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351.
A manganese catalyst containing a tetradentate ligand derived from triazacyclononane exhibits high catalytic activity in epoxidation reactions using peracetic acid as oxidant. The system exhibits broad substrate scope and requires small (0.1-0.15 mol %) catalyst loading. The catalyst is remarkably selective toward aliphatic cis-olefins. Mechanistic studies point toward an electrophilic oxidant delivering the oxygen atom in a concerted step. 相似文献
352.
Martínez A Rodríguez-Gironés MA Barbosa A Costas M 《The journal of physical chemistry. A》2008,112(38):9037-9042
Bright yellow and red colors in animals and plants are assumed to be caused by carotenoids (CAR). In animals, these pigments are deposited in scales, skin and feathers. Together with other naturally occurring and colorless substances such as melatonin and vitamins, they are considered antioxidants due to their free-radical-scavenging properties. However, it would be better to refer to them as "antiradicals", an action that can take place either donating or accepting electrons. In this work we present quantum chemical calculations for several CAR and some colorless antioxidants, such as melatonin and vitamins A, C and E. The antiradical capacity of these substances is determined using vertical ionization energy (I), electron affinity (A), the electrodonating power (omega(-)) and the electroaccepting power (omega(+)). Using fluor and sodium as references, electron acceptance (R(a)) and electron donation (R(d)) indexes are defined. A plot of R(d) vs R(a) provides a donator acceptor map (DAM) useful to classify any substance regarding its electron donating-accepting capability. Using this DAM, a qualitative comparison among all the studied compounds is presented. According to R(d) values, vitamin E is the most effective antiradical in terms of its electron donor capacity, while the most effective antiradical in terms of its electron acceptor capacity, R(a), is astaxanthin, the reddest CAR. These results may be helpful for understanding the role played by naturally occurring pigments, acting as radical scavengers either donating or accepting electrons. 相似文献
353.
Luciana Costas Licia M. Pera Azucena Gómez López Magdalena Mechetti Guillermo R. Castro 《Applied biochemistry and biotechnology》2012,167(5):1396-1407
Sulfasalazine (SLZ) is a synthetic nonsteroidal anti-inflammatory drug used mainly for the treatment of an inflammatory bowel and other diseases. Two pectins with different methylation degrees were blended to synthesized gel microspheres by ionotropic gelation for SLZ encapsulation. The encapsulation efficiency was found to be around of 99% in all formulations tested. However, different SLZ release profiles related to the methylation degrees of pectin were observed. Mixture of low methylated (LM) and high methylated (HM) pectins in the presence of calcium(II) displayed the best microsphere morphologies among the formulations tested determined by optical and electronic microscopies. The percentage of drug release using a mixture of LM and HM pectins after 255?min in simulated gastric fluid (pH?=?1.2), simulated intestinal fluid (pH?=?6.8), and phosphate buffer (pH?=?7.4) were 15.0%, 47.0%, and 52.2%, respectively. 相似文献
354.
Nikolaos P. Rachaniotis Tom K. Dasaklis Costas P. Pappis 《European Journal of Operational Research》2012,216(1):225-231
The resources available to tackle an epidemic infection are usually limited, while the time and effort required to control it are increasing functions of the starting time of the containment effort. The problem of scheduling limited available resources, when there are several areas where the population is infected, is considered. A deterministic model, appropriate for large populations, where random interactions can be averaged out, is used for the epidemic’s rate of spread. The problem is tackled using the concept of deteriorating jobs, i.e. the model represents increasing loss rate as more susceptibles become infected, and increasing time and effort needed for the epidemic’s containment. A case study for a proposed application of the model in the case of the mass vaccination against A(H1N1)v influenza in the Attica region, Greece and a comparative study of the model’s performance vs. the applied random practice are presented. 相似文献
355.
