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101.
Gerard Lligadas Juan C. Ronda Marina Galià Virginia Cádiz 《Journal of polymer science. Part A, Polymer chemistry》2013,51(10):2111-2124
As a consequence of the depleting of fossil reserves and environmental issues, today, plant oils and fatty acids derived therefrom have a respectable status within the polymer chemistry community. However, maximizing the benefits of these renewable feedstocks requires the utilization of sustainable and efficient chemical transformations. The emergence of click chemistry concept and especially the renaissance of thiol‐ene addition reaction have had an impact on the way to make plant oil‐derived polymers. This highlight discusses the applicability and success of thiol‐ene addition and other click reactions in the transformation of oleochemicals into monomers and polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 相似文献
102.
Targeting the Two Oncogenic Functional Sites of the HPV E6 Oncoprotein with a High‐Affinity Bivalent Ligand 下载免费PDF全文
103.
Vanézia L. Silva Ruy Carvalho Matheus P. Freitas Cláudio F. Tormena Walclée C. Melo 《Structural chemistry》2007,18(5):605-609
Spectrometric and theoretical tools have been employed in this study in order to elucidate the structures of DTPA (diethylenetriaminepentaacetic
acid) complexed to copper and lead. Mass spectrometry allowed determining the 1:1 stoichiometry of metal:ligand, while infrared
spectroscopy demonstrated that both N and O are sites for complexation. 13C NMR analysis showed the existence of free and complexed carboxyl groups, due to a straight singlet at 180.7 ppm (free carboxylic
13C) and to a broad signal at 179.3 ppm (complexed carboxylic 13C, 2
J
Pb…O=C). A distorted NMR signal were observed for the Cu–DTPA carboxyl group, due to the Cu2+ paramagnetism. Based on the spectrometric evidences for the metal–DTPA structures, DFT optimizations were carried out and
an octahedral-like arrangement for the Cu complex and a “shell-like” arrangement for the Pb complex, both hexa-coordinated,
were then proposed for the structures of the titled compounds.
相似文献
Ruy CarvalhoEmail: |
104.
Miyasaka H Nezu T Sugimoto K Sugiura K Yamashita M Clérac R 《Inorganic chemistry》2004,43(18):5486-5488
Heterometallic linear tetramers [Mn(5-R-saltmen)Ni(pao)(bpy)(2)](2)(ClO(4))(4) (5-R-saltmen(2-) = N,N'-1,1,2,2-tetramethylethylene bis(5-R-salicylideneiminate); pao(-) = pyridine-2-aldoximate; bpy = 2,2'-bipyridine, R = H, 1; Cl, 2; Br, 3; MeO, 4) have been synthesized and structurally characterized. These compounds exhibit a [Ni(II)-NO-Mn(III)-(O)(2)-Mn(III)-ON-Ni(II)] skeleton where -ON- is an oximate bridge between Mn(III) and Ni(II) ions and -(O)(2)- is a bi-phenolate bridge between Mn(III) ions. These tetramers can be seen as oligomeric units of the heterometallic Mn(III)(2)-Ni(II) chain observed in a family of single-chain magnets (Clérac, R.; Miyasaka, H.; Yamashita, M.; Coulon, C. J. Am. Chem. Soc. 2002, 124, 12837. Miyasaka, H.; Clérac, R.; Mizushima, K.; Sugiura, K.; Yamashita, M.; Wernsdorfer, W.; Coulon, C. Inorg. Chem. 2003, 42, 8203.). Magnetic measurements on these tetramers confirm the nature of the magnetic interactions reported for the Mn(III)(2)-Ni(II) chains: a strong antiferromagnetic Mn(III)/Ni(II) coupling via the oximate bridge (J(Ni-Mn) ranges from -23.7 to -26.1 K) and a weak ferromagnetic Mn(III)/Mn(III) coupling through the bi-phenolate bridge (J(Mn-Mn) ranges from +0.4 to +0.9 K). These magnetic interactions lead to tetramers with an S = 2 ground state. 相似文献
105.
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
106.
Lanthanide Complexes with Multidentate Oxime Ligands as Single‐Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems 下载免费PDF全文
Dr. Małgorzata Hołyńska Dr. Rodolphe Clérac Mathieu Rouzières 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13321-13329
The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 ( 1 : [La2(pop)2(acac)4(CH3OH)], 2 : [Dy2(pop)(acac)5]) are synthesized from the 2‐hydroxyimino‐N‐[1‐(2‐pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3 , 4 , and 5 ( 3 : [Dy2(naphthsaoH)2(acac)4H(OH)]?0.85 CH3CN?1.58 H2O; 4 : [Tb2(naphthsaoH)2(acac)4H(OH)]?0.52 CH3CN?1.71 H2O; 5 : [La6(CO3)2(naphthsao)5 (naphthsaoH)0.5(acac)8(CO3)0.5(CH3OH)2.76H5.5(H2O)1.24]?2.39 CH3CN?0.12 H2O) contain 1‐(1‐hydroxynaphthalen‐2‐yl)‐ethanone oxime (naphthsaoH2). In 1 – 4 , dinuclear [Ln2] complexes crystallize, whereas hexanuclear LaIII complex 5 is formed after fixation of atmospheric carbon dioxide. DyIII‐based complexes 2 and 3 display single‐molecule‐magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy3+ ions. 相似文献
107.
