Determinação da atividade antitríptica em proteínas de produtos do amendoim isoladas por cromatografia de afinidade

The peanut is an oleaginous plant of high nutritional value, a source of protein and a trypsin inhibitor. Trypsin inhibitors are proteins present in the vegetable kingdom, considered anti-nutritional factors for animals. However, there have been several recent reports about their heterologous and beneficial effects on human health. These important effects have been the focus of studies investigating these inhibitors in foods. The aim of the present study was to isolate and determine the estimated molecular mass and specific inhibitory activity, for trypsin in the Japanese peanut, peanut butter, and peanut nougat using the techniques of precipitation with ammonium sulfate and affinity chromatography on trypsin - Sepharose CNBr 4B. The techniques used in this study were efficient for isolating the protein inhibitors with antitryptic specific activity of 694 UI mg-1, 823 UI mg-1 and 108 UI mg-1 for the Japanese peanut, peanut nougat, and peanut butter, respectively. The techniques featured high selectivity of the adsorbent, with consequent efficiency in isolation, given the low amount of dosed proteins and specific antitryptic activity presented by the products studied. The various health-related benefits show the importance of detecting and isolating efficient trypsin inhibitors in foods, taking into account the health claims attributed to the vegetable and its high consumption by humans.

RAPID AND SENSITIVE DETERMINATION OF PALLADIUM USING HOMOGENEOUS LIQUID-LIQUID MICROEXTRACTION VIA FLOTATION ASSISTANCE FOLLOWED BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY

A method for the determination of trace amounts of palladium was developed using homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA) followed by graphite furnace atomic absorption spectrometry (GFAAS). Ammonium pyrrolidine dithiocarbamate (APDC) was used as a complexing agent. This was applied to determine palladium in three types of water samples. In this study, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added to the extraction cell which contained an appropriate mixture of extraction and homogeneous solvents. By using air flotation, the organic solvent was collected at the conical part of the designed cell. Parameters affecting extraction efficiency were investigated and optimized. Under the optimum conditions, the calibration graph was linear in the range of 1.0-200 µg L-1 with a limit of detection of 0.3 µg L-1. The performance of the method was evaluated for the extraction and determination of palladium in water samples and satisfactory results were obtained. In order to verify the accuracy of the approach, the standard addition method was applied for the determination of palladium in spiked synthetic samples and satisfactory results were obtained.

NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Extraction and spectrophotometric determination of Hg2+ as complex anion HgI3-

A method has been developed for the extraction and spectrophotometric determination of Hg2+ in a concentration range of 0.2-1.0 mg L-1; following the Lambert-Beer's law using high molecular weight quaternary ammonium salts dissolved in chloroform. The metal complex anion was determined in the extract in the region UV (260 nm).

Voimalaitos- ja jätevesitutkimus

Tässä työssä tutkittiin Stora Enso Oyj:n Heinolan Flutingtehtaan voimalaitos- ja jätevesien seuranta-analyysimenetelmien kehittämistä. Käytössä olevia menetelmiä vertailtiin vaihtoehtoisiin uusiin menetelmiin, jotka perustuvat erotustekniikoihin ja automaatioon. Flutingtehtaalla nykyisin käytössä olevat analyysimenetelmät perustuvat suurelta osin standardimäärityksiin, joissa käytetään pääasiassa titrausta. Määritykset vievät paljon aikaa, koska titraukset toteutetaan manuaalisesti. Titrausten päätepisteet tulkitaan esim. indikaattorin värinmuutoksella ja saostamalla, joten määritysten tarkkuus vaihtelee. Kokeellisessa osassa Flutingtehtaan puhtaista voimalaitosvesistä yhdistetty sekoitenäyte analysoitiin kahdella ionikromatografilla, liekkiatomiabsorptiospektrometrillä ja kapillaarielektroforeesilla. Yksittäisiä näytteitä ei tutkittu. Lisäksi vesilaboratoriossa määritettävistä jätevesistä yhdistettiin sekoitenäyte, joka analysoitiin kapillaarielektroforeesilla. Samat sekoitenäytteet analysoitiin myös nykyisillä menetelmillä tehtaan vesilaboratoriossa. Tulokset osoittivat, että kokeellisessa osassa tutkitut menetelmät soveltuvat sekoitenäytteen perusteella hyvin vesilaboratoriossa käytössä oleviin kuukausianalyyseihin. Automaattisella näytteensyötöllä varustettuna kaikki kolme kokeellisessa osassa tutkittua menetelmää ovat yksikertaisia käyttää ja ne nopeuttavat analyysejä. Päivittäisiä titrausanalyysejä voidaan tehostaa ja nopeuttaa automaation avulla. Erotustekniikoilla esimerkiksi typpi voidaan määrittää kokonaistyppenä, mutta myös komponentteinaan eli ammoniakkina, nitraattina ja nitriittinä. Lisäksi samalla erotuksella voidaan määrittää useita alkali- ja maa-alkalimetalleja sekä raskas-metalleja toistomittauksilla. Menetelmän käyttöalue on laajempi erotustekniikoilla kuin perinteisillä liuoskemian mittauksilla. Erotustekniikoilla tunnistetaan helposti määritysten oikeellisuus detektointimahdollisuuksien monipuolisuuden vuoksi.

