Determination of Copper, Iron, Nickel and Zinc in fuel kerosene by FAAS after adsorption and pre-concentration on 2-aminothiazole-modified silica gel

Silica gel chemically modified with 2-Aminotiazole groups, abbreviated as SiAT, was used for preconcentration of copper, zinc, nickel and iron from kerosene, normally used as a engine fuel for airplanes. Surface characteristics and surface area of the silica gel were obtained before and after chemical modification using FT-IR, Kjeldhal and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques. The experimental parameters, such as shaking time in batch technique, flow rate and concentration of the eluent (HCl- 0.25-2.00 mol L-1) and the amount of silica, on retention and elution, have been investigated. Detection limits of the method for copper, iron, nickel and zinc are 0.77, 2.92, 1.73 and 0.097 mg L-1, respectively. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in kerosene using flame AAS for their quantification.

Determination of Hg in water by CVAAS using 2-aminothiazole modified silica

This paper discusses a rapid and sensitive method developed to determine trace levels of mercury in natural water samples by cold vapor atomic absorption spectrometry using a preconcentration system composed by mini-column packed with 100 mg of 2-aminothiazol modified silica gel (SiAT) coupled on-line with the spectrometer's cold vapor generator system. The optimum preconcentration conditions are also described here. The preconcentrated Hg(II) ions were eluted directly from the column to the spectrometer's cold vapor generator system using 100 µL of 2 mol L-1 hydrochloric acid and the retention efficiency achieved exceeded 95%. The enrichment factors determined were 29, 38 and 46 using 3, 4 and 5 mL of preconcentrated aqueous solutions containing 400 ng L-1 of Hg. The detection limit calculated was 5 ng L-1. The preconcentration procedure was applied to determine trace level mercury in spiked river water samples.

Solid phase extraction of zinc with octadecyl silica membrane disks modified by N,N'-disalicylidene-1,2-phenylendiamine and determination by flame atomic absorption spectrometry

A procedure for separation and preconcentration of trace amounts of Zn(II) from aqueous media is proposed. The procedure is based on the adsorption of Zn2+ on octadecyl bonded silica membrane disk modified with N,N'-disalicylidene-1,2-phenylendiamine at pH 7. The retained zinc ions were then stripped from the disk with a minimal amount of 1.5 mol L-1 hydrochloric acid solution as eluent, and determined by flame atomic absorption spectrometry. Maximum capacity of the membrane disk modified with 5 mg of the ligand was found to be 226 µg Zn2+. The relative standard deviation of zinc for ten replicate extraction of 10 µg zinc from 1000 mL samples was 1.2%. The limit of detection of the proposed method was 14 ng of Zn2+ per 1000 mL. The method was successfully applied to the determination of zinc in natural water samples and accuracy was examined by recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry (GFAAS).

Thermal behavior of corn starch granules modified by acid treatment at 30 and 50°C

Unprocessed native starches are structurally too weak and functionally too restricted for application in today's advanced food technologies. Processing is necessary to engender a range of functionality. Naturals or natives starches can be modified by using several methods physical, chemical, enzymatic or combined, according industrial purposes. In this work, native corn starch was hydrolyzed by hydrochloric acid solution and investigated by using thermoanalytical techniques (thermogravimetry - TG, differential thermal analysis - DTA and differential scanning calorimetry - DSC), as well as optical microscopy and X-ray diffractometry. After acid treatment at 30 and 50°C, a decrease of gelatinization enthalpy (ΔHgel) was verified. Optical microscopy and X-ray diffractometry allowed us to verify the granules contorn and rugosity typical of cereal starches.

Microencapsulation of pequi pulp by spray drying: use of modified starches as encapsulating agent

The aim of this study was to evaluate the microencapsulation of pequi pulp by spray drying. A central composite rotational design was used in order to evaluate the effect of the independent variables: inlet air temperature, surfactant concentration and modified starch concentration. The dependent variables were assumed as yield of the process and the product features microencapsulated. A selection of the best process condition was performed to obtain the best condition of a product with the highest vitamin C and carotenoids content. Powders showed moisture content below 2%. The experimental values of hygroscopicity, yield, water activity, total carotenoids and vitamin C powders ranged from 7.96 to 10.67 g of adsorbed water/100g of solids, 24.34 to 49.80%, 0.13 to 0.30, 145.78 to 292.11 mg of ascorbic acid/g of pequi solids and 15.51 to 123.42 mg of carotenoids/g of pequi solids, respectively. The inlet air temperature 140°C, the surfactant concentration of 2.5% and the modified starch concentration of 22.5% was recommended as the selected condition. By the scanning electron microscopy, it was observed that most of the particles had spherical shape and smooth surface.

