Obtenção e caracterização de α-quitina e quitosanas de cascas de Macrobrachium rosembergii

The shells of Macrobrachium rosenbergii were submitted to deproteinization (Dp) and demineralization (Dm) aiming the extraction of α-chitin. The different parts of the shells were processed independently by carrying out sequence 1 (Dp/Dm) and sequence 2 (Dm/Dp). Both sequences allowed the extraction of chitins with low contents of calcium and magnesium, regardless of the part being processed. The sequence 1 lead to higher extraction yields while sequence 2 resulted in lower contents of inorganic compounds. Extensively deacetylated chitosans (GA<10%) of medium molecular weight (0,9 x 10(5) < Mv < 2 x 10(5) g/mol) resulted from the deacetylation of chitin.

Mecanismos químicos e mineralógicos de transformação da magnesioferrita de solo derivado de tufito, da região do Alto Paranaíba, MG

Magnetic soils forming on tuffite of the region of Alto Paranaíba, Minas Gerais, Brazil, usually contain iron-rich spinels exceptionally rich in magnesium and titanium. In this work, samples of the magnetically separated portion from the sand fraction of a Brunizém (Chernossolo) and from its mother-rock material were analyzed with synchrotron X-ray diffraction and 57Fe-Mössbauer spectroscopy. Magnesioferite (MgFe2O4) and maghemite (its pure non-stoichiometric spinel structure, Fe8/3 ⊕ 1/3 O4, where ⊕ = cation vacancy, corresponds to γFe2O3) were the magnetic iron oxides so identified. Basing on these data, a consistent chemical-mineralogical model is proposed for the main transformation steps involving these iron oxides in the pedosystem, starting on magnesioferrite to finally render hematite (αFe2O3), passing through maghemite as an intermediate specie.

Determinação direta de Ca, Mg, Mn e Zn em amostras de leite de búfala da Ilha de Marajó por espectrometria de absorção atômica com chama (FAAS)

This work proposes an analytical procedure for direct determination of calcium, magnesium, manganese and zinc in buffalo milk by flame atomic absorption spectrometry (FAAS). Samples were diluted with a solution containing 10% (v/v) of water-soluble tertiary amines (CFA-C) at pH 8. For comparison, buffalo milk samples were digested with HNO3 and H2O2. According to a paired t-test, the results obtained in the determination of Ca, Mg, Mn and Zn in digested samples and in 10% (v/v) CFA-C medium were in agreement at a 95% confidence level. The developed procedure is simple, rapid, decrease the possibility of contamination and can be applied for the routine determination of Ca, Mg, Mn and Zn in buffalo milk samples without any difficulty caused by matrix constituents, such as fat content, and particle size distribution in the milk emulsion.

Determinação de sibutramina em formas farmacêuticas através de espectroscopia no infravermelho com refletância difusa e métodos de calibração multivariada

The goal of this work is the development and validation of an analytical method for fast quantification of sibutramine in pharmaceutical formulations, using diffuse reflectance infrared spectroscopy and partial least square regression. The multivariate model was elaborated from 22 mixtures containing sibutramine and excipients (lactose, microcrystalline cellulose, colloidal silicon dioxide and magnesium stearate) and using fragmented (750-1150/ 1350-1500/ 1850-1950/ 2600-2900 cm-1) and smoothing spectral data. Using 10 latent variables, excellent predictive capacity were observed in the calibration (n=20, RMSEC=0.004, R= 0.999) and external validation (n=5, RMSEC= 9.36, R=0.999) phases. In the analysis of synthetic mixtures the precision (SD=3,47%) was compatible with the rules of the Agencia Nacional de Vigilância Sanitária (ANVISA-Brazil). In the analysis of commercial drugs good agreement was observed between spectroscopic and chromatographic methods.

Synthesis of liquid menthol by hydrogenation of dementholized peppermint oil over Ni catalysts

Hydrogenation of (-)-menthone and (+)-isomenthone was studied at 2.7 MPa and 100 ºC. The objective was to produce a liquid menthol mixture rich in (-)-menthol from dementholized peppermint oil. Ni-based catalysts were tested and compared for this reaction: a) 6 and 12% Ni dispersed into a nonstoichiometric magnesium aluminate (Ni-Mg-Al) with spinel structure; b) Ni-Raney catalyst. Both types of catalysts were active for (-)-menthone and (+)-isomenthone hydrogenation. Lower conversion but higher selectivity to (-)-menthol was obtained with Ni-Mg-Al catalysts. However, they rapidly lost their activity. Instead Ni-Raney catalysts kept its original activity even after several hydrogenation runs.

