Real-time MRI-guided hyperthermia treatment using a fast adaptive algorithm.

Magnetic resonance (MR) imaging is promising for monitoring and guiding hyperthermia treatments. The goal of this work is to investigate the stability of an algorithm for online MR thermal image guided steering and focusing of heat into the target volume. The control platform comprised a four-antenna mini-annular phased array (MAPA) applicator operating at 140 MHz (used for extremity sarcoma heating) and a GE Signa Excite 1.5 T MR system, both of which were driven by a control workstation. MR proton resonance frequency shift images acquired during heating were used to iteratively update a model of the heated object, starting with an initial finite element computed model estimate. At each iterative step, the current model was used to compute a focusing vector, which was then used to drive the next iteration, until convergence. Perturbation of the driving vector was used to prevent the process from stalling away from the desired focus. Experimental validation of the performance of the automatic treatment platform was conducted with two cylindrical phantom studies, one homogeneous and one muscle equivalent with tumor tissue (conductivity 50% higher) inserted, with initial focal spots being intentionally rotated 90 degrees and 50 degrees away from the desired focus, mimicking initial setup errors in applicator rotation. The integrated MR-HT treatment platform steered the focus of heating into the desired target volume in two quite different phantom tissue loads which model expected patient treatment configurations. For the homogeneous phantom test where the target was intentionally offset by 90 degrees rotation of the applicator, convergence to the proper phase focus in the target occurred after 16 iterations of the algorithm. For the more realistic test with a muscle equivalent phantom with tumor inserted with 50 degrees applicator displacement, only two iterations were necessary to steer the focus into the tumor target. Convergence improved the heating efficacy (the ratio of integral temperature in the tumor to integral temperature in normal tissue) by up to six-fold, compared to the first iteration. The integrated MR-HT treatment algorithm successfully steered the focus of heating into the desired target volume for both the simple homogeneous and the more challenging muscle equivalent phantom with tumor insert models of human extremity sarcomas after 16 and 2 iterations, correspondingly. The adaptive method for MR thermal image guided focal steering shows promise when tested in phantom experiments on a four-antenna phased array applicator.

Computational investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part I. Theoretical calculation of spectroscopically observable parameters.

Theoretical calculations are performed for the X2E"2 and A 2E"3 states of the cycloheptatrienyl (tropyl) radical C7H7. An important goal of these calculations is to predict and to guide the analysis of the experimentally observed A 2E"3-X 2E"2 electronic spectrum. Vibrational frequencies of the tropyl radical at the conical intersection and stationary points of its X and A state Jahn-Teller distorted potential energy surfaces are given. Spectroscopically obtainable parameters describing the Jahn-Teller effect are calculated for the X and A electronic states. Additionally, the stabilization energies for the X and A states are computed at the CASSCF(7,7) and EOMEA-CCSD levels of theory using various basis sets.

Experimental investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part II. Vibrational analysis of the A 2E"3-X 2E"2 electronic transition.

Laser-induced fluorescence (LIF) and laser-excited dispersed fluorescence (LEDF) spectra of the cycloheptatrienyl (tropyl) radical C7H7 have been observed under supersonic jet-cooling conditions. Assignment of the LIF excitation spectrum yields detailed information about the A-state vibronic structure. The LEDF emission was collected by pumping different vibronic bands of the A 2E"3<--X 2E"2 electronic spectrum. Analysis of the LEDF spectra yields valuable information about the vibronic levels of the X 2E"2 state. The X- and A-state vibronic structures characterize the Jahn-Teller distortion of the respective potential energy surfaces. A thorough analysis reveals observable Jahn-Teller activity in three of the four e'3 modes for the X 2E"2 state and two of the three e'1 modes for the A 2E"3 state and provides values for their deperturbed vibrational frequencies as well as linear Jahn-Teller coupling constants. The molecular parameters characterizing the Jahn-Teller interaction in the X and A states of C7H7 are compared to theoretical results and to those previously obtained for C5H5 and C6H6+.

Jahn-Teller and related effects in the silver trimer. I. The ab initio calculation of spectroscopically observable parameters for the X 2E' and A 2E" electronic states.

Extensive ab initio calculations were performed for the X2E' and A2E" states of Ag3, using a newly constructed basis set for Ag. An important goal of these calculations is to guide the analysis of the experimentally observed A 2E"-X2E' electronic spectrum. Vibrational frequencies of Ag(3) for both the X and A states are reported. Spectroscopically obtainable parameters describing the Jahn-Teller effect are calculated for the X and A states. The magnitude of the spin-orbit effects for this relativistic system was also calculated for the X2E' and A 2E" states. Using all this information, the X-A electronic spectrum is predicted for Ag(3). Additionally, the geometries and symmetries of the global minima and saddle points as well as the barrier to pseudorotation around the moat of the potential energy surface are determined for both states.

Jahn-Teller and related effects in the silver trimer. II: vibrational analysis of the A 2E"-X 2E' electronic transition.

The laser-excited, jet-cooled A 2E"-X 2E' electronic spectrum of the silver trimer yields detailed information about its A- and X-state vibronic structure. Following extensive parameter fitting, the absorption and emission spectra are simulated and the bands are assigned. The Jahn-Teller analysis includes both linear and quadratic coupling terms, considered simultaneously with spin-orbit coupling. The spin-orbit splitting is shown to be largely quenched in both the A and X electronic states. The Jahn-Teller analysis of the A and X vibronic structures reveals the distortion of their corresponding potential energy surfaces.

High resolution spectra and conformational analysis of 2-butoxy radical.

We have recorded five high resolution (200 MHz), rotationally resolved, vibrational bands of the B-X electronic transition of 2-butoxy. Two bands of the 2-butoxy spectrum have been rotationally analyzed and assigned to two different geometrical conformers of the molecule. The analyses allow the determination of the six experimental rotational constants defined by the geometry of the species in the ground (X) and excited (B) electronic states and also four spin-rotation constants for the X electronic state of the conformers. Comparison of the experimental rotational constants with the results of ab initio computations provides unambiguous conformational assignment of these bands. This approach can be extended to assign two other spectral bands to the third 2-butoxy conformer.