Spectrophotometric determination of methyldopa in pharmaceutical formulations

A new, simple, precise, rapid and low-cost spectrophotometric method for methyldopa determination in pharmaceutical preparations is described. This method is based on the complexation reaction of methyldopa with molybdate. Absorbance of the resulting yellow coloured product is measured at 410 nm. Beer's Law is obeyed in a concentration range of 50 - 200 µg ml-1 methyldopa with an excellent correlation coefficient (r = 0.9999). No interference was observed from common excipients in formulations. The results show a simple, accurate, fast and readily applied method to the determination of methyldopa in pharmaceutical products. The analytical results obtained for these products by the proposed method are in agreement with those of the Brazilian Pharmacopoeia procedure at 95% confidence level.

Use of modified silica gel for concentrating Pb (II) and Cd (II) occurring in form of complex anions

The performance of silica gel, modified by the impregnation with a high molecular weight quaternary amine (triethyl octadecyl ammonium iodide), used for the concentration of heavy metals occurring in water is studied. The material under study captures Cd, Pb, which are capable of forming stable complexes with I- ions.The results obtained about the metal capture, under dynamic conditions, are described and metal ions are removed by desorption with EDTA and quantified by AAS.

New reagents for the spectrophotometric determination of ranitidine hydrochloride

A new spectrophotometric method is proposed for the assay of ranitidine hydrochloride (RNH) in bulk drug and in its dosage forms using ceric ammonium sulphate (CAS) and two dyes, malachite (MAG) green and crystal violet (CV) as reagents. The method involves the addition of a known excess of ceric ammonium sulphate to ranitidine hydrochloride in acid medium, followed by the determination of unreacted CAS by reacting with a fixed amount of malachite green or crystal violet and measuring the absorbance at 615 or 582 nm respectively against the reagent blank. The Beer's law is obeyed in the concentration range of 0.4-8.0 µg/ ml of ranitidine hydrochloride (RNH) for RNH-MAG system and 0.2-1.6µg/ml of ranitidine hydrochloride for RNH-CV system. The molar Absorptivity, Sandell's sensitivity for each system were calculated. The method has been successfully applied to the determination of ranitidine hydrochloride in pure and dosage forms.

Kalsiumkarbonaatin kemiallisfysikaalinen käsittely ja materiaalin karakterisointi