Lecren L Wernsdorfer W Li YG Vindigni A Miyasaka H Clérac R 《Journal of the American Chemical Society》2007,129(16):5045-5051
An out-of-plane dimeric MnIII quadridentate Schiff-base compound, [Mn2(salpn)2(H2O)2](ClO4)2 (salpn(2-) = N,N'-(propane)bis(salicylideneiminate)), has been synthesized and structurally characterized. The crystal structure reveals that the [Mn2(salpn)2(H2O)2](2+) units are linked through weak H-bonds (OHwater...OPh) in one dimension along the c-axis, forming supramolecular chains. The exchange interaction between MnIII ions via the biphenolate bridge is ferromagnetic (J/kB = +1.8 K), inducing an ST = 4 ground state. This dinuclear unit possesses uni-axial anisotropy observed in the out-of-plane direction with DMn2/kB = -1.65 K. At low temperatures, this complex exhibits slow relaxation of its magnetization in agreement with a single-molecule magnet (SMM) behavior. Interestingly, the intermolecular magnetic interactions along the one-dimensional organization, albeit weak (J'/kB = -0.03 K), influence significantly the thermally activated and quantum dynamics of this complex. Thus, unique features such as M vs H data with multiple steps, hysteresis effects, and peculiar relaxation time have been explained considering SMMs in small exchange-field perturbations and finite-size effects intrinsic to the chain arrangement. The magnetic properties of this new complex can be regarded as an intermediate behavior between SMM and single-chain magnet (SCM) properties. 相似文献
108.
Gas chromatography-mass spectrometry (GC/MS) was employed for the determination of 30 widely used pesticides including various
transformation products and alkylphenols in water and agricultural soils with the aim of assessing the impact of these compounds
in agricultural soils and the underlying aquifer. The extraction, clean-up, and analytical procedures were optimized for both
water and soil samples to provide a highly robust method capable of determining target analytes at the ppb–ppt level with
high precision. For water samples, different solid-phase extraction cartridges and conditions were optimized; similarly, pressurized
liquid extraction conditions were tested to provide interference-free extracts and high sensitivity. Instrumental LODs of
3–4 pg were obtained. The multi-residue extraction procedures were applied to the analysis of groundwaters and agricultural
soils from the Ebro river basin (NE Spain). Most ubiquitous herbicides detected were triazines but some acetanilides and organophosphorus
pesticides were also found; the pesticide additive tributylphosphate was found in all water samples. Levels varied between
0.57 and 5.37 μg/L in groundwater, whereas nonylphenol was the sole compound detected in soil. Alkylphenols are used as adjuvants
in pesticide formulations and are present in sludges employed as soil fertilizers. Occurrence was found to be similar to other
environmental studies. 相似文献
109.
M. G. Ferreira Da Silva J. M. Fernàndez Navarro 《Journal of Sol-Gel Science and Technology》1994,2(1-3):895-901
The effect of thermal treatment on the structural incorporation of Cr2O3 in xCr2O3·(100 – x)SiO2 and 5R
n
O·xCr2O3·(95 – x)SiO2 (where x=0.01–1 mol.% and R=Li, Na and Ca) gel glasses was studied by optical absorption spectrophotometry, DTA-TG, XRD and electron microscopy.Samples heat treated at 60°C have green color due to the presence of Cr3+ in octahedral coordination. The optical transmission, and color (yellow, orange or ambar), of the samples heat treated between 200 and 700°C prove that Cr3+ (octahedrally coordinated) and Cr6+ (tetrahedrally coordinated) are both present. Segregation of Cr2O3 take place at temperatures above 800°C.In reducing conditions the gel glasses were green due to the presence of a high content of Cr3+ ions. Samples containing Li or Na show crystalline phases at temperatures below 850°C. 相似文献
110.
The dielectric properties of a series of poly(ester-ether-carbonate) multiblock terpolymers have been investigated as a function of ether and carbonate composition in the frequency range of 103–106 Hz. The degree of polymerization of the samples was determined by viscosimetry measurements. The weight fraction, degree of crystallinity, and melting temperatures were characterized by means of x-ray diffraction and DSC methods. Dielectric behavior has been discussed in terms of Havriliak-Negami formulation. The variation of the dielectric properties with temperature has been associated with two relaxation processes: a) the -relaxation process observed at low temperature, which is associated to local motion of polar groups attached to both the soft and the hard segments, and b) the process assigned to long-range molecular motions above the glass transition temperature. 相似文献