Structural studies of indium and thallium insertion into the framework of the cluster compound Ti2Nb6Cl14O4

We have investigated the possibility of altering the electronic configuration of the niobium oxochloride cluster compound Ti2Nb6Cl14O4 (I) by doping this material with monovalent cations that can fit into cavities present in its cluster framework. The doping of I with In+ and Tl+ ions resulted in the formation of MxTi2Nb6Cl14-xO4+x (M = In, x = 0.10, 0.20, 0.27; M = Tl, x = 0.10, 0.20) in which the M+ ions partially occupy these cavities. The crystal structure analysis indicated that the additional charge provided by M+ ions is compensated by substitution of chlorine by oxygen, which leads to the cluster electronic configuration being intact. Crystal data: In0.272Ti2Nb6Cl13.728O4.272, space group C2/c (No. 15), a = 12.679(2) A, b = 14.567(2) A, c = 12.632(3) A, beta = 95.26(2) degrees, Z = 4; Tl0.196Ti2Nb6Cl13.804O4.196, space group C2/c (no. 15), a = 12.732(1) A, b = 14.607(2) A, c = 12.662(2) A, beta = 95.28(1) degrees, Z = 4.     

High-resolution MR venography of cerebral arteriovenous malformations

The purpose of this study was to evaluate the diagnostic potential of a high-resolution magnetic resonance (MR) venography technique in patients with cerebral arteriovenous malformations (AVMs). A high-resolution 3D gradient echo sequence was used with a long echo time TE to obtain venous information down to sub-pixel sized vessel diameters of several hundred microns. The method is based on the paramagnetic property of deoxyhemoglobin, and the resulting developing phase difference between veins and brain parenchyma at long echo times which leads to signal cancellation. The reconstructed venograms were compared with time-of-flight (TOF)-MR angiography using qualitative and quantitative criteria with the conventional digital subtraction angiography serving as the reference gold standard. In 17 patients with angiographically proven cerebral AVMs, the method indicates its potential in clinical applications. Venography was able to detect all AVMs whereas TOF-MRA failed in three patients. In the delineation of venous drainage patterns MR venography was superior to TOF-MRA, however, the method failed in the detection of about half of the main feeding arteries, as expected. Due to susceptibility artifacts at air/tissue boundaries and interference with paramagnetic hemosiderin, venography was limited with respect to the delineation of the exact nidus sizes and shapes in ten patients with AVMs located close to the skull base or having suffered from previous bleeding. Although the visualization of draining veins represents an important prerequisite in the surgical and radiosurgical treatment planning of cerebral AVMs, application of high resolution MR venography may be limited in the diagnostic work-up in some of these patients. On the other hand, it may be of special importance in the early detection and assessment of small AVMs that are difficult to diagnose with other MR methods.     

Disappearance of tumor contrast on contrast-enhanced FLAIR imaging of cerebral gliomas

Contrast-enhanced fluid-attentuated inversion recovery (FLAIR) magnetic resonance (MR) imaging has shown to be a valuable diagnostic modality in the assessment of cerebral gliomas. In this study we report of a potential pitfall regarding the delineation of enhancing tumor parts on contrast enhanced FLAIR imaging. In a limited number of patients, the administration of gadolinium obscures the area of contrast enhancement on contrast enhanced FLAIR images. Therefore the delineation of the macroscopic tumor parts, which are of great importance for the treatment planning is substantially worsened.     

Photolithographic Encoding of Metal Complexes

A platform technology for the creation of spatially resolved surfaces encoded with a monolayer consisting of different metal complexes was developed. The concept entails the light‐triggered activation of a self‐ assembled monolayer (SAM) of UV‐labile anchors, that is, phenacylsulfides, and the subsequent cycloaddition of selected diene‐functionalized metal complexes at defined areas on the surface. The synthesis and characterization of the metal complexes for the UV‐light assisted anchoring on the surface and a detailed study of a short‐chain oligomer model system in solution confirm the high efficiency of the photoreaction. The hybrid materials obtained by this concept can potentially be utilized for the design of highly valuable catalytic or (opto‐)electronic devices.     