Saostettua karbonaattia voidaan käyttää useiden eri teollisuuksien tuotteissa. Pääosin saostettua kalsiumkarbonaattia kuitenkin käytetään paperin, maalien, muovien sekä elintarviketuotteiden täyteaineena. Koska monet käyttökohteet vaativat saostetulta kalsiumkarbonaatilta tiettyjä puhtausvaatimuksia, sen koostumuksen tutkiminen on suuren kiinnostuksen kohteena. Työn perimmäisenä tarkoituksena on ollut määrittää saostetun kalsiumkarbonaatin kemiallinen koostumus ja selvittää, vaikuttavatko materiaalin kemiallisfysikaalinen modifiointi sen ominaisuuksiin. Kirjallisuusosassa käsitellään yleisesti kalsiumkarbonaattimateriaaleja, saostetun kalsiumkarbonaatin valmistusmenetelmiä ja vastaavanlaisen materiaalin esikäsittelymenetelmiä. Lisäksi tarkastellaan erilaisia analyysimenetelmiä, joita voidaan käyttää kiinteiden epäorgaanisten tai mineraalinäytteiden kemiallisen koostumuksen sekä fysikaalisten ja kemiallisten reaktioiden määrittämiseen. Kokeellisessa osassa tutkittiin käsittelemättömiä saostettuja kalsiumkarbonaattinäytteiden ominaisuuksia ja kemiallista koostumusta erilaisilla alkuaine-, ioni-/spesies- sekä pyrolyysimittauksilla. Näytteitä modifioitiin lämmityksen ja jauhatuksen avulla. Modifioinnin vaikutusta näytteiden kemiallisiin koostumuksiin tutkittiin vertailemalla tuloksia käsittelemättömien näytteiden antamiin tuloksiin. Tutkimus osoitti, että näytteiden lämpökäsittelyllä ei ollut lähes ollenkaan vaikutusta näytteiden kemialliseen koostumukseen. Toisin osoitti näytteiden jauhatus, joka laski ammoniumin pitoisuutta näytteissä. Laitetekniikkaa käytettäessä kapillaarielektroforeesi, ionikromatografi, ICP-AES ja SEM (FTIR) antoivat luotettavinta tietoa näytteiden kemiallisista koostumuksista. Näytteiden fysikaalisia ja kemiallisia reaktioita voitiin havainnollistaa parhaiten käyttäen STA-QMS -laitetta.

Ammoniumkloridi Porvoon ja Naantalin jalostamoiden vetyverkoissa

Tässä työssä on käsitelty ammoniumkloridia Porvoon ja Naantalin jalostamoiden vetyverkoissa. Tietoa ammoniumkloridin aiheuttamista ongelmista ja niihin vaikuttavista tekijöistä on kerätty ja niiden pohjalta on pyritty löytämään keinoja, joilla ongelmaa voidaan vähentää tai poistaa. Kirjallisuusosassa on käsitelty ammoniumkloridia, sen aiheuttamaa korroosiota ja materiaalien ammoniumkloridikestävyyttä. Lisäksi kirjallisuusosassa on käsitelty ammoniumkloridin muodostumiseen tarvittavan vetykloridin määritysmenetelmiä sekä ammonium- ja kloridi-ionien määritysmenetelmiä. Työn soveltavassa osassa kerättiin tietoa ammoniumkloridin aiheuttamista ongelmista ja ammoniumkloridin muodostumiseen vaikuttavista tekijöistä. Lisäksi Porvoon jalostamolla suoritettiin mittauksia, joilla määritettiin ammoniakki- ja vetykloridipitoisuuksia vetyvirroista. Tulosten perusteella saatiin käsitys jalostamon ammoniumkloridiongelman nykytilanteesta ja tutkittiin ammoniumkloridia muodostavien ammoniakin ja vetykloridin lähteitä. Lisäksi keinoja vähentää ammoniumkloridin muodostumista tunnistettiin.

Lannoitetehtaan prosessivesien käsittelyvaihtoehtojen soveltuvuuden arviointi

Phosphorus and nitrogen cause eutrophication of water bodies, causing severe damage to the ecosystem. Eutrophication of the waters causes oxygen depletion, which in turn increases fish mortality, releasing toxins in waters. The released toxins can cause damage to animals and humans, which is the reason in many countries to set emission limits for waste water. Nutrients exist naturally, but due to human activities there is high nutrient leaching to water bodies. Human activity is one of the main reasons to the eutrophication. The aim of this thesis was to estimate the suitability of different water treatment options for Yara Finland’s fertilizer plant’s process waters in Siilinjärvi. The fertilizer plant process waters are high concentrate and especially nitrogen concentrations are high, which bring challenge to the treatment. At the theoretical part was investigated conventional and as well advanced wastewater treatment methods like reverse osmosis, adsorption and ion exchange. Beside different treatment methods corporate environmental requirements, responsibility and strategies were researched. At the empirical part of the thesis the goal was to find out possibil-ities to intensify the efficiency of purification at lamella clarifier with chemical precipitation. In addition possibility to use already existing chemical purifying plant for process waters was estimated. As a result of the research Yara has a possibility to intensify lamella clarifier’s action by addi-tion of calcium hydroxide and thus to obtain the phosphorus and fluorine to precipitate out of the water. But in practice this would be too expensive. It is possible to eliminate nitrogen compounds by adsorption or ammonia stripping, both methods requires additional testing. It is possible to process waters in chemical purifying plant, if ammonium nitrogen has been reduced before. Reverse osmosis is possible to exploit for the phosphoric acid plant’s waters.

