Publications

CuI reacts with SEt(2) in hexane to afford the known strongly luminescent 1D coordination polymer [(Et(2)S)(3)Cu(4)(mu(3)-I)(4)](n) (1). Its X-ray structure has been redetermined at 115, 235, and 275 K in order to address the behavior of the cluster-centered emission and is built upon Cu(4)(mu(3)-I)(4) cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging SEt(2) ligands. However, we could not reproduce the preparation of a coordination polymer with composition [(Et(2)S)(3)Cu(4)(mu(3)-Br)(4)](n) as reported in Inorg. Chem. 1975, 14, 1667. In contrast, the autoassembly reaction of SEt(2) with CuBr results in the formation of a novel 1D coordination polymer of composition [(Cu(3)Br(3))(SEt(2))(3)](n) (2). The crystal structure of 2 has been solved at 115, 173, 195, and 235 K. The framework of the luminescent compound 2 consists of a corrugated array with alternating Cu(mu(2)-Br)(2)Cu rhomboids, which are connected through two bridging SEt(2) ligands to a tetranuclear open-cubane Cu(4)Br(4) SBU, ligated on two external Cu atoms with one terminal SEt(2). The solid-state luminescence spectra of 1 and 2 exhibit intense halide-to-metal charge-transfer emissions centered at 565 and 550 nm, respectively, at 298 K. A correlation was also noted between the change in the full width at half-maximum of the emission band between 298 and 77 K and the relative flexibility of the bridging ligand. The emission properties of these materials are also rationalized by means of density functional theory (DFT) and time-dependent DFT calculations performed on 1.

Williams Syndrome (WS) is described as displaying a dissociation within memory systems. As the integrity of hippocampal formation (HF) is determinant for memory performance, we examined HF volumes and its association with memory measures in a group of WS and in a typically development group. A significantly reduced intracranial content was found in WS, despite no differences were observed for HF absolute volumes between groups. When volumes were normalized, left HF was increased in WS. Moreover, a lack of the normal right > left HF asymmetry was observed in WS. No positive correlations were found between volumetric and neurocognitive data in WS. In sum, a relative enlargement of HF and atypical patterns of asymmetry suggest abnormal brain development in WS.

We demonstrate an automated, multi-level method to segment white matter brain lesions and apply it to lupus. The method makes use of local morphometric features based on multiple MR sequences, including T1-weighted, T2-weighted, and fluid attenuated inversion recovery. After preprocessing, including co-registration, brain extraction, bias correction, and intensity standardization, 49 features are calculated for each brain voxel based on local morphometry. At each level of segmentation a supervised classifier takes advantage of a different subset of the features to conservatively segment lesion voxels, passing on more difficult voxels to the next classifier. This multi-level approach allows for a fast lesion classification method with tunable trade-offs between sensitivity and specificity producing accuracy comparable to a human rater.

The freezing of monomeric mixtures is known to concentrate solutes in a nonfrozen phase in the area surrounding the ice crystals. The concentration of such solutes is determined by the freezing temperature. Although salts or solvents do not directly react in the polymerization reaction, they do change the composition and properties of the nonfrozen phase. In this study, we investigated the influence of the addition of various salts and solvents on the structure of macroporous hydrogels formed in a semifrozen state through aqueous free-radical polymerization. The change in composition of the nonfrozen phase was studied using NMR to monitor the freezing of water, and the structural changes of the gels were observed using scanning electron microscopy. It was found that the addition of methanol or acetone caused the formation of reaction-induced phase separation polymerization due to cryoconcentration, which caused a significant increase of methanol or acetone in the nonfrozen phase. This resulted in a material with bimodal pore size distribution with pores of 10-80 μm in diameter caused by cryogelation, and with pores in the polymeric matrix with a diameter of less than 1 μm due to the reaction-induced phase separation. Addition of salts to the monomeric mixture resulted in a structure with only pores of 10-80 μm in diameter due to cryogelation. Increasing the amount of salts added resulted in the formation of thicker pore walls and thus a slight reduction in pore size compared to a sample with no added solute. The possibility of changing the structure and properties of the gels by adding different solutes could open up new applications for these materials, for example, chromatography applications.

Few studies have reported the reduced suppression of brain activity within the default network in schizophrenia. The relationship, however, between task-specific activation and default network suppression, as well as impact of this relationship on brain function, is still not clear, and it has not been studied in schizophrenia so far. We used previously published data showing a relationship between semantic encoding and white matter integrity in schizophrenia (Jeong et al., 2009), and reanalyzed the data using an independent component analysis (ICA). Participants comprised 10 healthy control subjects and 10 patients with chronic schizophrenia who underwent an fMRI scan during which they performed the Levels of Processing paradigm. The semantic processing-related independent components were compared between two groups using tensor-ICA. An independent component of semantic repetition priming showed a significant difference between the two groups. The component consisted of both less activated and less suppressed regions within the patients’ brains. The less activated regions included the bilateral inferior frontal gyri and the supramarginal gyri. The less suppressed regions included the medial frontal gyrus, the posterior cingulate gyrus, the precuneus and the right cerebellum. Our results suggest two components of semantic repetition priming deficit in schizophrenia: one related to weaker suppression of default network, mainly precuneus and medial frontal gyrus, the other related to weaker activation of regions directly involved in semantic repetition priming.

