Influence of Zn2+ co-doping ion on Eu3+-O2- associate luminescence in Sr2SiO4

This work reports on the study about the luminescence behavior of Eu3+-O2- associates in Sr2SiO4 doped with Eu3+, or simultaneously doped with Eu3+ and Zn2+ ions, where the Zn2+ doping ion acts as a charge compensating agent. Both Sr2SiO4:Eu3+ and Sr2SiO4:Eu3+,Zn2+ emission spectra show two types D-5(0)-->F-7(0) type transitions, one type related to Eu3+ in the Sr2+ Site, at 577 and 580 nm and the other one related to Eu3+-O2- associates, at 574 nm. Excitation spectra present two CT bands at 275 and 324 nm related to each emission center, respectively. Comparing the relative intensities between the emission spectra, the 0-->0 transition at 574 nm assigned to Eu3+-O2- associates in the Sr2SiO4:Eu3+ emission spectrum is much more intense than the same transition in the Sr2SiO4:Eu3+,Zn2+ emission spectrum. Moreover, in the Sr2SiO4:Eu3+ excitation spectrum, the intensity ratio between the CT band related to the Eu3+-O2- emission center and Eu3+ F-7-->L-5(6) transition is also larger than in the Sr2SiO4:Eu3+,Zn2+ one. Therefore, the presence of Zn2+ species provides an extra charge compensating mechanism, which decreases the formation of Eu3+-O2- associates. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Factors which affect the catalytic activity of iron(III) meso tetrakis(2,6-dichlorophenyl)porphyrin chloride in homogeneous system

An optimization study of the reaction conditions of Fe(TDCPP)Cl when it is used as catalyst in the hydroxylation of cyclohexane by iodosylbenzene (PhIO) has been carried out, It was found that Fe(TDCPP)Cl follows the classical PhIO mechanism described for Fe(TPP)Cl, which involves the monomeric active species Fe-IV(O)P-+. (I). In the optimized condition ([Fe(TDCPP) = 3.0 X 10(-4) mol l(-1) in 1,2-dichloroethane (DCE); ultrasound stirring at 0 degrees C; PhIO/FeP molar ratio = 100), this FeP led to a yield of cyclohexanol (C-ol) of 96% and a turnover number of 96, Therefore, Fe(TDCPP)Cl may be considered a good biomimetic model and a very stable, resistant and selective catalyst, which yields C-ol as the sole product. DCE showed to be a better solvent than dichloromethane (DCM), 1 DCE:1 MeOH mixture or acetonitrile (ACN). Since the Fe-IV(O)P-+. is capable of abstracting hydrogen atom from DCM, MeOH or ACN, the solvent competes with the substrate. Presence of O-2 lowers the yield of C-ol, as it can further oxidize this alcohol to carboxylic acid in the presence of radicals, Presence of H2O also causes a decrease in the yield, since it converts the active species I into Fe-IV(OH)P, which cannot oxidize cyclohexane. Addition of excess imidazole or OH- to the system results in a decrease in the yield of C-ol, due to the formation of the hexacoordinated complexes Fe(TDCPP)Im(2)(+) (low-spin, beta(2) = 2.5 X 10(8) mol(-2) l(2)) and Fe(TDCPP)(OH)(2)(-) (high-spin, beta(2) = 6.3 X 10(7) mol(-2) l(2)), the formation of both Fe(TDCPP)Im(2)(+) and Fe(TDCPP)(OH)(2)(-) complexes were confirmed by EPR studies. The catalytic activities of Fe(TDCPP)C and Fe(TFPP)Cl were compared, the unusually high yields of C-ol with Fe(TFPP)Cl obtained when ultrasound, DCM and O-2 atmosphere were used, suggest that a parallel mechanism involving the mu-oxo dimer form, O-2 and radicals may also be occurring with this FeP, besides the PhIO mechanism.

Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel

In this work we have made use of the study of the interaction between Fe(TDCPP)(+) and the axial ligands OH- and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 X 10(-6) mol Fe(TDCPP)(+)/g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin (FeP)-P-III species. In Fe(TDCPP)IPG 1 (containing 1.1 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-4) mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP)(+) is present as a mixture of low-spin (FeP)-P-III and (FeP)-P-II species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the (FeP)-P-III to the support partially blocks the reaction between Fe(TDCPP)(+) and PhIO, thus leading to the formation of only a small amount of the active species Fe-IV(OP+, while the (FeP)-P-II species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP)(+) and decreasing the amount of imidazole in the support led to the obtention of high-spin (FeP)-P-III EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-5) mol imidazole/g of IPG), together with low-spin (FeP)-P-III species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it.

CYTOGENETIC AND DNA CONTENT IN 6 GENERA OF THE FAMILY CALLICHTHYIDAE (PISCES, SILURIFORMES)

Cytogenetic studies involving conventional Giemsa staining, C-banding analysis and silver staining of NORs were performed on nine species belonging to six genera of the family Callichthyidae. The diploid number ranged from 2n = 44 to 2n = 100, the number of chromosomal pairs with NORs ranged from 1 to 4 and constitutive heterochromatin was mainly distributed in the centromeric and/or pericentromeric position of the chromosomes. The DNA content of erythrocytes from six species studied ranged from 1.18 +/- 0.07 to 2.77 +/- 0.22 pg/nucleus. The extensive variability in karyotypes and in nuclear DNA content detected are in accordance with the initial hypothesis that chromosome rearrangements and polyploidy have played a significant role in the evolutionary history of Callichthyidae.