Water application uniformity and fertigation in a dripping irrigation set

The purpose of this study was to evaluate the uniformity of distribution coefficient (UDC) and coefficient of variation (CV) of a familiar set of irrigation, classifying it the ASAE standard. The irrigation and fertigation are determined by two methods the KELLER & KARMELI and DENÍCULI . The two experiments were subjected to varying pressures: 12, 14, 16 and 18 kPa, in a completely randomized design of twenty samples composed of flows with three replications. Urea, potassium chloride (KCl) and ammonium phosphate (MAP) were the elements used for fertigation. The system consisted of a 200 L tank, which supplied another container of 30 L, it was moved vertically to control the pressure. The data was statistically compared between treatments for each methodology. In fertigation the best pressure was 16 kPa and was classified as "excellent" for UDC (91.03%) and "marginal" for C.V. (7.47%). For the irrigation treatment, the best pressure was 16 kPa rated "excellent" for UDC (91.2%) and "marginal" for C.V. (7.68%). The DENÍCULI et al. (1980) methodology proved more reliable for the evaluation of drip systems. It was observed that this set has good uniformity of distribution, but with great variability in flows.

Nitrogen fertilization by deep-bedding swine production and its effects on the properties of a Quartzarenic Neosol

The objective of this study was to evaluate the effects of the nitrogen fertilization in the form of swine deep bed in the properties of a quartz-sand neosol. The organic compound used was the deep bed made with rice hulls, from a commercial swine finishing system farm. Deep bed samples have been collected at various points in the installation in order to obtain a representative composite sample which has been fractionated in a 2.0 mm sieve and submitted to a 50-day maturation period. Then, agronomic value analyses were done. The experimental design was completely randomized. The treatments consisted of 0; 75; 150 and 300 mg dm-3 of N doses of deep bed as well as an additional treatment with ammonium sulfate at a 150 mg dm-3 of N. The experimental period in the greenhouse was 45 days, where the soil was cultivated with maize. After the experiment completion, further soil properties analyses were done. From the results, it was noted that the organic fertilization with deep bed provided a significant increase in the levels of potassium, in the sum of the bases, in the effective CEC, in the CEC at pH 7.0 and in the percentage of saturation.

Selection of microorganisms producer of lipase for fat removal from biodiesel purification water

The objective this study has been the selection of lipase productor microorganism, for removal of oils and grease, in the pre-treatment of biodiesel wastewater washing. For this, analyses of the physicist-chemistries characteristics had been made with the wastewater of the biodiesel washing, and then it had been isolated and chosen, by means of determinations of the lipase activity. Following, it was made a test of fat biodegradation, in the conditions: pH (5.95), temperature (35 ºC), rotation (180 rpm) and ammonium sulfate as nitrogen source (3 g L-1) and establishing as variable the two microorganism preselected and the time (24; 48; 72; 96 and 120 h). The biodiesel purification wastewater had presented high potential of environmental impact, presenting a concentration of O of 6.76 g L-1. From the six isolated microbiological cultures, two microorganisms (A and B) had been selected, with enzymatic index of 0.56 and 0.57, respectively. The treatment of the wastewater using the isolated microorganism (Klebsiella oxytoca) had 80% of the fatty removal in 48 h.

Nitrogen fertilization by deep bedding swine production and its effects on dry matter production and accumulation of nutrients by maize

The goal of this study was to evaluate the nitrogen fertilization as deep litter for pigs in order to produce biomass and accumulate nutrients by the corn. A deep litter made of rice husk as organic compound, from a commercial pig farm during finishing phase, was used. After three consecutive batches of pigs, the deep litter was subjected to a maturation period of 50 days, and samples of this material were taken for analysis of agronomic value. The experimental design was completely randomized with five replicates. The treatments consisted of doses of 0, 75, 150 and 300mg dm-3 of N of deep litter, as well as an additional treatment with ammonium sulfate, with a dosage of 150mg dm-3 of N. After 45 days, corn plants were harvested in order to evaluate the total dry weight and nutrient concentrations of their aerial parts. Dry matter increases were found with more application of deep litter. Regarding control fertilization, the use of increasing dosages of deep litter allowed accumulation of K, reduced the availability of P, Ca, Mg, Zn and B and did not alter the concentrations of N, Cu, Fe and Mn.