Search

To enable wireless MRI receive arrays, per-channel power consumption must be reduced by a significant factor. To address this, a low-power SiGe alternative to industry standard MRI pre-amplifier blocks has been proposed and its impact on imaging performance evaluated in a benchtop environment. The SiGe amplifier reduces power consumption 28x, but exhibits increased non-linearity and reduced dynamic range relative to industry standard amplifiers. This distorts the images, causing reduced contrast and a blurring of fine features. In conjunction with the amplifier, a semi-blind calibration and compensation framework has been proposed to remove artifacts caused by this non-linearity. Requiring the knowledge of the calibration signal bandwidth, the associated peak transmit powers, and the distorted baseband signals, a second non-linearity is constructed that when cascaded with the receive chain produces a linear response. This method was evaluated for both knee and phantom image datasets of peak input power -20dBm with a -40dBm peak input power image as reference. In the benchtop environment, industry standard amplifiers produced input normalized RMSEs of 0.0199 and 0.0310 for phantom and knee datasets, respectively. The low-power SiGe amplifier resulted in RMSEs of 0.0869 and 0.1130 which were reduced to 0.0158 and 0.0168 following compensation, for phantom and knee images respectively. The ability to effectively compensate for this reduced dynamic range encourages further investigation of low-power SiGe amplifiers for power limited MRI receive arrays.

This study investigates the feasibility of non-contact retrospective respiratory gating and cardiac sensing using continuous wave Doppler radar deployed in an MRI system.

Three isomers of [(Cp*Ru)2 C2 B10 H12 ], the first examples of 14-vertex heteroboranes containing 14-skeletal electron pairs, have been synthesized by the direct electrophilic insertion of a {Cp*Ru(+) } fragment into the anion [4-Cp*-4,1,6-RuC2 B10 H12 ](-) . All three compounds have the same unique polyhedral structure having an approximate Cs symmetry and featuring a four-atom trapezoidal face. X-ray diffraction studies could confidently identify only one of the two cage C atoms in each structure. The other C atom position has been established by a combination of i) best fitting of computed and experimental (11) B and (1) H NMR chemical shifts, and ii) consideration of the lowest computed energy for series of isomers studied by DFT calculations. In all three isomers, one cage C atom occupies a degree-4 vertex on the short parallel edge of the trapezium.

The naphthalene ruthenacarboranes 3-(η-C10H8)-3,1,2-closo-RuC2B9H11 (1), 4-(η-C10H8)-4,1,6-closo-RuC2B10H12 (2) and 4-(η-C10H8)-4,1,10-closo-RuC2B10H12 (4) have been synthesised by the general method of reaction of a carborane dianion with [RuCl2(COD)]x in the presence of excess naphthalene under THF reflux. Compounds 4-(η-C10H8)-4,1,8-closo-RuC2B10H12 (3) and 4-(η-C10H8)-4,1,12-closo-RuC2B10H12 (5) were prepared from 2 and 4, respectively, by thermolysis in refluxing toluene. Compounds 1–5 were characterised spectroscopically and crystallographically. For the supraicosahedral ruthenacarboranes 2–5 the main structural point of interest was the conformation of the naphthalene ligand with respect to the ruthenacarborane cage, in comparison with conformations of the analogous ferracarboranes 4-(η-C10H8)-4,1,x-closo-FeC2B10H12 previously studied computationally. Good agreement is found between experimental and computational conformations for compounds 2, 3 and 4. Crystallographic disorder in 5 renders comparison between theoretical and experimental conformations difficult in this case.

In the title compound, [Rh(C2H11B9)(NO3)(C18H15P)2]·2.2CH2Cl2, studied as a 2.2-solvate of what was assumed to be dichloromethane, the nitrate ligand liesciswith respect to both cage C atoms. Accordingly, the compound displays a pronounced preferred exopolyhedral ligand orientation (ELO) which is traced to both the greatertransinfluence of the cage B over the cage C atoms and the greatertransinfluence of the triphenylphosphane ligands over the nitrate ligand. The overall molecular architecture therefore agrees with that of a number of similar 3-L-3,3-L′2-3,1,2-closo-MC2B9H11species in the literature.

