Synthesis and characterization of the titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands and their behavior in ethylene polymerization

A series of new titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands (3a-h and 6a-h), [PhN=CRCHC(CF3)O](2)TiCl2 (3a, R = Me; 3b, R = n-C5H11; 3c, R = i-Pr; 3d, R = Cy; 3e, R = t-Bu; 3f, R = CH=CHPh; 3g, R = Et; 3h, R = n-C11H23) and [PhN=C(CF3)CHC(R)O](2)TiCl2 (6a, R = Ph; 6b, R = n-C5H11; 6c, R = i-Pr; 6d, R = Cy; 6e, R = t-Bu; 6f, R = CH=CHPh; 6g, R = CHPh2; 6h, R = CF3) have been synthesized and characterized. X-ray crystal structures analyses suggest that complexes 3c-e and 6c-d all adopt a distorted octahedral geometry around the titanium center. Complexes 3c, 3d and 6c display a cis-configuration of the two chlorine atoms around the titanium center, while complex 6d shows a trans-configuration of the two chlorine atoms. Especially, the configurational isomers (cis and trans) of complex 3e were identified both in solution and in the solid state by NMR and X-ray analyses. With modified methylaluminoxane as a cocatalyst, all the complexes are active towards ethylene polymerization, and produce high molecular weight polymers.

Switch-on transient behavior of vanadium phthalocyanine based organic transistors

The authors investigated the switch-on transient properties of p-type vanadium phthalocyanine (VOPc) transistors, which were fabricated by weak epitaxy growth on ordered para-sexiphenyl (p-6P) layer. The overshoot phenomenon of drain current had been observed in the VOPc/p-6P transistors, which was explained by the filling of carriers in traps of organic films. The small overshoot value of about 35% and transient duration time of 2 ms demonstrated the low trap concentration in organic films, which were comparable to the reported hydrogenated amorphous-silicon thin-film transistors. Therefore, the VOPc/p-6P transistors can be applied in active matrix liquid crystal display as switch elements.

Synthesis, structure and norbornene polymerization behavior of nickel complexes bearing two beta-ketoiminato chelate ligands

A series of nickel(II) complexes bearing two nonsymmetric bidentate beta-ketoiminato chelate ligands have been prepared, and the structures of complexes [(2,6-Me2C6H3)NC(CH3)C(H)C(Ph)O](2)Ni (4a) and [(2,6-Me2C6H3)NC(CH3)C(H)C(CF3)O](2)Ni (4c) have been confirmed by X-ray crystallographic analysis. These nickel(II) complexes were investigated as catalysts for the vinylic polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display very high activities and produce high molecular weight polymers. Catalytic activity of up to 1.16 x 10(4) kg/mol(Ni) .h and the viscosity-average molecular 9 weight of polymer of up to 870 kg/mol were observed. Catalyst activity, polymer yield, and polymer molecular weight could be controlled over a wide range by the variation of the reaction parameters such as Al/Ni molar ratio, norbornene/catalyst molar ratio, monomer concentration, polymerization reaction temperature and time.

Synthesis, structure and norbornene polymerization behavior of neutral palladium complexes

A series of neutral palladium(II) complexes bearing non-symmetric bidentate pyrrole-iminato or salicylaldiminato chelate ligands have been synthesized, and the structure of representative complexes (3a, 4a, and 5a) have been confirmed by X-ray crystallographic analysis. These palladium complexes have been investigated as catalysts for the polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display high activities and produce vinyl-addition polynorborenes. Catalytic activity of up to 8.52 x 10(3) kg/mol(Pd) h has been observed. Wide-angle X-ray diffraction (WAXD) has been used to investigate the polymer microstructure and it has been found that they are non-crystalline.

New neutral nickel(II) complexes bearing pyrrole-imine chelate ligands: synthesis, structure and norbornene polymerization behavior

New neutral nickel(II) complexes bearing nonsymmetric bidentate pyrrole-imine chelate ligands (4a-d), [2-(ArNCH)C4H3N]Ni(PPh3)Ph [Ar=2,6-diisopropylphenyl (a), 2-methyl-6-isopropylphenyl (b), 2,6-diethylphenyl (c), 2-tert-butylphenyl (d)], have been prepared in good yields from the sodium salts of the corresponding ligands and trans-Ni(PPh3)(2)(Ph)Cl, and the structure of complex 4a has been confirmed by X-ray crystallographic analysis. These neutral Ni(II) complexes were investigated as catalysts for the vinylic polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display very high activities and produce great mass polymers. Catalyst activity of up to 4.2 x 10(7) g (mol Ni h)(-1) and the viscosity-average molecular weight of polymer of up to 9.2 x 10(5) g mol(-1) were observed. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by the variation of reaction parameters such as Al-Ni ratio, norbornene-catalyst ratio, monomer concentration, polymerization reaction temperature and time.

