Reaction pathway to the synthesis of anatase via the chemical modification of titanium isopropoxide with acetic acid

Anatase nanoparticles were obtained through a modified sol-gel route from titanium isopropoxide modified with acetic acid in order to control hydrolysis and condensation reactions. The modification of Ti(O(i)Pr)(4) with acetic acid reduces the availability of groups that hydrolyze and condense easily through the formation of a stable complex whose structure was determined to be Ti(OCOCH(3))(O(i)Pr)(2) by means of FTIR and (13)C NMR. The presence of this complex was confirmed with FTIR in the early stages of the process. A doublet in 1542 and 1440 cm(-1) stands for the asymmetric and symmetric stretching vibrations of the carboxylic group coordinated to Ti as a bidentate ligand. The gap of 102 cm(-1) between these signals suggests that acetate acts preferentially as a bidentate rather than as a bridging ligand between two titanium atoms. The use of acetic acid as modifier allows the control of both the degree of condensation and oligomerization of the precursor and leads to the preferential crystallization of TiO(2) in the anatase phase. A possible reaction pathway toward the formation of anatase is proposed on the basis of the intermediate species present in a 1:1 Ti(O(i)Pr)(4):CH(3)COOH molar system in which esterification reactions that introduce H(2)O into the reaction mixture were seen to be negligible. The Rietveld refinement and TEM analysis revealed that the powder is composed of isotropic anatase nanocrystallites.

Synthesis and reactivity in salt metathesis reactions of trivalent [La(Tp(Me2))(2)X] (X = Cl, I) complexes: crystal structures of [La(Tp(Me2))(2)Cl] and [La(Tp(Me2))(2)(kappa(2)-pz(Me2))]

Reaction of LaX3(THF)(n) (X = Cl, 1) with two equiv. of K(Tp(Me2)) gave good yields of the bis-Tp complexes [La(Tp(Me2))(2)X] (X = Cl (1); I (3)). However, the formation of 1 and 3 is always accompanied by significant amounts of La(Tp(Me2))(2)(kappa(2)-pz(Me2)) ([pz(Me2)](-) = 3,5-dimethyl-pyrazolato) (2). The pyrazolato complex 2, which presumably arises from decomposition of the [Tp(Me2)](-) moiety during salt metathesis, was independently prepared in good yield from 1 and in situ generated [pz(Me2)](-). The solid-state structures of 1 and 2 were determined by single-crystal X-ray diffraction studies. Subsequent reactions of halogeno-Tp(Me2) complexes 1 and 3 with various alkali metal salts MR (M = Li, R = CH2SiMe3, Ph, N(SiMe3)(2); M = K, R = OAr) gave M(Tp(Me2)) as the major product. Alternatively, the mono-Tp bis(aryloxide) derivatives [Ln(Tp(Me2))(OC6H2-2,6-'Bu-4-Me)(2)] (Ln = La (4); Nd (5)) were obtained in high yields by salt metathesis of [Ln(OC6H2-2,6-'Bu-4-Me)(3)] with one equiv. of K(Tp(Me2)). (C) 2004 Elsevier Ltd. All rights reserved.

Thermal-optical properties of Ga : La : S glasses measured by thermal lens technique

In this work the quantitative theoretical treatment for two beam mode mismatched thermal lens spectrometry is applied to investigate the thermo-optical properties of chalcohalide (chalcolgenides and halides mixture) glasses. For the three kinds of glass studied the thermal diffusivity varied between 2.5 and 2.7 x 10(-3) cm(2) s(-1). Using these results and supposing Dulong-Petit specific heats we estimated the thermal conductivity and temperature ratio of optical path length (ds/dT) and temperature coefficient of refractive index (dn/dT). All samples had positive ds/dT(similar to 3.3 x 10(-6) K-1) and negative dn/dT (similar to -26 x 10(-6) K-1). The difference between these parameters and the change of signal are consequences of the expansion coefficient (13 x 10(-6) K-1) and refractive index (n similar to 2.6) of chalcohalides. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Modification of glassy carbon electrodes with a poly-L-lysine/glutaraldehyde film

A film of poly-L-lysine (PLL) adheres better to the surface of a glassy carbon electrode when the PLL is partially cross-linked by means of glutaraldehyde. A film composition of 97.5% PLL/2.5% glutaraldehyde gives good adhesion and retains the anionic exchange capability of the PLL. The performance of the film was tested with hexacyanoferrate(III) using electrochemical and nonelectrochemical accumulation.