INTRODUCTION: Persons diagnosed with schizophrenia demonstrate deficits in prosody recognition. To examine prosody along the schizophrenia spectrum, antipsychotic-na ıve schizotypal personality disorder (SPD) subjects and healthy control subjects were compared. It was hypothesized that SPD subjects would perform more poorly; with cognitive and demographic factors contributing to the poor performance. The superior temporal gyrus (STG) was selected as the region-of-interest (ROI) given its known abnormalities in SPD and its important role in the processing of prosody.

OBJECTIVE: To quantify size and localization differences between tumors presenting with seizures vs nonseizure neurological symptoms. DESIGN: Retrospective imaging survey. We performed magnetic resonance imaging-based morphometric analysis and nonparametric mapping in patients with brain tumors. SETTING: University-affiliated teaching hospital. PATIENTS OR OTHER PARTICIPANTS: One hundred twenty-four patients with newly diagnosed supratentorial glial tumors. MAIN OUTCOME MEASURES: Volumetric and mapping methods were used to evaluate differences in size and location of the tumors in patients who presented with seizures as compared with patients who presented with other symptoms. RESULTS: In high-grade gliomas, tumors presenting with seizures were smaller than tumors presenting with other neurological symptoms, whereas in low-grade gliomas, tumors presenting with seizures were larger. Tumor location maps revealed that in high-grade gliomas, deep-seated tumors in the pericallosal regions were more likely to present with nonseizure neurological symptoms. In low-grade gliomas, tumors of the temporal lobe as well as the insular region were more likely to present with seizures. CONCLUSIONS: The influence of size and location of the tumors on their propensity to cause seizures varies with the grade of the tumor. In high-grade gliomas, rapidly growing tumors, particularly those situated in deeper structures, present with non-seizure-related symptoms. In low-grade gliomas, lesions in the temporal lobe or the insula grow large without other symptoms and eventually cause seizures. Quantitative image analysis allows for the mapping of regions in each group that are more or less susceptible to seizures.

A compression cell designed to fit inside an NMR spectrometer was used to investigate the in situ mechanical strain response, structural changes to the internal pore structure, and the diffusion and flow of interstitial water in full-thickness cartilage samples as it was deforming dynamically under a constant compressive load (pressure). We distinguish between the hydrostatic pressure acting on the interstitial fluid and the pore pressure acting on the cartilage fibril network. Our results show that properties related to the pore matrix microstructure such as diffusion and hydraulic conductivity are strongly influenced by the hydrostatic pressure in the interstitial fluid of the dynamically deforming cartilage which differ significantly from the properties measured under static i.e. equilibrium loading conditions (when the hydrostatic pressure has relaxed back to zero). The magnitude of the hydrostatic fluid pressure also appears to affect the way cartilage’s pore matrix changes during deformation with implications for the diffusion and flow-driven fluid transport through the deforming pore matrix. We also show strong evidence for a highly anisotropic pore structure and deformational dynamics that allows cartilage to deform without significantly altering the axial porosity of the matrix even at very large strains. The insensitivity of the axial porosity to compressive strain may be playing a critical function in directing the flow of pressurized interstitial fluid in the compressed cartilage to the surface, to support the load, and provide a protective interfacial fluid film that ’weeps’ out from the deforming tissue and thereby enhances the (elasto)hydrodynamic efficacy of sliding joints. Our results appear to show a close synergy between the structure of cartilage and both the hydrodynamic and boundary lubrication mechanisms.

Disturbances in selective attention represent a core characteristic of schizophrenia, whose neural underpinnings have yet to be fully elucidated. Consequently, we recorded brain activation using functional magnetic resonance imaging (fMRI) while 15 patients with schizophrenia and 15 age-matched controls performed a well-established measure of selective attention-the color Stroop negative priming task. We focused on two aspects of performance: overriding pre-potent responses (Stroop effect) and inhibition of prior negatively primed trials (negative priming effect). Behaviorally, controls demonstrated both significant Stroop and negative priming effects, while schizophrenic subjects only showed the Stroop effect. For the Stroop effect, fMRI indicated significantly greater activation in frontal regions-medial frontal gyrus/anterior cingulate gyrus and middle frontal gyrus for controls-but greater activation in medial parietal regions (posterior cingulate gyrus/precuneus) for patients. Negative priming elicited significant activation in right dorsolateral prefrontal cortex for both groups, but also in left dorsolateral prefrontal cortex for patients. These different patterns of fMRI activation may reflect faulty interaction in schizophrenia within networks of brain regions that are vital to selective attention.