Denticity governs the formation of ß-thioketiminato tri-copper(I) and mono-copper(I) complexes.

Two classes of ß-thioketiminate ligands, SN chelators (HL1 and HL2) and SNN chelators (HL3 and HL4), were prepared to understand their coordination behavior in copper(I) complex formation. The formation of these copper(I) complexes bearing ß-thioketiminate ligands and their corresponding adducts toward isocyanide, PPh3, and CO was investigated to address two important issues. First, whether the denticity governs the copper(I) thiolate species formation between SN chelators and SNN chelators. Second, how the length of the pendant pyridyl arm affects the coordination and reactivity behaviors of copper(I) complexes. Based on the characterization results, it was found that the denticity of SN chelators and SNN chelators led to different nuclearity of copper(I)-thiolate species. The coordination modes of the pendant pyridyl arm were confirmed by FTIR measurements, which allow us to conclude that the electron donating ability of the LCu fragment is in the order of SNN-chelator (SNN bound) > SNN-chelators (SN bound) > SN-chelator.

Proton magnetic resonance spectroscopy and diffusion-weighted imaging in intracranial cystic mass lesions.

BACKGROUND: The differential diagnosis of various intracranial cystic lesions is sometimes difficult on the basis of CT or MRI findings. Our objective was to evaluate (1)H MRS and DWI in the differential diagnosis of these lesions and in comparison with conventional MRI. METHODS: Fifty patients with intracranial cystic lesions (21 pyogenic abscesses, 23 tumor cysts, 3 epidermoid cysts, and 3 arachnoid cysts) were evaluated with conventional MRI, DWI, and in vivo (1)H MRS. Preoperative diagnosis of the lesions was based on the results of DWI and in vivo MRS. All DWI and (1)H MRS studies were performed with a clinical 1.5-T system. The DWI was performed using single-shot spin-echo echo-planar pulse sequence with b = 1000 s/mm(2). The ADC value was measured. Diagnostic accuracy of conventional MRI, DWI, and in vivo (1)H MRS was calculated with respect to a final diagnosis of brain abscess vs nonabscess cystic tumor. RESULTS: Lactate and cytosolic amino acids with/without succinate, acetate, and alanine were observed in 18 of 21 cases of abscesses on MRS. In 3 cases of epidermoid cysts, lactate was observed and could be differentiated from 3 cases of arachnoid cysts, which showed only minimal lactate. Only lactate was seen in 14 of 23 patients with tumor cysts, whereas both lipid/lactate and choline were visible in 9 patients with tumor cysts. Increased signal was seen in 20 of 21 patients with abscesses and 3 patients with epidermoid cysts on DWI. Decreased signal was observed in 22 of 23 patients with tumor cysts and 3 patients with arachnoid cyst on DWI. Diagnostic accuracy, sensitivity, specificity, positive predictive value, and negative predictive value of conventional MRI for the differentiation of brain abscess from nonabscess cystic tumor were 61.4%, 61.9%, 60.9%, 59.1%, and 63.6%, respectively, whereas they were 93.2%, 85.7%, 100%, 100%, and 88.5% with MRS; 95.5%, 95.2%, 95.7%, 95.2%, and 95.7% with DWI; and 97.7%, 95.2%, 100%, 100%, and 95.8% with MRS and DWI. Magnetic resonance imaging, when combined with in vivo MRS and DWI, accurately predicted the diagnosis in 47 (94%) of 50 and 48 (96%) of 50 of the cases, respectively. CONCLUSIONS: Proton MRS and DWI are useful as additional diagnostic modalities in differentiating intracranial cystic lesions. Combination of DWI with calculated ADC values and metabolite spectrum acquired by MRS add more information to MRI in the differentiation of intracranial cystic mass lesions.

[Synthesis, characterization and relaxivity of dimeric DTPA-gadonium (III) complexes with long chain alkyl esters of L-lysine].

To look for new MRI (magnetic resonance imaging) contrast agents with higher relaxivity as well as liver-selecsivity, four novel ester-amino ligands were synthesized by bis-acylation of octadecanyl, hexadecanyl, tetradecanyl and dedecanyl L-lysine with diethylenetriaminepentaacetic acid mono-anhydride (DTPA-MA), respectively. The corresponding dimeric Gd(III) complexes were gained by the reaction of these ligands with GdCl3 x 6H2O. All ligands and complexes were characterized by FTIR, 1H NMR and elemental analysis. The longitudinal relaxation time (T1) was measured, and relevant longitudinal relaxivity (R1) of these neatral binuclear Gd(III) complexes is: 6.48, 6.02, 5.76 and 5.68 L x mmol(-1) x s(-1), respectively, and all are higher than that of Gd-DTPA (4.98 L x mmol(-1) x s(-1)) (300 MHz).

Role of diffusion-weighted imaging and proton MR spectroscopy in distinguishing between pyogenic brain abscess and necrotic brain tumor.

Brain abscesses and brain tumors may have similar clinical presentations. For example, only 50% brain abscess patients have fever, which could be masked by corticosteroid therapy. Also, the differential diagnosis of brain abscesses versus cystic or necrotic tumors may be difficult based on computed tomography (CT) or magnetic resonance (MR) imaging findings. However, the strategies of management for abscess and neoplasm are very different, and it is especially imperative to have a correct diagnosis before any surgical intervention of cystic brain lesions. The MR special techniques, e.g. diffusion-weighted imaging (DWI) and proton (1H) MR spectroscopy, are useful as additional diagnostic modalities for differentiating brain abscesses from cystic or necrotic brain tumors. DWI shows high signal intensity in most cases of pyogenic abscesses and low signal intensity in most cases of cystic or necrotic tumors. MR spectroscopy shows characteristic metabolites in pyogenic abscesses, distinct from those in cystic or necrotic tumors.