Experimental model for transanal endorectal pull-through surgery. Technique of de la Torre and Ortega

Background: We describe an experimental model for transanal endorectal pull-through surgery using the method of de]a Torre and Ortega that can be used for training purposes in experimental laboratories.Methods: Ten rabbits were submitted to the transanal endorectal pull-through technique of de la Torre and Ortega. Animals were randomly selected in the Botucatu School of Medicine experimental laboratory. Animals weighted between 2800 and 4400 g. Colons were not prepared, and antibiotic therapy was not used; dipyrone(1) was administered postoperatively for analgesic purposes. We standardized resected segment size, recorded surgical time, and observed Survival and possible complications for 1 month.Results: All animals survived the initial follow-up period without infection. Bowel movements returned quickly, and all animals were evacuating regularly within the first 24 hours. Mean surgical time was 48.6 minutes.Conclusions: the experimental model proposed in this study is very useful for training and improving surgical techniques using the method of de la Torre and Ortega. The rabbit is an excellent animal for this surgery because of its size and postoperative resistance. (c) 2005 Elsevier B.V. All rights reserved.

Surface modification of Ti dental implants by Nd: YVO4 laser irradiation

Surface modifications have been applied in endosteal bone devices in order to improve the osseointegration through direct contact between neoformed bone and the implant without an intervening soft tissue layer. Surface characteristics of titanium implants have been modified by addictive methods, such as metallic titanium, titanium oxide and hydroxyapatite powder plasma spray, as well as by subtractive methods, such as acid etching, acid etching associated with sandblasting by either AlO2 or TiO2, and recently by laser ablation. Surface modification for dental and medical implants can be obtained by using laser irradiation technique where its parameters like repetition rate, pulse energy, scanning speed and fluency must be taken into accounting to the appropriate surface topography. Surfaces of commercially pure Ti (cpTi) were modified by laser Nd:YVO4 in nine different parameters configurations, all under normal atmosphere. The samples were characterized by SEM and XRD refined by Rietveld method. The crystalline phases alpha Ti, beta Ti, Ti6O, Ti3O and TiO were formed by the melting and fast cooling processes during irradiation. The resulting phases on the irradiated surface were correlated with the laser beam parameters: the aim of the present work was to control titanium oxides formations in order to improve implants osseointegration by using a laser irradiation technique which is of great importance to biomaterial devices due to being a clean and reproducible process. (c) 2007 Elsevier B.V. All rights reserved.

Modification of surface properties of Ti-16Si-4B powder alloy by plasma immersion ion implantation

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

An implementation of modified scatter search algorithm to transmission expansion planning

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

Micellar modification of drug stability: analysis of the effect of hexadecyltrimethylammonium halides on the rate of degradation of cephaclor

The intra- and intermolecular rates of degradation of cephaclor were determined with and without hexadecyltrimethylammonium bromide (CTABr). Micellar-derived spectral shifts were used to measure the association of the ionic forms as well as to determine the effect of CTABr on the apparent acid dissociation constant of the antibiotic. The rate of degradation of cephaclor increased with detergent and was salt sensitive. Micellar effects were analyzed quantitatively within the frame-work of the speudophase ion exchange model. All experimental data were fitted to this model which was used to predict the combined effects of pH and detergent concentration. Micelles increased the rate of OH- attack on cephaclor; most of the effect was due to the concentration of reagents in the micellar pseudophase. The intramolecular degradation was catalyzed 25-fold by micelles, and a working hypothesis to rationalize this effect is proposed. The results demonstrate that quantitative analysis can be utilized to assess and predict effects of detergents on drug stability.

