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61.
Luminescent Di‐ and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization, and Application in OLEDs 下载免费PDF全文
Dr. D. Suresh Dr. Clara S. B. Gomes Patrícia S. Lopes Dr. Cláudia A. Figueira Bruno Ferreira Prof. Pedro T. Gomes Dr. Roberto E. Di Paolo Prof. António L. Maçanita Prof. M. Teresa Duarte Dr. Ana Charas Prof. Jorge Morgado Diogo Vila‐Viçosa Prof. Maria José Calhorda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9133-9149
New bis‐ and tris(iminopyrrole)‐functionalized linear (1,2‐(HNC4H3‐C(H)?N)2‐C6H4 ( 2 ), 1,3‐(HNC4H3‐C(H)?N)2‐C6H4 ( 3 ), 1,4‐(HNC4H3‐C(H)?N)2‐C6H4 ( 4 ), 4,4′‐(HNC4H3‐C(H)?N)2‐(C6H4‐C6H4) ( 5 ), 1,5‐(HNC4H3C‐(H)?N)2‐C10H6 ( 6 ), 2,6‐(HNC4H3C‐(H)?N)2‐C10H6 ( 7 ), 2,6‐(HNC4H3C‐(H)?N)2‐C14H8 ( 8 )) and star‐shaped (1,3,5‐(HNC4H3‐C(H)?N‐1,4‐C6H4)3‐C6H3 ( 9 )) π‐conjugated molecules were synthesized by the condensation reactions of 2‐formylpyrrole ( 1 ) with several aromatic di‐ and triamines. The corresponding linear diboron chelate complexes (Ph2B[1,3‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 10 ), Ph2B[1,4‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 11 ), Ph2B[4,4′‐bis(iminopyrrolyl)‐biphenyl]BPh2 ( 12 ), Ph2B[1,5‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 13 ), Ph2B[2,6‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 14 ), Ph2B[2,6‐bis(iminopyrrolyl)‐anthracenyl]BPh2 ( 15 )) and the star‐shaped triboron complex ([4′,4′′,4′′′‐tris(iminopyrrolyl)‐1,3,5‐triphenylbenzene](BPh2)3 ( 16 )) were obtained in moderate to good yields, by the treatment of 3 – 9 with B(C6H5)3. The ligand precursors are non‐emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π‐conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time‐dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13 , in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples ( 11 , 12 , 14 , and 15 ), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO–LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π‐system, to afford green to yellow emissions. Organic light‐emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m?2, for single layer devices, increasing to 4400 cd m?2 when a hole‐transporting layer is used. 相似文献
62.
Prof. Dr. Francesc Teixidor Dr. Ariadna Pepiol Prof. Dr. Clara Viñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10650-10653
A new class of globular polybranched macromolecules that contain multiple anionic metallacarborane clusters at the o‐carborane periphery is reported. The water soluble high boron rich containing molecules could be of interest for boron neutron capture therapy (BNCT) as well as for drug delivery. The reinforced electrostatic noncovalent interactions between anionic polyethylene glycol cobaltabisdicarbollide (PEG‐COSAN) branches and the ammonium cation have been shown using ESI‐MS. 相似文献
63.
Erik L. RegaladoGregory Genta-Jouve Deniz TasdemirPhilippe Amade Clara NogueirasOlivier P. Thomas 《Tetrahedron》2011,67(5):1011-1018
Seven novel steroid glycosides, acanthifoliosides A-F (1-6), and the methyl ester of 6 (7), were isolated from the marine sponge Pandaros acanthifolium as minor components. Acanthifoliosides are characterized by a rare C-15 and C-16 oxidized D ring, which was previously found in saponins produced by starfishes. Very uncommon is the presence of additional sugar residues at C-15 or C-16. Their structures were determined on the basis of extensive spectroscopic analyses, including two-dimensional NMR and HRESIMS data. The absolute configurations of the aglycones were assigned by comparison between experimental and TDDFT calculated CD spectra of 1, whereas the absolute configurations of the monosaccharide units were determined by chiral GC analyses of the acid methanolysates. Some of the acanthifoliosides exhibit moderate antiprotozoal activity but to a lesser extent than the most potent pandarosides. 相似文献
64.