The ontogenesis of lateralized behavior in the domestic cat, Felis silvestris catus

For the first time, the development of paw preferences in the domestic cat, Felis silvestris catus, is explored. Twelve cats were tested at ages 12 weeks, 6 months, and 1 year on a challenge requiring them to use one of their paws to retrieve food. To control for repeated testing of the same cats at different ages, the subjects' paw preferences were compared with those of cats tested just once, at 6 months (n = 11) or 1 year (n = 14) of age. Analysis revealed a significant effect of age on the distribution of cats' paw preferences. Cats were significantly more likely to be ambilateral than paw preferent at 12 weeks and at 6 months but more likely to display a lateral bias in paw use at 1 year. There was a significant positive correlation between cats' paw preferences at 6 months and at 1 year. Lateralized behavior was strongly sex related. Females had a greater preference for using their right paw; males were significantly more inclined to adopt their left. Analysis revealed no significant difference in the direction or strength of paw preferences of cats tested longitudinally or cross-sectionally at 6 months or 1 year of age. Findings indicate that cats develop paw preferences by 1 year and hint at a relative stability in preferred paw use over time. The strong sex effect observed strengthens the case for the influence of a biological mechanism in the emergence of motor asymmetry in cats.

Molecular variation at a candidate gene implicated in the regulation of fire ant social behavior

The fire ant Solenopsis invicta and its close relatives display an important social polymorphism involving differences in colony queen number. Colonies are headed by either a single reproductive queen (monogyne form) or multiple queens (polygyne form). This variation in social organization is associated with variation at the gene Gp-9, with monogyne colonies harboring only B-like allelic variants and polygyne colonies always containing b-like variants as well. We describe naturally occurring variation at Gp-9 in fire ants based on 185 full-length sequences, 136 of which were obtained from S. invicta collected over much of its native range. While there is little overall differentiation between most of the numerous alleles observed, a surprising amount is found in the coding regions of the gene, with such substitutions usually causing amino acid replacements. This elevated coding-region variation may result from a lack of negative selection acting to constrain amino acid replacements over much of the protein, different mutation rates or biases in coding and non-coding sequences, negative selection acting with greater strength on non-coding than coding regions, and/or positive selection acting on the protein. Formal selection analyses provide evidence that the latter force played an important role in the basal b-like lineages coincident with the emergence of polygyny. While our data set reveals considerable paraphyly and polyphyly of S. invicta sequences with respect to those of other fire ant species, the b-like alleles of the socially polymorphic species are monophyletic. An expanded analysis of colonies containing alleles of this clade confirmed the invariant link between their presence and expression of polygyny. Finally, our discovery of several unique alleles bearing various combinations of b-like and B-like codons allows us to conclude that no single b-like residue is completely predictive of polygyne behavior and, thus, potentially causally involved in its expression. Rather, all three typical b-like residues appear to be necessary.

Do virtual platforms impact user behavior? An experimental comparison between messages on the company's website and Facebook page.

Companies have looked for many new ways to communicate with their customers. In the current scenario, Facebook has proven to be an efficient communication tool between consumers and businesses. This study aims to understand the differences in the complaint messages sent to companies, through an experiment that measured the emotional tone and the lack of formality in each message received by the website and the Facebook page of the company. As expected, people are more informal on Facebook. However, contrary to our intuition, participants tended to display more emotions on the company website. The social norms theory and the impression management contributed to explain the phenomena found.

Do equity and foreign currency risk premiums display common patterns?

In da Costa et al. (2006) we have shown how a same pricing kernel can account for the excess returns of the S&:P500 over the US short term bond and of the uncovered over the covered trading of foreign government bonds. In this paper we estimate and test the overidentifying restrictiom; of Euler equations associated with "ix different versions of the Consumption Capital Asset Pricing I\Iodel. Our main finding is that the same (however often unreasonable) values for the parameters are estimated for ali models in both nmrkets. In most cases, the rejections or otherwise of overidentifying restrictions occurs for the two markets, suggesting that success and failure stories for the equity premium repeat themselves in foreign exchange markets. Our results corroborate the findings in da Costa et al. (2006) that indicate a strong similarity between the behavior of excess returns in the two markets when modeled as risk premiums, providing empirical grounds to believe that the proposed preference-based solutions to puzzles in domestic financiaI markets can certainly shed light on the Forward Premium Puzzle.