Dental implants: Surface modification of cp-Ti using plasma spraying and the deposition of hydroxyapatite

The commercial pure titanium (cp-Ti) is currently being used with great success in dental implants. In this work we investigate how the cp-Ti implants can be improved by modifying the metal surface morphology, on which a synthetic material with properties similar to that of the inorganic part of the bone, is deposited to facilitate the bone/implant bonding. This synthetic material is the hydroxyapatite, HA, a calcium-phosphate ceramic. The surface modification consists in the application of a titanium oxide (TiO2) layer, using the thermal aspersion - plasma spray technique, with posterior deposition of HA, using the biomimetic method. The X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) techniques have been used for characterizing phases, microstructures and morphologies of the coatings. The TiO2 deposit shows a mixture of anatase, rutilo and TiO2-x phases, and a porous and laminar morphology, which facilitate the HA deposition. After the thermal treatment, the previously amorphous structured HA coating, shows a porous homogeneous morphology with particle size of about 2-2.5 μm, with crystallinity and composition similar to that of the biological HA.

Inactivation of vesicular stomatitis virus through inhibition of membrane fusion by chemical modification of the viral glycoprotein

Membrane fusion is an essential step in the entry of enveloped viruses into their host cells triggered by conformational changes in viral glycoproteins. We have demonstrated previously that modification of vesicular stomatitis virus (VSV) with diethylpyrocarbonate (DEPC) abolished conformational changes on VSV glycoprotein and the fusion reaction catalyzed by the virus. In the present study, we evaluated whether treatment with DEPC was able to inactivate the virus. Infectivity and viral replication were abolished by viral treatment with 0.5 mM DEPC. Mortality profile and inflammatory response in the central nervous system indicated that G protein modification with DEPC eliminates the ability of the virus to cause disease. In addition, DEPC treatment did not alter the conformational integrity of surface proteins of inactivated VSV as demonstrated by transmission electron microscopy and competitive ELISA. Taken together, our results suggest a potential use of histidine (His) modification to the development of a new process of viral inactivation based on fusion inhibition. © 2006 Elsevier B.V. All rights reserved.

Equine Perineal and Vulvar Conformation Correction Using a Modification of Pouret's Technique

An incompetent vulvar seal leads to reproductive failure, and a surgical intervention might be required. The present paper describes modifications to Pouret's surgery. We suggest the use of a simple interrupted vertical mattress suture, which avoids seroma. Eighteen Brazilian Jumping Horse mares, older than 20 years and barren for 3-5 consecutive years, underwent modified Pouret's surgery. A horizontal skin incision of 3-4 cm was made half way between the anus and upper commissure of the vulva. The submucosal and connective tissue were dissected, and the rectovaginal shelf was split horizontally by sectioning the muscular and ligamentous connections between the anus, vulva, caudal portion of the rectum, and vagina until the vulva was oriented vertically. The wound was changed from a horizontal plane to a vertical plane by placing the suture vertically using approximately eight interrupted U sutures distributed in two layers with polyamide thread. The modified Pouret's surgical technique provided a perfect coaptation of the vulvar lips and a correct perineal position. Those mares that presented with horizontally tipped vulvar lips due to advanced age and stretching of the pelvic tissues by multiple foaling had their vulvas replaced. Also, the surgical procedure was easy to perform. As to fertility, of the 18 initial mares, 14 were inseminated, and all became pregnant. Thus, it was possible to conclude that the anatomical changes performed throughout the surgical procedure predisposed to a better vulvar coaptation, correcting the pneumovagina. © 2013 Elsevier Inc. All rights reserved.

Interlacing of zeros of orthogonal polynomials under modification of the measure

We investigate the mutual location of the zeros of two families of orthogonal polynomials. One of the families is orthogonal with respect to the measure dμ (x), supported on the interval (a, b) and the other with respect to the measure |x -c|τ|x -d|γdμ (x), where c and d are outside (a, b) We prove that the zeros of these polynomials, if they are of equal or consecutive degrees, interlace when either 0 < τ, γ ≤ 1 or γ = 0 and 0 < τ ≤ 2. This result is inspired by an open question of Richard Askey and it generalizes recent results on some families of orthogonal polynomials. Moreover, we obtain further statements on interlacing of zeros of specific orthogonal polynomials, such as the Askey-Wilson ones. © 2013 Elsevier Inc.