The fac-[Re(CO) 3 (deeb)L] + complex (C2) where L is the (E)-2-((3-amino-pyridin-4-ylimino)-methyl)-4,6di-tert-butylphenol ancillary ligand, which presents an intramolecular hydrogen bond, has been synthesized and characterized using UV-vis, 1 H-NMR, FT-IR, cyclic voltammetry and DFT calculations.The UV-vis absorption and emission properties have been studied at room temperature and the results were compared with TDDFT calculations including spin-orbit effects. We report an alternative synthesis route for the fac-Re(CO) 3 (deeb)Br (C1) complex where deeb = (4,4 0 -diethanoate)-2,2 0 -bpy. Besides, wehave found that the C1 shows a red shift in the emission spectrum due to the nature of the ancillary electron donating ligand, while the C2 complex shows a blue shift in the emission spectrum suggesting that the ancillary ligand L has electron withdrawing ability and the importance of the intramolecular hydrogen bond. The calculations suggest that an experimental mixed absorption band at 361 nm could be assigned to MLCT and LLCT transitions. The electron withdrawing nature of the ancillary ligand in C2 explains the electrochemical behavior, which shows the oxidation of Re I at 1.83 V and the reduction of deeb at À0.77 V. 1.44 [s, 6H, (-CH 3 )], 4.49 [m, 4H], 5.92 [s, 2H, -NH 2 ], 6.45 [d; J = 5.5 Hz; 1H], 7.28 [d; J = 1.5 Hz; 1H], 7.47 [s, 1H], 7.51 [s, 1H], 7.53 [s, 1H], 8.11 [s, 1H], 8.20 [d; J = 5.5 Hz; 2H], 8.91 [s, 2H], Scheme 1 Structures of deeb and L ligands used in this work.

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2,5-Dimethyl-1,4-bis(carboxyalkyl)benzenes were prepared in almost quantitative yield by alkylation of malonic esters from 2,5-dimethyl-1,4-dibromomethylbenzene obtained by bromomethylation of 1,4-dimethylbenzene. The methyl groups on the central benzene ring induce intramolecular, regiospecific cycloeliminations leading selectively to the diketones, the precursors of the corresponding 1,5-dihydro-s-indacenes, which also were obtained in very high yield. These new ligand precursors were easily converted to the mono- or dianions, which were characterized by means of the mono- or disilylated compounds. Disilylation occurs in cis and trans position. The structure of the trans-1,5-bis(trimethylsilyl)-2,6-diethyl-4,8-dimethyl-s-indacene was obtained by X-ray diffraction. Hexaalkyl-1,5-dihydro-s-indacenes underwent regioselective monosilylation and regiospecific and stereoselective disilylation. Disilylation of the less hindered tetraalkyl-1,5-dihydro-s-indacenes was regioselective and stereoselective.

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Background Mucosal involvement is frequently seen in cutaneous lupus erythematosus (CLE) and systemic lupus erythematosus (SLE). There is no consensus regarding the prevalence, and a wide range of lesions has been reported. Its prognostic significance is currently unknown and a matter of controversy. Objective To classify oral lesions in lupus, evaluate their prevalence and assess their possible association with disease activity. Methods We conducted a descriptive study between 2016 and 2017. A total of 150 lupus patients were matched by sex, age and smoking status with 151 healthy individuals. All subjects underwent a careful evaluation of oral mucosa. On the same day of the clinical assessment, each patient underwent a peripheral venous blood and urine analysis. All patients underwent a full medical history, physical examination and a careful examination of the oral cavity. For each one, we obtained photographs of ten areas of the oral cavity. Two dermatologists of our group blindly recorded the presence and morphology of oral lesions. The disease activity of CLE patients was scored using the Revised Cutaneous Lupus Erythematosus Disease Area and Severity Index, and in SLE patients, activity was measured using the Systemic Lupus Erythematosus Disease Activity Index. Results In CLE patients, there was a statistically significant correlation between higher cutaneous disease activity and the following oral findings: discoid plaques, cobblestone and red/brown‐pigmented macules. In patients with CLE, red macules on jugal mucosa were statistically associated with anaemia and positive antinuclear antibodies titres; additionally, the presence of gingivitis was related to systemic inflammation. In SLE patients, gingival telangiectases were statistically significantly associated with leucopenia, hypocomplementemia and systemic inflammation. Limitations Biopsies on mucosal lesions were not performed. Conclusion Some specific oral lesions correlate with disease activity in CLE and SLE.

Hydrosilylation of fatty acid methyl esters (FAMEs) were efficiently catalyzed by Speier's and Wilkinson's catalysts in the case of vinylic acid esters, but less efficiently in the case of non-vinylic ones, which gave non-regiospecific additions. In the latter case, initiation by radicals led to regiospecific reactions for oleic esters (C10-silylation). This regiospecificity can be attributed to the higher stability of the C10-silylated adduct and of the corresponding radical intermediate. Only regioselective addition was observed for linoleic esters (C13-silylation % 70%, C10 % 20%, C9 % 10%). Molecular modeling was used to examine the stability of the isomeric products and radicals. The new concept of radical initiation sequence has been successfully applied to FAMEs and then was extended to crude fish oil.

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