“IT’S ALL RIGHT”. Multimodal rightward spatial bias modified by age and praxis

The general goal of the present work was to study whether spatial perceptual asymmetry initially observed in linguistic dichotic listening studies is related to the linguistic nature of the stimuli and/or is modality-specific, as well as to investigate whether the spatial perceptual/attentional asymmetry changes as a function of age and sensory deficit via praxis. Several dichotic listening studies with linguistic stimuli have shown that the inherent perceptual right ear advantage (REA), which presumably results from the left lateralized linguistic functions (bottom-up processes), can be modified with executive functions (top-down control). Executive functions mature slowly during childhood, are well developed in adulthood, and decline as a function of ageing. In Study I, the purpose was to investigate with a cross-sectional experiment from a lifespan perspective the age-related changes in top-down control of REA for linguistic stimuli in dichotic listening with a forced-attention paradigm (DL). In Study II, the aim was to determine whether the REA is linguistic-stimulus-specific or not, and whether the lifespan changes in perceptual asymmetry observed in dichotic listening would exist also in auditory spatial attention tasks that put load on attentional control. In Study III, using visual spatial attention tasks, mimicking the auditory tasks applied in Study II, it was investigated whether or not the stimulus-non-specific rightward spatial bias found in auditory modality is a multimodal phenomenon. Finally, as it has been suggested that the absence of visual input in blind participants leads to improved auditory spatial perceptual and cognitive skills, the aim in Study IV was to determine, whether blindness modifies the ear advantage in DL. Altogether 180-190 right-handed participants between 5 and 79 years of age were studied in Studies I to III, and in Study IV the performance of 14 blind individuals was compared with that of 129 normally sighted individuals. The results showed that only rightward spatial bias was observed in tasks with intensive attentional load, independent of the type of stimuli (linguistic vs. non-linguistic) or the modality (auditory vs. visual). This multimodal rightward spatial bias probably results from a complex interaction of asymmetrical perceptual, attentional, and/or motor mechanisms. Most importantly, the strength of the rightward spatial bias changed as a function of age and augmented praxis due to sensory deficit. The efficiency of the performance in spatial attention tasks and the ability to overcome the rightward spatial bias increased during childhood, was at its best in young adulthood, and decreased as a function of ageing. Between the ages of 5 and 11 years probably at first develops movement and impulse control, followed by the gradual development of abilities to inhibit distractions and disengage attention. The errors especially in bilateral stimulus conditions suggest that a mild phenomenon resembling extinction can be observed throughout the lifespan, but especially the ability to distribute attention to multiple targets simultaneously decreases in the course of ageing. Blindness enhances the processing of auditory bilateral linguistic stimuli, the ability to overcome a stimulus-driven laterality effect related to speech sound perception, and the ability to direct attention to an appropriate spatial location. It was concluded that the ability to voluntarily suppress and inhibit the multimodal rightward spatial bias changes as a function of age and praxis due to sensory deficit and probably reflects the developmental level of executive functions.

Modified method for bronchial suture by Ramirez Gama compared to separate stitches suture: experimental study

OBJECTIVE: To experimentally compare two classic techniques described for manual suture of the bronchial stump.METHODS: We used organs of pigs, with isolated trachea and lungs, preserved by refrigeration. We dissected 30 bronchi, which were divided into three groups of ten bronchi each, of 3mm, 5mm, and 7mm, respectively. In each, we performed the suture with simple, separated, extramucosal stitches in five other bronchi, and the technique proposed by Ramirez and modified by Santos et al in the other five. Once the sutures were finished, the anastomoses were tested using compressed air ventilation, applying an endotracheal pressure of 20mmHg.RESULTS: the Ramirez Gama suture was more effective in the bronchi of 3, 5 and 7 mm, and there was no air leak even after subjecting them to a tracheal pressure of 20mmHg. The simple interrupted sutures were less effective, with extravasation in six of the 15 tested bronchi, especially in the angles of the sutures. These figures were not significant (p = 0.08).CONCLUSION: manual sutures of the bronchial stumps were more effective when the modified Ramirez Gama suture was used in the caliber bronchi arms when tested with increased endotracheal pressure.