Samakashvili S Ibáñez C Simó C Gil-Bea FJ Winblad B Cedazo-Mínguez A Cifuentes A 《Electrophoresis》2011,32(19):2757-2764
Chiral micellar electrokinetic chromatography with laser-induced fluorescence detection (chiral-MEKC-LIF) was used to investigate D- and L-amino acid contents in cerebrospinal fluid (CSF) samples related to different Alzheimer disease (AD) stages. CSF samples were taken from (i) control subjects (S1 pool), (ii) subjects showing a mild cognitive impairment who remained stable (S2 pool), (iii) subjects showing an mild cognitive impairment that progressed to AD (S3 pool) and (iv) subjects diagnosed with AD (S4 pool). The optimized procedure only needed 10 μL of CSF and it included sample cleaning, derivatization with FITC and chiral-MEKC-LIF separation. Eighteen standard amino acids were baseline separated with efficiencies up to 703,000 plates/m, high sensitivity (LODs in the nM range) and good resolution (values ranging from 2.6 to 9.5). Using this method, L-Arg, L-Leu, L-Gln, γ-aminobutyric acid, L-Ser, D-Ser, L-Ala, Gly, L-Lys, L-Glu and L-Asp were detected in all the CSF samples. S3 and S4 samples (i.e. AD subjects) showed significant lower amounts of L-Arg L-Lys, L-Glu and L-Asp compared to the non-AD S1 and S2 samples, showing in the S4 group the lowest amounts of L-Arg L-Lys, L-Glu and L-Asp. Moreover, γ-aminobutyric acid was significantly higher in AD subjects with the highest amount also found for S4. No significant differences were observed for the rest of amino acids including D-Ser. Based on the obtained chiral-MEKC-LIF data, it was possible to correctly classify all the samples into the four groups. These results demonstrate that the use of enantioselective procedures as the one developed in this work can provide some new light on the investigations of AD, including the discovery of new biomarkers related to different stages of AD. 相似文献
65.
Isothermal titration calorimetry (ITC) is used to study the complexation thermodynamics of Ni(II) with histidine (His) and with N-2-aminoethylglycine (EDMA). The titrations were performed in HEPES and Tris buffers at various ionic strengths and pH values around 8. The results show the influence of the experimental conditions on the shape and fitting parameters of the calorimetric curves. For the studied systems, the main reaction is concomitant with a number of side reactions which contribute to the global energy measured. From the calorimetric data measured, the formation constants for the species NiHEPES+, Tris+His−, TrisNiHis+ and [Ni(EDMA)2OH]− have been evaluated for the first time and the values obtained properly validated. 相似文献
66.
Abnormal reactivity has been observed in Negishi, Suzuki-Miyaura, and Kumada-Tamao-Corriu cross-couplings in which PEPPSI-IPr (where PEPPSI stands for pyridine enhanced precatalyst preparation, stabilization, and initiation and IPr refers to the NHC ligand) is employed, implicating the presence of two distinct Pd(0) species in the catalytic cycle. Polybrominated arenes and organometallic reagents react selectively to give the product of exhaustive polysubstitution regardless of the initial reaction stoichiometry. Competition experiments suggest that, after an initial activation controlled oxidative addition, reductive elimination produces an ultrareactive Pd(0) species which consumes all remaining C-Br bonds in the molecule under diffusion control. 相似文献
67.
68.
Pieters G Gaucher A Prim D Besson T Giner Planas J Teixidor F Viñas C Light ME Hursthouse MB 《Chemical communications (Cambridge, England)》2011,47(27):7725-7727
Valuable amino benzo[g,h,i]perylenes have been obtained through a one pot electrophilic aromatic substitution--Scholl reaction sequence. Novel molecular architectures combining 3D-o-carborane and planar amino benzo[g,h,i]perylene units are described. Photophysical properties of amino benzo[g,h,i]perylene and the carborane-appended derivatives are discussed. 相似文献
69.
Imura Y Tanuma H Sugimoto H Ito R Hojo S Endo H Morita C Kawai T 《Chemical communications (Cambridge, England)》2011,47(22):6380-6382
Straight ultrathin Au nanowires (NWs) with diameters less than 2 nm were synthesized using the lamellar structure of C18AA in an organogel and its selective adsorption for specific gold surfaces. In addition, the potential to form a bilayer structure with interdigitated hydrocarbon chains enabled the production of water-dispersible Au NWs without morphological change. 相似文献
70.
Apetrei CL Tuchilus C Aprotosoaie AC Oprea A Malterud KE Miron A 《Molecules (Basel, Switzerland)》2011,16(9):7773-7788
The chemical constituents and biological activity of Pinus cembra L. (Pinaceae), native to the Central European Alps and the Carpathian Mountains, are not well known. The aim of the present work was to examine the phenolic content, antioxidant and antimicrobial effects of hydromethanolic extracts of Pinus cembra L. bark and needles. Bark extract had higher concentrations of total phenolics (299.3 vs. 78.22 mg gallic acid equivalents/g extract), flavonoids (125.3 vs. 19.84 mg catechin equivalents/g extract) and proanthocyanidins (74.3 vs. 12.7 mg cyanidin equivalents/g extract) than needle extract and was more active as a free radical scavenger, reducing agent and antimicrobial agent. The EC?? values in the 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) diammonium salt (ABTS) and reducing power assays were 71.1, 6.3 and 26 mg/mL for bark extract and 186.1, 24 and 104 mg/mL for needle extract, respectively. In addition, needle extract showed ferrous ions chelating effects (EC?? = 1,755 μg/mL). The antimicrobial effects against Staphylococcus aureus, Sarcina lutea, Bacillus cereus, Escherichia coli, Pseudomonas aeruginosa and Candida albicans were assessed by the agar diffusion method. Both extracts (4 mg/well) were active against all the microorganisms tested; bark extract showed higher inhibition on all strains. These results indicate that Pinus cembra L. bark and needles are good sources of phytochemicals with antioxidant and antimicrobial activities. 相似文献