An unusual C-6-C-6 '' linked flavonoid from Miconia cabucu (Melastomataceae)

Chromatographic fractionation of the methanolic extract from the leaves of Miconia cabucu Hoehne (Melastomataceae) afforded the first example of a C-6-C-6 linked flavone dimer, 5-hydroxy-4',7-dimethoxyflavone-(6-C-6)-5-hydroxy-3 4',7-trimethoxyflavone as well as the known compounds, quercetin- 3-O-alpha-L- rhamnopyranosyl-(2 -> 1)-O-beta-D-xylopyranoside, quercetin-3-O-alpha-L-rhamnopyranoside, myricetin-3-O-alpha-L-rhamnopyranoside, quercetin-3-O-beta-D-glucopyranoside, kaempferol -3-O-beta-D-(6-coumaroyl) -glucopyranoside and gallic acid. Their chemical identities were established by application of NMR spectroscopic methods including 2D-NMR, as well as UV and ESI-MS analyses. (c) 2007 Elsevier Ltd. All rights reserved.

4f-4f intensities of the Tm3+ ions in fluoroindate glasses: the influence of third-order effects through odd intensity parameters

In this work an analysis of the phenomenological Omega(lambda) intensity parameters for the Tm3+ ion in fluoroindate glass is made using the standard Judd-Ofelt theory, and a modified oscillator strength taking into account odd-order contributions is utilized. Different sets of phenomenological intensity parameters Omega(lambda) (lambda=1,2,3,4,5,6) are discussed. The set of better quality is used to analyze the influence of third-order effects through odd intensity parameters in the new approximation. Fluoroindate glasses of compositions (40-x)InF3-20ZnF(2)-20SrF(2)-16BaF(2)-2GdF(3)-2NaF-xTmF(3) with x=1, 2 and 3 mol% were prepared, and the absorption spectra at room temperature in the spectral range from 300 to 2500 nm were obtained. The experimental oscillator strengths determined from the area under the absorption band are compared to the calculated ones. (C) 1998 Elsevier B.V. S.A.

Titania-based organic-inorganic hybrid planar waveguides

Eu3+ -doped titania-silica planar waveguides were prepared from tetraethylorthotitanate (TEOT) and modified silane 3-amino-propyltriethoxysilane (APTS). Films were deposited on borosilicate glass substrates by a dip-coating technique. The refractive index, the thickness and the total attenuation coefficient of the waveguides were measured at 632.8 and 1550 nm by prism coupling technique. Starting from pure titania films, the addition of modified silane leads to a decrease in the refractive index and an increase in thickness. Squared electric field simulation has shown that the light confinement in the waveguide increases with the silane content of the so]. Emission spectra present a broad emission band due to the modified silane and EU emission transitions arising mainly from the D-5(0) level to the F-7(J) (J = 0-4) manifolds. The dependence of transition intensities and excited state lifetimes on the initial composition and also on the heat treatment performed was interpreted in terms of structural changes occurring during the preparation process. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Effect of apparent viscosity on the pressure drop during fluidized bed drying of soursop pulp

Pressure drop and minimum fluidization velocity were experimentally studied in a vibro-fluidized bed of inert particles subjected to different vibration intensities during drying of soursop pulp. Maltodextrin was added to the pulp in order to prevent stickiness between particles and the consequent bed collapse. Pulps were initially concentrated, resulting in pastes with different soluble solids content, and a constant fraction of maltodextrin was guaranteed in the final pulp samples. The pulp theological behavior as affected by temperature and total soluble solids content, including maltodextrin, was evaluated and the effect of pulp apparent viscosity on pressure drop and minimum vibro-fluidization velocity were investigated. Two types of inert particles -3.6 mm glass beads and 3 mm Teflon cylinders (length and diameter) - were tested and, due to lower pressure drop presented by Teflon cylinders during operation of the dry vibro-fluidized bed, these particles were adopted for pulp drying process. Increasing pulp apparent viscosity caused a considerable increase in the vibro-fluidized bed pressure drop during pulp drying and, as a consequence resulted in a larger value of minimum vibro-fluidization velocity. on the other hand, the negative effect of increasing apparent viscosity could be attenuated by increasing the fluidized bed vibration intensity, which could prevent stickiness between particles. (c) 2006 Elsevier B.V. All rights reserved.

Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films

Strong interest in developing technology for visual information. stimulates research for thin film electroluminescent devices. Here, for the first time, we report that thulium- and terbium-doped zinc-oxide films are suitable for electroluminescence applications. Two different devices were assembled as lTO/LiF/ZnO:RE/LiF/Al or ITO/SiO2/ZnO:RE/SiO2/Al, where ZnO:RE is a film of zinc oxide containing 10 at% of Tb3+ or Tm3+. Electroluminescence spectra show that besides a broad emission band with maximum around 650 nm assigned to ZnO, also emission lines from Tb3+ at 484 nm (D-5(4) -> F-7(6)), 543 nm (D-5(4) -> F-7(6)), and 589 nm (D-5(4) -> F-7(4)), or from Tm3+ at 478 nm ((1)G(4) -> H-3(6)), and 511 mn (D-1(2) -> H-3(5)) were detected. Intensity of emission as function of applied voltage and current-voltage characteristic are shown and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Ovarian follicle diameter at timed insemination and estrous response influence likelihood of ovulation and pregnancy after estrous synchronization with progesterone or progestin-based protocols in suckled Bos indicus cows

The objectives of the present study were to evaluate factors associated with estrous synchronization responses and pregnancy per insemination (P/AI) in Bos indicus beef cows submitted to progesterone-based fixed-time artificial insemination (FTAI) protocols. A total of 2388 cows (1869 Nellore and 519 crossbred Nellore x Angus) from 10 commercial farms were evaluated to determine the relationships among breed, body condition score (BCS) on the first day of the FTAI protocol, the occurrence of estrus between progesterone device removal and FTAI and diameter of largest ovarian follicle (LF) at FTAI on estrous synchronization responses and P/AI. Cows (n=412 primiparous; 1976 multiparous) received an intravaginal device containing progesterone or an ear implant containing norgestomet (a progestin), and an injection of estradiol at the beginning of the estrous synchronization protocol. Body condition was scored using a 1-5 scale on the first day of the FTAI protocol and at 30-60 days postpartum. Females received 300IU of equine chorionic gonadotropin (eCG) and PGF(2 alpha) on the day the progesterone device/implant was removed and were inseminated 48-60h later. At insemination, cows (n=2388) were submitted to an ultrasonographic exam to determine the diameter of the LF. Follicles were classified into four categories based on mean and standard deviation (SD) of the LF (LF1 = two SD below the mean; LF2 = mean minus one SD; LF3 = mean plus one SD; LF4 = two SD above the mean). Ovulation rate was determined in a subset of cows (n=813) by three consecutive ultrasonographic exams: (1) at time of progesterone device/implant removal, (2) at time of FTAI and (3) 48 h after FTAI. Ovulation was defined as the disappearance of a large follicle (>= 8.0 mm) that was previously recorded. Estrus was determined in a subset of the cows (n = 445) by the activation of a detection of estrous patch placed on the tail head on the day of progesterone device/implant removal. Pregnancy was diagnosed 30 days after FTAI. Pregnancy was influenced (P = 0.001) by follicle diameter [LF1 = 27.5% (81/295), LF2 = 46.6% (328/705), LF3 = 57.9% (647/1118), LF4 = 63.3% (171/270)] and the occurrence of estrus [estrus = 67.7% (174/257) and no estrus = 36.2% (68/188)]. Follicle diameter at FTAI influenced ovulation rate [LF1 = 42.5% (34/80), LF2 = 73.9% (161/218), LF3 = 95.8% (407/425), LF4 = 97.8% (88/90)], the occurrence of estrus [LF1 = 54.8% (51/93), LF2 = 33.6% (43/128), LF3 = 68.9% (126/183), LF4 = 90.2% (37/41)] and P/AI among cows that had ovulations [LF1 =32.4% (11/34), LF2 = 50.3% (81/161), LF3 = 60.0% (244/407), LF4 = 68.2% (60/88)]. Improving estrous responses between progesterone device withdrawal and FTAI and increasing the diameter of the LF at FTAI may be important aspects to achieve improved estrous synchronization responses and P/AI following progesterone/progestin and estradiol based FTAI protocols in suckled Bos indicus cows. (C) 2010 Elsevier B.V. All rights reserved.

Effects of dispersion by Gd3+ upon europium diphenylphosphinate luminescence

A series of binary diphenylphosphinates with Eu3+ and Gd3+ were prepared. The compounds have the general formula Gd1-xEux(DPP)(3), where x ranges from 0 to 1. The spectroscopic measurements show interesting behavior. The intensity of the D-5(0) --> F-7(2) transitions decreases relative to D-5(0) --> F-7(1) With an increase in europium dispersion. Inside the temporal domain, the same decrease is observed with increasing delay after excitation. The lifetimes are also affected, which can be seen in the x = 1 compound, where the decay is a first-order process and lifetime values are 4.81 ms. In the binary compound, as an effect of dispersion, the lifetime of the D-5(0) level measured at the D-5(0) --> F-7(1) transition increases with europium dispersion, and the average along the series is 6.25 ms. The decay measured at the D-5(0) --> F-7(2) transitions reveals a second-order process with lifetimes ranging from 1.90 to 6.00 ms. (C) 2001 Elsevier B.V. B.V. All rights reserved.

SAE 1045 steel/WC-Co/Ni-Cu-Ni/SAE 1045 steel joints prepared by dynamic diffusion bonding: Microelectrochemical studies in 0.6 M NaCl solution

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

Comparative study between atropine and hyoscine-N-butylbromide for reversal of detomidine induced bradycardia in horses

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