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131.
Leonardo M. da Costa Stanislav R. Stoyanov Raimundo N. Damasceno José Walkimar de M. Carneiro 《International journal of quantum chemistry》2013,113(24):2621-2628
Density Functional Theory (UB3LYP/6‐311++G(d,p)) calculations of the affinity of the pentaaqua nickel(II) complex for a set of phosphoryl [O?P(H)(CH3)(PhR)], imino [HN?C(CH3)(PhR)], thiocarbonyl [S?C(CH3)(PhR)] and carbonyl [O?C(CH3)(PhR)] ligands were performed, where R?NH2, OCH3, OH, CH3, H, Cl, CN, and NO2 is a substituent at the para‐position of a phenyl ring.The affinity of the pentaaqua nickel(II) complex for these ligands was analized and quantified in terms of interaction enthalpy (ΔH), Gibbs free energy (ΔG298), geometric and electronic parameters of the resultant octahedral complexes. The ΔH and ΔG298 results show that the ligand coordination strength increases in the following order: carbonyl < thiocarbonyl < imino < phosphoryl. This coordination strength order is also observed in the analysis of the metal‐ligand distances and charges on the ligand atom that interacts with the Ni(II) cation. The electronic character of the substituent R is the main parameter that affects the strength of the metal‐ligand coordination. Ligands containing electron‐donating groups (NH2, OCH3, OH) have more exothermic ΔH and ΔG298 than ligands with electron‐withdrawing groups (Cl, CN, NO2). The metal‐ligand interaction decomposed by means of the energy decomposition analysis (EDA) method shows that the electronic character of the ligand modulates all the components of the metal‐ligand interaction. The absolute softness of the free ligands is correlated with the covalent contribution to the instantaneous interaction energy calculated using the EDA method. © 2013 Wiley Periodicals, Inc. 相似文献
132.
As part of our program to prepare substituted rtaphthoquinones with potential biological activity1 we have synthetized 6, 7-methyleriedioxy-3-alky 1 lawsones (5a-g) from natural safrole (1) and carboxylic' acids (~50% overall yield). 相似文献
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134.
M. H. Godinho C. Cruz P. I. C. Teixeira A. J. Ferreira C. Costa P. S. Kulkarni 《Liquid crystals》2013,40(2):103-107
The phase behaviour of a number of N‐alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X‐ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50°C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at “Plateau borders” with three or more sides. Where walls meet three at a time, they do so at approximately 120° angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self‐organised monodomains, as observed in these systems, is expected to play an important role in potential applications. 相似文献
135.
Dr. Rubén D. Costa Dr. Juan Aragó Prof. Dr. Enrique Ortí Dr. Ted M. Pappenfus Prof. Dr. Kent R. Mann Dr. Katarzyna Matczyszyn Prof. Dr. Marek Samoc Dr. José L. Zafra Prof. Dr. Juan T. López Navarrete Prof. Dr. Juan Casado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1476-1488
The linear and non‐linear optical properties of a family of dumbbell‐shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2′‐bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non‐linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4 , with 3 and 6 thiophene rings, respectively), owing to the presence of the 3π? π* state of the conjugated bridge below the 3MLCT‐emitting states of the end‐capping RuII complexes. In contrast, the compound with the shortest bridge ( 2 , one thiophene ring) shows excellent photophysical features. Non‐linear optical experiments showed that the investigated compounds were strong non‐linear absorbers in wide energy ranges. Indeed, their non‐linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two‐photon absorption (TPA) but also noteworthy three‐photon‐absorption behavior, with a cross‐section value of 4×10?78 cm6 s2 at 1450 nm. This characteristic was complemented by the strong excited‐state absorption (ESA) that was observed for compounds 3 and 4 . As a matter of fact, the overlap between the non‐linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical‐power‐limiting applications. 相似文献
136.
M. C. Neves C. S. R. Freire B. F. O. Costa C. Pascoal Neto T. Trindade 《Cellulose (London, England)》2013,20(2):861-871
Cellulose/iron oxide hybrids were prepared by the controlled hydrolysis of FeC2O4 in the presence of vegetable and bacterial cellulose fibres as substrates. By varying the relative amount of FeC2O4 and NaOH, either hematite or magnetic iron oxides were grown at the cellulose fibres surfaces. This chemical strategy was used for the production of a number of materials, whose coloristic properties associated to their reinforcement role allowed their use as new hybrid pigments for thermoplastic starch (TPS) based products. The TPS reinforced materials were characterized by several techniques in order to evaluate: the morphology and the compatibility between the matrix and the fillers; the mechanical reinforcement effect of the cellulose/iron oxide pigments on TPS and the coloristic properties of the composites. All materials showed good dispersion and strong adhesion for the cellulose/iron oxide nanocomposites in the TPS matrix thus resulting in improved mechanical properties. 相似文献
137.
We study random 2‐dimensional complexes in the Linial–Meshulam model and prove that for the probability parameter satisfying a random 2‐complex Y contains several pairwise disjoint tetrahedra such that the 2‐complex Z obtained by removing any face from each of these tetrahedra is aspherical. Moreover, we prove that the obtained complex Z satisfies the Whitehead conjecture, i.e. any subcomplex is aspherical. This implies that Y is homotopy equivalent to a wedge where Z is a 2‐dimensional aspherical simplicial complex. We also show that under the assumptions where c > 3 and , the complex Z is genuinely 2‐dimensional and in particular, it has sizable 2‐dimensional homology; it follows that in the indicated range of the probability parameter p the cohomological dimension of the fundamental group of a random 2‐complex equals 2. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46, 261–273, 2015 相似文献
138.
139.
Silas Arandas Monteiro e Silva Michele Fernanda Costa Valarini Marlus Chorilli Stig E. Friberg 《Journal of Dispersion Science and Technology》2014,35(8):1191-1199
Formulations with lyotropic liquid crystals were prepared from a Brazilian nut vegetable oil, guarana extract and combination of sorbitan monooleate (Span 80) and sorbitan monolaurate ethoxylate EO 20 (Tween 20) in the ratio 1:3 (surfactant component) and their physical–chemical aspects and rheological properties were determined. Compositions with liquid crystals were found in the pseudoternary diagram in a surfactant range of 70–90% and polarized light microscopy, small-angle x-ray scattering (SAXS) showed them to be lamellar. The preparations were furthermore characterized rheologically by shear stress shear rate sweeps finding plastic and pseudoplastic behavior without thixotropy. Electric conductivity and pH measurements demonstrated a potential for future application as dermatological delivery system of the active compounds in the Bertholletia excelsa and Paullinia cupana. 相似文献
140.