and the number of OSEM iterations. A lower root mean squared error was observed when convolution of the ground truth image was performed with the perturbation-estimated PSF, compared with convolution using a different PSF. Regional mean values following PVC using the perturbation-estimated PSF were more accurate than uncorrected data, or data corrected with PVC using an unsuitable PSF. This was the case for both simple and anthropomorphic phantoms. For the simple phantom, regional mean values were within 0.7% of the ground truth values. Accuracy improved after 5 or more OSEM iterations (10 subsets). For the anthropomorphic phantoms, post-correction regional mean values were within 1.6% of the ground truth values for noise-free uniform lesions. CONCLUSION: Perturbation using a simulated point source could potentially improve quantitative SPECT accuracy via the application of PVC, provided that sufficient reconstruction iterations are used