Aplicação de métodos quimiométricos na otimização da extração de Ca, Mg, K, Fe, Zn, Cu e Mn em folhas de braquiária

This work applied a 2² factorial design to the optimization of the extraction of seven elements (calcium, magnesium, potassium, iron, zinc, copper and manganese) in brachiaria leaves, determined by flame atomic absorption spectrometry. The factors sample mass and digestion type were evaluated at two levels: 200/500 mg, and dry/wet, respectively. Principal component analysis allowed simultaneous discrimination of all the significant effects in one biplot. Wet digestion and mass of 200 mg were considered the best conditions. The decrease of 60% in sample mass allowed to save costs and reagents. The method was validated through the estimation of figures of merit.

Método QuEChERS para determinação de ocratoxina a e citrinina em arroz e farelo de arroz

The present study was carried out to establish the optimal conditions for performing ochratoxin A (OTA) and citrinin (CIT) extraction using the QuEChERS method in rice. Employing the factorial experimental design, variables that significantly influenced the extraction stages were determined. The following variables were analyzed: addition of water, acidification of acetonitrile with glacial acetic acid, as well as amounts of magnesium sulfate, sodium acetate, sodium citrate and diatomaceous earth. The best combining procedure resulted in a predictive model using more water and less diatomaceous earth. Recoveries of CIT and OTA were 78-105%.

PCA: uma ferramenta para identificação de traçadores químicos para água de formação e água de injeção associadas à produção de petróleo

This study describes the use of Principal Component Analysis to evaluate the chemical composition of water produced from eight oil wells in three different production areas. A total of 609 samples of produced water, and a reference sample of seawater, were characterized according to their levels of salinity, calcium, magnesium, strontium, barium and sulphate (mg L-1) contents, and analyzed by using PCA with autoscaled data. The method allowed the identification of variables salinity, calcium and strontium as tracers for formation water, and variables magnesium and sulphate as tracers for seawater.

Application of fourier transform infrared spectroscopy, chemical and chemometrics analyses to the characterization of agro-industrial waste

Agroindustrial waste in general presents significant levels of nutrients and organic matter and has therefore been frequently put to agricultural use. In this context, the objective of this study was to determine the chemical composition, nitrogen, phosphorus, potassium, calcium, magnesium and carbon content, as well as the qualitative characteristics through Fourier transform infrared spectroscopy of four samples of poultry litter and one sample of cattle manure, from the southwestern region of Paraná, Brazil. Results revealed that, in general, the poultry litter presented higher amount of nutrients and carbon than the cattle manure. The infrared spectra allowed identification of the functional groups present and the differences in degree of sample humification. The statistical treatment confirmed the quantitative and qualitative differences revealed.

Magnesiumhydroksidialkalin käytön vaikutukset päällystämättömän aikakauslehtipaperin valmistukseen

Magnesiumhydroksidin on havaittu soveltuvan natriumhydroksidin korvaajaksi mekaanisen massan peroksidivalkaisun alkalina. Työssä selvitettiin, miten magnesiumhydroksidi vaikuttaa paperin valmistukseen ja valmiin paperin ominaisuuksiin. Laboratoriokokeet osoittivat magnesiumhydroksidin soveltuvan mekaanisen massan peroksidivalkaisun alkaliksi, sillä vaaleustavoite saavutettiin sen avulla. Valkaistun massan varaustila, johtokyky sekä ζ -potentiaali laskivat magnesiumhydroksidin vaikutuksesta. Nämä johtivat huomattavasti korkeampaan paperin täyteaineretentioon. Massan vedenpidätyskyky kasvoi korvattaessa natriumhydroksidi magnesiumhydroksidilla. Arkkien ominaisuuksista vetoindeksi, valonsirontakerroin ja taivutusjäykkyys kasvoivat. Kaikki edellä mainitut ominaisuudet viittaavat siihen, että magnesiumhydroksidin käyttö parantaa hienoaineen sitoutumista paperiin.