Reduction and metalation of 1,2-(4′-F3CC6F4)2-1,2-closo-C2B10H10 affords 4,1,12-MC2B10 compounds directly at room temperature with no evidence of intermediate 4,1,6- or 4,1,8-analogues. For M = CpCo this species is the only isolable product. The M = Cp*Co analogue is produced together with an icosahedral dimetallacarborane that remarkably has lost a cage C vertex.

The development of catheters and guidewires that are safe from radiofrequency (RF) -induced heating and clearly visible against background tissue is a major challenge in interventional MRI. An interventional imaging approach using a toroidal transmit-receive (transceive) coil is presented. This toroidal transceiver allows controlled, low levels of RF current to flow in the catheter/guidewire for visualization, and can be used with conductive interventional devices that have a localized low-impedance tip contact.Toroidal transceivers were built, and phantom experiments were performed to quantify transmit power levels required for device visibility and to detect heating hazards. Imaging experiments in a pig cadaver tested the extendibility to higher field strength and nonphantom settings. A photonically powered optically coupled toroidal current sensor for monitoring induced RF currents was built, calibrated, and tested using an independent image-based current estimation method.Results indicate that high signal-to-noise ratio visualization is achievable using milliwatts of transmit power-power levels orders of magnitude lower than levels that induce measurable heating in phantom tests. Agreement between image-based current estimates and RF current sensor measurements validates sensor accuracy.The toroidal transceiver, integrated with power and current sensing, could offer a promising platform for safe and effective interventional device visualization.

Replacing a boron vertex in a [B(n)H(n)](2-) cluster with a smaller atom, e.g. carbon, results in the distance from that atom to the polyhedral centroid being shorter. This forms the basis of a simple but very effective method of distinguishing between B and C atoms in (hetero)carboranes that have been studied crystallographically, the Vertex-to-Centroid Distance (VCD) method. Examples of well-characterised icosahedral and sub-icosahedral closo carboranes, nido carboranes, icosahedral metallacarboranes and supraicosahedral metallacarboranes are used to illustrate the generality of the VCD method. In this process a number of structures are identified in which the method suggests B/C disorder not previously recognised and some structures in which it appears that a cage C atom has been wrongly assigned. The largest sub-group of heterocarboranes is the family of 3,1,2-MC(2)B(9) compounds, and for these species consideration of Exopolyhedral Ligand Orientation (ELO) can sometimes be used to quickly suggest when a literature structure is suspect in terms of cage C atom positioning. The crystal structure of one such compound, 3,3-NO(3)-3-PPh(3)-3,1,2-closo-RhC(2)B(9)H(11), has been redetermined and the correct location of the cage C atoms established.

An integrated Overhauser-enhanced MRI-Prepolarized MRI system was developed to obtain radiobiological information that could be accurately coregistered with diagnostic quality anatomic images. EPR and NMR images were acquired through the double resonance technique and field cycling of the main magnetic field from 5 mT to 0.5 T. Dedicated EPR and NMR coils were devised to minimize radiofrequency power deposition with high signal-to-noise ratio. Trityl and nitroxide radicals were used to characterize oxygen and redox sensitivities of multispin echo Overhauser-enhanced MRI. Oxygen resolution of 3 mmHg was obtained from 2 mM deoxygenated trityl phantoms. Trityl radicals were stable in reducing environments and did not alter the redox-sensitive decaying rate of the nitroxide signals. Nitroxide radicals had a compounding effect for the trityl oximetry. Tumor oxygenation and redox status were acquired with anatomical images by injecting trityl and nitroxide probes subsequently in murine tumors. The Overhauser-enhanced MRI-Prepolarized MRI system is ready for quantitative longitudinal imaging studies of tumor hypoxia and redox status as radiotherapy prognostic factors.