Behavioral changes induced by cocaine in mice are modified by a hyperlipidic diet or recombinant leptin

The objective of the present study was to determine if the acute behavioral effects of cocaine acutely administered intraperitoneally (ip) at doses of 5, 10 and 20 mg/kg on white male CF1 mice, 90 days of age, would be influenced by leptin acutely administered ip (at doses of 5, 10 and 20 µg/kg) or by endogenous leptin production enhanced by a high-fat diet. The acute behavioral effects of cocaine were evaluated in open-field, elevated plus-maze and forced swimming tests. Results were compared between a group of 80 mice consuming a balanced diet and a high-fat diet, and a group of 80 mice fed a commercially available rodent chow formula (Ralston Purina) but receiving recombinant leptin (rLeptin) or saline ip. Both the high-fat-fed and rLeptin-treated mice showed decreased locomotion in the open-field test, spent more time in the open arms of the elevated plus-maze and showed less immobility time in the forced swimming test (F(1,68) = 7.834, P = 0.007). There was an interaction between diets and cocaine/saline treatments in locomotion (F(3,34) = 3.751, P = 0.020) and exploration (F(3,34) = 3.581, P = 0.024). These results suggest that anxiolytic effects and increased general activity were induced by leptin in cocaine-treated mice and that low leptin levels are associated with behavioral depression. Chronic changes in diet composition producing high leptin levels or rLeptin treatment may result in an altered response to cocaine in ethologic tests that measure degrees of anxiety and depression, which could be attributed to an antagonistic effect of leptin.

Determination of low tetanus or diphtheria antitoxin titers in sera by a toxin neutralization assay and a modified toxin-binding inhibition test

A method for the screening of tetanus and diphtheria antibodies in serum using anatoxin (inactivated toxin) instead of toxin was developed as an alternative to the in vivo toxin neutralization assay based on the toxin-binding inhibition test (TOBI test). In this study, the serum titers (values between 1.0 and 19.5 IU) measured by a modified TOBI test (Modi-TOBI test) and toxin neutralization assays were correlated (P < 0.0001). Titers of tetanus or diphtheria antibodies were evaluated in serum samples from guinea pigs immunized with tetanus toxoid, diphtheria-tetanus or triple vaccine. For the Modi-TOBI test, after blocking the microtiter plates, standard tetanus or diphtheria antitoxin and different concentrations of guinea pig sera were incubated with the respective anatoxin. Twelve hours later, these samples were transferred to a plate previously coated with tetanus or diphtheria antitoxin to bind the remaining anatoxin. The anatoxin was then detected using a peroxidase-labeled tetanus or diphtheria antitoxin. Serum titers were calculated using a linear regression plot of the results for the corresponding standard antitoxin. For the toxin neutralization assay, L+/10/50 doses of either toxin combined with different concentrations of serum samples were inoculated into mice for anti-tetanus detection, or in guinea pigs for anti-diphtheria detection. Both assays were suitable for determining wide ranges of antitoxin levels. The linear regression plots showed high correlation coefficients for tetanus (r² = 0.95, P < 0.0001) and for diphtheria (r² = 0.93, P < 0.0001) between the in vitro and the in vivo assays. The standardized method is appropriate for evaluating titers of neutralizing antibodies, thus permitting the in vitro control of serum antitoxin levels.

The modified 2VO ischemia protocol causes cognitive impairment similar to that induced by the standard method, but with a better survival rate

Permanent bilateral occlusion of the common carotid arteries (2VO) in the rat has been established as a valid experimental model to investigate the effects of chronic cerebral hypoperfusion on cognitive function and neurodegenerative processes. Our aim was to compare the cognitive and morphological outcomes following the standard 2VO procedure, in which there is concomitant artery ligation, with those of a modified protocol, with a 1-week interval between artery occlusions to avoid an abrupt reduction of cerebral blood flow, as assessed by animal performance in the water maze and damage extension to the hippocampus and striatum. Male Wistar rats (N = 47) aged 3 months were subjected to chronic hypoperfusion by permanent bilateral ligation of the common carotid arteries using either the standard or the modified protocol, with the right carotid being the first to be occluded. Three months after the surgical procedure, rat performance in the water maze was assessed to investigate long-term effects on spatial learning and memory and their brains were processed in order to estimate hippocampal volume and striatal area. Both groups of hypoperfused rats showed deficits in reference (F(8,172) = 7.0951, P < 0.00001) and working spatial memory [2nd (F(2,44) = 7.6884, P < 0.001), 3rd (F(2,44) = 21.481, P < 0.00001) and 4th trials (F(2,44) = 28.620, P < 0.0001)]; however, no evidence of tissue atrophy was found in the brain structures studied. Despite similar behavioral and morphological outcomes, the rats submitted to the modified protocol showed a significant increase in survival rate, during the 3 months of the experiment (P < 0.02).