Design and implementation of a multipurpose reactor for scale-up studies

In the theoretical part, the different polymerisation catalysts are introduced and the phenomena related to mixing in the stirred tank reactor are presented. Also the advantages and challenges related to scale-up are discussed. The aim of the applied part was to design and implement an intermediate-sized reactor useful for scale-up studies. The reactor setting was tested making one batch of Ziegler–Natta polypropylene catalyst. The catalyst preparation with a designed equipment setting succeeded and the catalyst was analysed. The analyses of the catalyst were done, because the properties of the catalyst were compared to the normal properties of Ziegler–Natta polypropylene catalyst. The total titanium content of the catalyst was slightly higher than in normal Ziegler–Natta polypropylene catalyst, but the magnesium and aluminium content of the catalyst were in the normal level. By adjusting the siphonation tube and adding one washing step the titanium content of the catalyst could be decreased. The particle size of the catalyst was small, but the activity was in a normal range. The size of the catalyst particles could be increased by decreasing the stirring speed. During the test run, it was noticed that some improvements for the designed equipment setting could be done. For example more valves for the chemical feed line need to be added to ensure inert conditions during the catalyst preparation. Also nitrogen for the reactor needs to separate from other nitrogen line. With this change the pressure in the reactor can be kept as desired during the catalyst preparation. The proposals for improvements are presented in the applied part. After these improvements are done, the equipment setting is ready for start-up. The computational fluid dynamics model for the designed reactor was provided by cooperation with Lappeenranta University of Technology. The experiments showed that for adequate mixing with one impeller, stirring speed of 600 rpm is needed. The computational fluid dynamics model with two impellers showed that there was no difference in the mixing efficiency if the upper impeller were pumping downwards or upwards.

Potentiometric determination of captopril in pharmaceutical formulations

A simple, precise, rapid and low-cost potentiometric method for captopril determination in pure form and in pharmaceutical preparations is proposed. Captopril present in tablets containing known quantity of drug was potentiometrically titrated in aqueous solution with NaOH using a glass pH electrode, coupled to an autotitrator. No interferences were observed in the presence of common components of the tablets as lactose, microcrystalline cellulose, croscarmellose sodium, starch and magnesium stearate. The analytical results obtained by applying the proposed method compared very favorably with those obtained by the United States Pharmacopoeia Standard procedure. Recovery of captopril from various tablet dosage formulations range from 98.0 to 102.0%.

Spectrophotometric determination of diclofenac in pharmaceutical preparations assisted by microwave oven

In this work, an effective and low-cost method for the determination of sodium or potassium diclofenac is proposed in its pure form and in their pharmaceutical preparations. The method is based on the reaction between diclofenac and tetrachloro-p-benzoquinone (p-chloranil), in methanol medium. This reaction was accelerated by irradiating of reactional mixture with microwave energy (1100 W) during 27 seconds, producing a charge transfer complex with a maximum absorption at 535 nm. The optimal reaction conditions values such as reagent concentration, heating time and stability of the reaction product were determined. Beer's law is obeyed in a concentration range from of 1.25x10-4 to 2.00x10-3 mol l-1 with a correlation coefficient of 0.9993 and molar absorptivity of 0.49 x10³ l mol-1 cm-1. The limit of detection (LOD) was 1.35x10-5 mol l-1 and the limit of quantification (LOQ) was 4.49x10-5 mol l-1. In the presence of the common excipients, such as glucose, lactose, talc, starch, magnesium stearate, sodium sulphite, titanium dioxide, polyethyleneglycol, polyvinylpirrolidone, mannitol and benzilic alcohol no interferences were observed. The analytical results obtained by applying the proposed method compare very favorably with those given by the United States Pharmacopeia standard procedure. Recoveries of diclofenac from various pharmaceutical preparations were within 95.9% to 103.3%, with standard deviations ranging from 0.2% to 1.8%.

Jatkuvatoiminen ioninvaihto ja kompleksoituvien metallien sorptio kloridiympäristössä