Terminal Ligand and Packing Effects on Slow Relaxation in an Isostructural Set of [Dy(H2dapp)X2]+ Single Molecule Magnets**

We report three structurally related single ion Dy compounds using the pentadentate ligand 2,6-bis((E)-1-(2-(pyridin-2-yl)-hydrazineylidene)ethyl)pyridine (H₂dapp) [Dy(H₂dapp)(NO₃)₂]NO₃ ( 1 ), [Dy(H₂dapp)(OAc)₂]Cl ( 2 ) and [Dy(H₂dapp)(NO₃)₂]Cl_0.92(NO₃)_0.08 ( 3 ). The (H₂dapp) occupies a helical twisted pentagonal equatorial arrangement with two anionic ligands in the axial positions. Further influence on the electronic and magnetic structure is provided by a closely associated counterion interacting with the central N−H group of the (H₂dapp). The slow relaxation of the magnetisation shows that the anionic acetates give the greatest slowing down of the magnetisation reversal. Further influence on the relaxation properties of compounds 1 and 2 is the presence of short nitrate-nitrate intermolecular ligand contact opening further lattice relaxation pathways.     

Comparison of diffusion anisotropy measurements in combination with the flair-technique.

Fluid-attenuated inversion recovery (FLAIR) technique offers an effective tool to diminish partial-volume averaging effects from cerebrospinal (CSF) signal with in vivo magnetic resonance imaging. CSF-suppressed and unsuppressed direction-dependent diffusion-weighted (DW) images are obtained with a DW spin-echo EPI sequence in a single acquisition scheme. Comparison of unsuppressed and CSF-suppressed apparent diffusion coefficient (ADC) maps yields consistent values for brain tissue in volunteers when no partial-volume effects are expected, but differs considerably at borders of parenchyma to ventricles and sulci. From theory and phantom studies, a corrected anisotropy index is introduced considering differences of statistical fit errors. Anisotropy of white matter is observed in normal brain of volunteers. Anisotropy index maps reveal destruction of fiber tracts in pathologic areas. Results of a preliminary study on 12 patients with intra-axial tumors indicate an improved delineation of tumor boundaries of FLAIR ADC maps against unsuppressed acquisition.     

Transition between corrugated metal films and?split-ring-resonator arrays

We fabricate split-ring-resonator arrays via direct laser writing of polymers, followed by atomic-layer deposition of titania, chemical vapor deposition of silver, and focused-ion-beam milling. While structures like that have been fabricated previously by other means, our approach here allows for a direct comparison with the optical properties of corrugated metal surfaces, which are fabricated along the same lines. This comparison reveals substantial differences regarding the magnetic metamaterial properties. In particular, we find that the optical response of the corrugated metal surfaces is due to a higher-order magnetic resonance, whereas that of the split-ring resonators stems from their fundamental magnetic resonance.     

Serial MR imaging of intracranial metastases after radiosurgery

Purpose: To evaluate the spatiotemporal evolution of radiosurgical induced changes both in metastases and in normal brain tissue adjacent to the lesions by serial magnetic resonance (MR) imaging. Methods and Materials: Thirty-five intracranial metastases of different primaries were treated in 25 patients by single high-dose radiosurgery. MR images acquired before radiosurgery were available in all patients. Sixty-three follow-up MR studies were performed in these patients including T₂- and contrast-enhanced T₁-weighted MR images. The average follow-up time was 9 ± 5 months (mean ± standard deviation [SD]). Based on contrast-enhanced T₁-weighted MR images, tumor response was radiologically classified in the following four groups: stable disease was assumed if the average tumor diameter after treatment did not show a tumor shrinkage of more than 50% and an increase of more than 25%, partial remission as a shrinkage of tumor size of more than 50%, a disappearance of contrast-enhancing tumor as a complete remission, and an increase of tumor diameter of more than 25% as tumor progress. Moreover, we analysed signal changes on T₂-weighted images in brain parenchyma adjacent to the enhancing metastases. Results: The overall mean survival time was 10.5 ± 7 months, with a 1-year actuarial survival rate of 40%. Stable disease, partial or complete remission of the metastatic tumor was observed in 22 patients (88%). Central or homogeneous loss of contrast enhancement appeared to be a good prognostic sign for stable disease or partial remission. This association was statistically significant (p < 0.05). Three patients (12%) suffered from tumor progression. In eight patients (32%) with stable disease or partial remission, signal changes on T₂-weighted images were observed in tissue adjacent to the contrast enhancing lesions. A progression of the high signal on T₂-weighted images was seen in seven of the eight patients between 3 and 6 months after therapy, followed by a signal regression 6–18 months after irradiation. Conclusion: MR imaging is a sensitive imaging tool to evaluate tumor response as well as the presence or absence of adjacent parenchymal changes following radiosurgery. Loss of homogeneous or central contrast enhancement on Gd-enhanced MR images appeared to be a good prognostic sign for tumor response. Tumor shrinkage seems not to be dependent on time. In addition, most cases of radiation induced changes in normal brain parenchyma observed on T₂-weighted images seem to be self limited.