Particle size and cholesterol content of a mayonnaise formulated by OSA-modified potato starch

Egg yolk was partially replaced (0, 25, 50, 75, and 100%) with octenyl succinic anhydride (OSA)-modified potato starch in a reduced-fat mayonnaise formulation to curtail the problems associated with high cholesterol and induced allergic reactions. The physicochemical properties included parameters such as: pH, fat content, and emulsion stability of the formulations analyzed. The samples with 75% and 100% egg yolk substitute showed the maximum emulsion stability (>95% after two of months storage), and they were selected according to cholesterol content, particle size distributions, dynamic rheological properties, microstructure, and sensory characteristic. A significant reduction (84-97%) in the cholesterol content was observed in the selected samples. Particle size analysis showed that by increasing the amount of OSA starch, the oil droplets with the peak size of 70 µm engulfed by this compound became larger. The rheological tests elucidated that in the absence of egg yolk, OSA starch may not result in a final product with consistent texture and that the best ratio of the two emulsifiers (OSA starch/egg yolk) to produce stable reduced-fat, low cholesterol mayonnaise is 75/25. The microscopic images confirmed the formation of a stable cohesive layer of starch surrounding the oil droplets emulsified in the samples selected.

A comparative study of protoheme and heme d catalases : role of the heme and the heme pocket in catalysis and ligand binding

Catalase dismutes H20 2 to O2 and H20. In successive twoelectron reactions H20 2 induces both oxidation and reduction at the heme group. In the first step the protoheme prosthetic group of beef liver catalase forms compound I, in which the heme has been oxidized from Fe3+ to Fe4+=0 and a porphyrin radical has been created. Compound II is formed by the oneelectron reduction of comp I. It retains Fe4+=0 but lacks the porphyrin radical and is catalytically inert. Molecular structures are available for Escherichia coli Hydroperoxidase II, Micrococcus Iysodeiktus, Penicillium vitale and beef liver enzymes, which contain different hemes and heme pockets. In the present work, the pockets and substrate access channels of protoheme (beef liver & Micrococcus) and heme d (HPII of E. coli and Penicillium) catalases have been analysed using Quanta™ and CharmMTM molecular modeling packages on the Silicon Graphics Iris Indigo 2 computer. Experimental studies have been carried out with two catalases, HPII (and its mutants) and beef liver. Fluoride and formate' are inhibitors of both enzymes, and their binding is modulated by the heme and by distal residues N201 & H128. Both HPII and beef liver enzymes form compound I with H202 or peracetate. The reduction of beef liver enzyme compound I to II and the decay of compound II are accelerated by fluoride. The decay of compound II is also accelerated by formate, and this reagent acts as a 2-electron donor towards compound I of both enzymes. It is concluded that heme d enzymes (Penicillium and HPII of E. coli) are formed by autocatalytic transformation of protoheme in a modified pocket which contains a characteristic serine residue as well as a partially occluded heme channel. They are less active than protoheme enzymes but also do not form the inactive compound II species. Binding of peroxide as well as fluoride and formate is prevented by mutation of H128 and modulated by mutation of N201.

Synthesis and utilization of guanidine catalysts for applications directed towards the preparation of butenolide and modified amino acid derivatives

Development of guanidine catalysts is explored through direct iminium chloride and amine coupling, alongside a 2-chloro-l,3-dimethyl-IH-imidazol-:-3-ium chloride (DMC) induced thiourea cyclization. Synthesized achiral catalyst N-(5Hdibenzo[ d,t][1,3]diazepin-6(7H)-ylidene)-3,5-bis(trifluoromethyl) aniline proved unsuccessful towards O-acyl migrations, however successfully catalyzed the vinylogous aldol reaction between dicbloro furanone and benzaldehyde. Incorporating chirality into the guanidine catalyst utilizing a (R)-phenylalaninol auxiliary, generating (R)-2-((5Hdibenzo[ d,t] [1,3 ]diazepin-6(7H)-ylidene ) amino )-3 -phenylpropan-l-ol, demonstrated enantioselectivity for a variety of adducts. Highest enantiomeric excess (ee) was afforded between dibromofuranone and p-chlorobenzaldehyde, affording the syn conformation in 96% ee and the anti in 54% ee, with an overall yield of30%. Attempts to increase asymmetric induction were focused on incorporation of axial chirality to the (R)phenylalaninol catalyst using binaphthyl diamine. Incorporation of (S)-binaphthyl exhibited destructive selectivity, whereas incorporation of (R)-binaphthyl demonstrated no effects on enantioselectivity. Current studies are being directed towards identifying the catalytic properties of asymmetric induction with further studies are being aimed towards increasing enantioselectivity by increasing backbone steric bulk.

Inhibition of respiratory syncytial virus by nasally administered siRNA modified with F-ANA

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.