Reproductive behavior of the swimming crab Arenaeus cribrarius (Lamarck, 1818) (Crustacea, Brachyura, Portunidae) in captivity

In this study, the reproductive behavior exhibited by Arenaeus cribrarius in captivity was described, and the duration of each behavioral stage was measured. Swimming crabs were trawled in Ubatuba, northern littoral of São Paulo State, Brazil, and maintained in aquaria. Water conditions and food items were provided according to this species' natural requirements in the wild. In the presence of premolt females, intermolt males exhibited a courtship display that became intensified when the potential mate was visually perceived. After mate selection, the male carried the female under itself (precopulatory position) for 29.8 +/- 5.1 d until the female molted. Afterwards, the male manipulated the recently molted female, and inverted her position under itself as to penetrate her with his first pair of pleopods (copulation), a process that took 17.1 +/- 4.6 h. After copulation the male continued to carry his soft-shelled mate for 29.7 +/- 5.8 d (postcopulatory position). The time elapsed between copulation and spawning was 57.8 +/- 3.8 d and the time interval between successive spawns 33.8 +/- 7.1 d. Total embryonic development took 13.5 +/- 2.1 d in temperature conditions of 25.0 +/- 2.0 degrees C. During the last 4.7 +/- 1.4 d embryos' eyes were already visible. The reproductive behavior pattern in A. cribrarius is very similar to those previously described in other portunids.

Anting behavior by the White-bearded Manakin (Manacus manacus, Pipridae): an example of functional interaction in a frugivorous lekking bird

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Reproductive behavior and seasonal occurrence of Psecas viridipurpureus (Salticidae, Araneae)

O comportamento reprodutivo e a ocorrência sazonal de Psecas viridipurpureus foram estudados na Estação Ecológica do Noroeste Paulista, uma pequena área de conservação na região noroeste do Estado de São Paulo, Brasil (49º22'50W e 20º48'36S). P. viridipurpureus ocorreu em gravatás, uma bromeliácea (Bromelia balansae, Bromeliaceae) que não acumula água de chuva. Durante a exibição de corte, o casal ocupou a região mediana das folhas de gravatás, com o macho sempre localizado em uma posição superior à da fêmea. Os machos de P. viridipurpureus apresentaram um comportamento de corte complexo, que incluiu cinco padrões motores. O comportamento de corte e a cópula ocorreram preponderantemente durante a estação chuvosa e o recrutamento de jovens entre dezembro e julho. O abrigo de P. viridipurpureus difere do padrão de Salticidae, pois as ootecas são recobertas por uma cobertura de seda plana e não são incluídas em casulos.

Thermal behavior of cellulose acetate produced from homogeneous acetylation of bacterial cellulose

Cellulose acetate (CA) is one of the most important cellulose derivatives and its main applications are its use in membranes, films, fibers, plastics and filters. CAs are produced from cellulose sources such as: cotton, sugar cane bagasse, wood and others. One promissory source of cellulose is bacterial cellulose (BC). In this work, CA was produced from the homogeneous acetylation reaction of bacterial cellulose. Degree of substitution (DS) values can be controlled by the acetylation time. The characterization of CA samples showed the formation of a heterogeneous structure for CA samples submitted to a short acetylation time. A more homogeneous structure was produced for samples prepared with a long acetylation time. This fact changes the thermal behavior of the CA samples. Thermal characterization revealed that samples submitted to longer acetylation times display higher crystallinity and thermal stability than samples submitted to a short acetylation time. The observation of these characteristics is important for the production of cellulose acetate from this alternative source. (C) 2008 Elsevier B.V. All rights reserved.

Aqueous solution behavior of thermosensitive (N-isopropylacrylamide-acrylic acid-ethyl methacrylate) terpolymers

A series of N-isopropylacrylamide (NIPAM)-acrylic acid-ethyl methacrylate terpolymers with varied monomer compositions was prepared by radical polymerization. The solution behavior of these polymers was studied in dilute aqueous solution using spectrophotometry, fluorescence spectroscopy and high-sensitivity differential scanning calorimetry. The results obtained revealed that the lower critical solution temperatures depend strongly on the copolymer composition, solution pH and ionic strength. At a high pH, the ionization of acrylic acid (AA) units leads to an increase in solution cloud points (T-c). Solutions of polymers containing 10% or less of AA display a constant T-c for pH above 5.5, with 15% there is a continuous increase in T-c with pH and, for higher AA contents, no clouding was observed within the studied temperature range. Fluorescence probe studies were conducted by following the I (1)/I (3) ratio of pyrene vibronic bands and the emission of anilinonaphtalene sulfonic acid, sodium salt (ANS), both approaches revealing the existence of hydrophobic domains for polymers with higher ethyl methacrylate content at temperatures lower than T-c, suggesting some extent of aggregation and/or a coil-to-globule transition. Scanning calorimetry measurements showed an endothermic transition at temperatures agreeing with the previously detected cloud points. Moreover, the transition curves became broader and with a smaller transition enthalpy, as both the AA content and the solution pH were increased. These broader transitions were interpreted to be the result of a wider molecular distribution upon polymer ionization, hence, displaying varied solution properties. The decrease in transition enthalpy was rationalized as a consequence of reminiscent hydration of NIPAM units, even after phase separation, owing to the presence of electric charges along the polymer chain.

The Effect of Water Immersion and UV Radiation Aging on the Shear Behavior of Woven Continuous Fiber/PEI Laminates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)