Costas M Ribas X Poater A López Valbuena JM Xifra R Company A Duran M Solà M Llobet A Corbella M Usón MA Mahía J Solans X Shan X Benet-Buchholz J 《Inorganic chemistry》2006,45(9):3569-3581
Density functional theory (DFT) calculations have been carried out for a series of Cu(I) complexes bearing N-hexadentate macrocyclic dinucleating ligands and for their corresponding peroxo species (1c-8c) generated by their interaction with molecular O2. For complexes 1c-7c, it has been found that the side-on peroxodicopper(II) is the favored structure with regard to the bis(mu-oxo)dicopper(III). For those complexes, the singlet state has also been shown to be more stable than the triplet state. In the case of 8c, the most favored structure is the trans-1,2-peroxodicopper(II) because of the para substitution and the steric encumbrance produced by the methylation of the N atoms. Cu(II) complexes 4e, 5e, and 8e have been obtained by O2 oxidation of their corresponding Cu(I) complexes and structurally and magnetically characterized. X-ray single-crystal structures for those complexes have been solved, and they show three completely different types of Cu(II)2 structures: (a) For 4e, the Cu(II) centers are bridged by a phenolate group and an external hydroxide ligand. The phenolate group is generated from the evolution of 4c via intramolecular arene hydroxylation. (b) For 5e, the two Cu(II) centers are bridged by two hydroxide ligands. (c) For the 8e case, the Cu(II) centers are ligated to terminally bound hydroxide ligands, rare because of its tendency to bridge. The evolution of complexes 1c-8c toward their oxidized species has also been rationalized by DFT calculations based mainly on their structure and electrophilicity. The structural diversity of the oxidized species is also responsible for a variety of magnetic behavior: (a) strong antiferromagnetic (AF) coupling with J = -482.0 cm(-1) (g = 2.30; rho = 0.032; R = 5.6 x 10(-3)) for 4e; (b) AF coupling with J = -286.3 cm(-1) (g = 2.07; rho = 0.064; R = 2.6 x 10(-3)) for 5e; (c) an uncoupled Cu(II)2 complex for 8e. 相似文献
356.
Adam Janiak Tomasz Krysiak Costas P. Pappis Theodore G. Voutsinas 《European Journal of Operational Research》2009
This paper deals with a problem of scheduling jobs on the identical parallel machines, where job values are given as a power function of the job completion times. Minimization of the total loss of job values is considered as a criterion. We establish the computational complexity of the problem – strong NP-hardness of its general version and NP-hardness of its single machine case. Moreover, we solve some special cases of the problem in polynomial time. Finally, we construct and experimentally test branch and bound algorithm (along with some elimination properties improving its efficiency) and several heuristic algorithms for the general case of the problem. 相似文献
357.
358.
Sanghoon Ahn David J. Hwang Hee K. Park Costas P. Grigoropoulos 《Applied Physics A: Materials Science & Processing》2012,108(1):113-120
The rear contact solar cell concept has been implemented to increase the solar cell efficiency. Practically, it necessitates rapid fabrication of a large number of via holes to form low-loss current paths. It is not a trivial task to drill a number of microscopic holes through a typical Si wafer of ??200???m thickness at reasonable processing throughput and yield. In this research, a femtosecond laser is employed to drill via holes in both crystalline silicon (c-Si) and multicrystalline silicon (mc-Si) thin wafers of ??170???m thickness with various laser parameters such as number of laser shots and pulse energy. Since a significantly high pulse energy compared to ablation threshold is mainly applied, aiming to achieve a rapid drilling process, the femtosecond laser beam is subjected to complex non-linear characteristics. Therefore, the relative placement of the sample with respect to the laser focal position is also rigorously examined. While the non-linear effect at high pulse energy regime is complex, it also facilitates the drilling process in terms of achieving high-aspect ratio, for example, by extending the effective depth of focus by non-linear effect. Cross-sectional morphological analysis in conjunction with on-line emission and shadowgraph imaging are carried out in order to elucidate the drilling mechanism. 相似文献
359.
360.
Maria Vamvakaki Edna N. Yamasaki Stella C. Hadjiyannakou Costas S. Patrickios 《Macromolecular Symposia》2001,171(1):209-224
Group transfer polymerization was used to synthesize several series of hydrophilic random and model networks. Cationic random networks were prepared both in bulk and in tetrahydrofuran (THF) using a monofunctional initiator and simultaneous polymerization of monomer and branch units, while a bifanctional initiator was employed in THF for the synthesis of model networks comprising basic or acidic chains. Upon polymerization of the monomer, the latter initiator gives linear polymer chains with two “living” ends, which are subsequently interconnected to a polymer network by the addition of a branch unit. Homopolymer network star polymers were also synthesized in THF by a one‐pot procedure. The synthesis involved the use of a monofunctional initiator and the four‐step addition of the following reagents: (i) monomer, to give linear homopolymers; (ii) branch unit, to form “arm‐first” star polymers; (iii) monomer, to form secondary arms and give “in‐out” star polymers; and, finally (iv) branch unit again, to interconnect the “in‐out” stars to networks. Different networks were prepared for which the degree of polymerization (DP) of the linear chains between junction points was varied systematically. For all networks synthesized, the linear segments, the “arm‐first” and the “in‐out” stars were characterized in terms of their molecular weight (MW) and molecular weight distribution (MWD) using gel permeation chromatography (GPC). The degrees of swelling of both the random and model networks in water were measured and the effects of DP, pH, and monomer type were investigated. 相似文献