Työn tarkoituksena oli tutkia kompleksoituvien metallien erotusta kloridiliuoksesta ioninvaihdolla. Kirjallisessa osassa perehdyttiin metallikompleksien muodostumiseen, ja erityisesti hopean, kalsiumin, magnesiumin, lyijyn ja sinkin muodostamiin komplekseihin kloridin ja nitraatin kanssa. Kirjallisessa osassa käsiteltiin myös metallien erottamista kiintopetikolonneissa jatkuvatoimisilla ioninvaihtomenetelmillä. Tässä työssä jatkuvatoimisen ioninvaihdon prosessivaihtoehdot jaoteltiin pyöriviin ja paikallaan pysyviin kolonneihin, sekä tarkasteltiin eri prosessivaihtoehtoja kolonnien kytkentöjen suhteen. Työn kokeellisessa osassa tutkittiin kahdenarvoisten metallien erottamista yhdenarvoisista metalleista sekä luotiin koedataa vastaavanlaisen erotusprosessin simulointiin. Kokeissa käytettiin anioninvaihtohartsia ja kelatoivaa selektiivistä ioninvaihtohartsia. Kahdenarvoisen kalsiumin, magnesiumin, lyijyn ja sinkin adsorptiota hartseihin tutkittiin tasapaino-, kinetiikka- ja kolonnikokeilla. Anioninvaihtohartsilla tehtyjen tasapaino- ja kolonnikokeiden tulokset osoittivat, että hartsi adsorboi tehokkaasti sinkkiä kloridiliuoksista, koska sinkki muodostaa stabiileja anionisia klorokomplekseja. Muiden tutkittujen kahdenarvoisten metallien adsorptio hartsiin oli huomattavasti vähäisempää. Tulosten perusteella tutkittu anioninvaihtohartsi on hyvä vaihtoehto sinkin erottamiseen muista tutkituista kahdenarvoisista metalleista kloridiympäristössä. Kelatoivalla hartsilla tehdyt tasapaino- ja kolonnikokeet osoittivat, että hartsi adsorboi kloridiliuoksista hyvin kahdenarvoista kalsiumia, magnesiumia, lyijyä ja sinkkiä, mutta ei adsorboi yhdenarvoista hopeaa. Tulosten perusteella kahdenarvoisten metallien erottaminen yhdenarvoisista metalleista voidaan toteuttaa kokeissa käytetyllä kelatoivalla ioninvaihtohartsilla.

Effect of hydrodynamics on modelling, monitoring and control of crystallization

Crystallization is a purification method used to obtain crystalline product of a certain crystal size. It is one of the oldest industrial unit processes and commonly used in modern industry due to its good purification capability from rather impure solutions with reasonably low energy consumption. However, the process is extremely challenging to model and control because it involves inhomogeneous mixing and many simultaneous phenomena such as nucleation, crystal growth and agglomeration. All these phenomena are dependent on supersaturation, i.e. the difference between actual liquid phase concentration and solubility. Homogeneous mass and heat transfer in the crystallizer would greatly simplify modelling and control of crystallization processes, such conditions are, however, not the reality, especially in industrial scale processes. Consequently, the hydrodynamics of crystallizers, i.e. the combination of mixing, feed and product removal flows, and recycling of the suspension, needs to be thoroughly investigated. Understanding of hydrodynamics is important in crystallization, especially inlargerscale equipment where uniform flow conditions are difficult to attain. It is also important to understand different size scales of mixing; micro-, meso- and macromixing. Fast processes, like nucleation and chemical reactions, are typically highly dependent on micro- and mesomixing but macromixing, which equalizes the concentrations of all the species within the entire crystallizer, cannot be disregarded. This study investigates the influence of hydrodynamics on crystallization processes. Modelling of crystallizers with the mixed suspension mixed product removal (MSMPR) theory (ideal mixing), computational fluid dynamics (CFD), and a compartmental multiblock model is compared. The importance of proper verification of CFD and multiblock models is demonstrated. In addition, the influence of different hydrodynamic conditions on reactive crystallization process control is studied. Finally, the effect of extreme local supersaturation is studied using power ultrasound to initiate nucleation. The present work shows that mixing and chemical feeding conditions clearly affect induction time and cluster formation, nucleation, growth kinetics, and agglomeration. Consequently, the properties of crystalline end products, e.g. crystal size and crystal habit, can be influenced by management of mixing and feeding conditions. Impurities may have varying impacts on crystallization processes. As an example, manganese ions were shown to replace magnesium ions in the crystal lattice of magnesium sulphate heptahydrate, increasing the crystal growth rate significantly, whereas sodium ions showed no interaction at all. Modelling of continuous crystallization based on MSMPR theory showed that the model is feasible in a small laboratoryscale crystallizer, whereas in larger pilot- and industrial-scale crystallizers hydrodynamic effects should be taken into account. For that reason, CFD and multiblock modelling are shown to be effective tools for modelling crystallization with inhomogeneous mixing. The present work shows also that selection of the measurement point, or points in the case of multiprobe systems, is crucial when process analytical technology (PAT) is used to control larger scale crystallization. The thesis concludes by describing how control of local supersaturation by highly localized ultrasound was successfully applied to induce nucleation and to control polymorphism in reactive crystallization of L-glutamic acid.