13-vertex indenyl cobaltacarboranes with 4,1,6-, 4,1,10- and 4,1,2-CoC(2)B(10) architectures have been synthesised by reduction of the corresponding closo carborane and metallation with an {(eta-C(9)H(7))Co} fragment. Variants of the 4,1,6-isomer were prepared with no, one and two methyl groups on cage C atoms, whilst 4,1,2-species were obtained both with two methyl groups and a trimethylene tether on the cage C atoms. Thermolysis of the 4,1,6-isomers yielded the corresponding 4,1,8-isomers, which in turn were converted to 4,1,12-isomers by thermolysis at higher temperatures. Alternatively relatively mild heating of the 4,1,10-isomer led to the 4,1,12-isomer directly. Products were characterised by mass spectrometry, (1)H and (11)B NMR spectroscopies and, in most cases, elemental analysis, and nine compounds were studied crystallographically. The 4,1,6-, 4,1,8-, 4,1,10- and 4,1,12- species have docosahedral cages whilst the 4,1,2-species are henicosahedral. In the structural studies attention focused on the orientation of the indenyl ligand with respect to the carborane ligand since this affords experimental information on the metal-cage bonding through the structural indenyl effect. There is a general tendency for the indenyl ligand to adopt orientations in which the ring junction C atoms lie trans to cage B atoms. In cases where the orientation is not compromised by the presence of a non-H substituent on the face of the carborane there is generally good agreement between the experimental orientation and that computed by DFT calculations for the related naphthalene ferracarboranes (eta-C(10)H(8))FeC(2)B(10)H(12). The presence of C-methyl substituents in the indenyl cobaltacarboranes tends to override this preference except in the case of 1,6-Me(2)-4-(eta-C(9)H(7))-4,1,6-closo-CoC(2)B(10)H(10) where the indenyl ligand instead is forced to incline away from the cage methyl groups. In DCM solution the 4,1,6-, 4,1,8-, 4,1,10- and 4,1,12- isomers of (eta-C(9)H(7))CoC(2)B(10)H(12) exhibit two, stepwise, 1-electron reductions assigned to Co(III)/Co(II)/Co(I) couples at less negative potentials than those of the corresponding Cp compounds. Moreover these reductions are easier for those isomers (4,1,6- and 4,1,10-) in which there are two cage C atoms in the carborane face to which the metal atom is bound. By spectroelectrochemical and EPR measurements it is concluded that the reductions of these indenyl cobaltacarboranes are largely metal-based.

Reduction of the tethered carborane 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) followed by metallation with {CpCo} or {(p-cymene)Ru} fragments affords both C,C'-dimethyl 4,1,2-MC(2)B(10) and 4,1,6-MC(2)B(10) species. DFT calculations indicate that the barriers to isomerisation of both 4-Cp-4,1,2-closo-CoC(2)B(10)H(12) and 4-(η-C(6)H(6))-4,1,2-closo-RuC(2)B(10)H(12) to their respective 4,1,6-isomers are too high for this to be the origin of the unexpected formation of 4,1,6-MC(2)B(10) products (in marked contrast to the related isomerisation of 1,2-closo-C(2)B(11)H(13) to 1,6-closo-C(2)B(11)H(13)), and, indeed, the 4,1,2-species are recovered unchanged from refluxing toluene. Equally, the DFT-calculated profile for the isomerisation of [7,8-nido-C(2)B(10)H(12)](2-) to [7,9-nido-C(2)B(10)H(12)](2-) suggests that the unexpected formation of 4,1,6-metallacarboranes is unlikely to result from isomerisation of a reduced (nido) carborane following desilylation. Instead, the source of the 4,1,6-MC(2)B(10) compounds is traced to desilylation of 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) by Li or Na prior to reduction. The supraicosahedral metallacarboranes 1,8-Me(2)-4-Cp-4,1,8-closo-CoC(2)B(10)H(10), 1,12-Me(2)-4-Cp-4,1,12-closo-CoC(2)B(10)H(10) and 1,12-Me(2)-4-(p-cymene)-4,1,12-closo-RuC(2)B(10)H(10) are also reported with all new species characterised both spectroscopically and crystallographically.