Autoagrega����o da 5,10,15,20-tetrakis(4-metoxifenil)porfirina (tmpp): estudos espectrosc��picos e an��lises multivariadas

In this work, the spectroscopic properties of 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin (TMPP) in solvents of different polarities and water/ethanol mixtures were studied by electronic absorption spectroscopy and resonance light scattering associated with statistical analysis. The molar absorption coefficient and emission maximum of TMPP were dependent on solvent polarity. In the water/ethanol mixture, TMPP remained monomeric up to 25% of water, when it reaches its critical aggregation percentage. Oblique head-to-tail aggregate was found at intermediate water content (35 - 55%), while formation of a J-type aggregate was observed at higher water content (> 60%).

Epoxida����o do β-cariofileno com lipases imobilizadas em gel de ��gar

The immobilization of enzymes and microorganisms on solid supports has been developed in recent years. These biocatalysts may be used in organic media allowing their storage and reuse, thus reducing costs of the process. Herein, lipases from various sources were immobilized in agar gel and used as catalysts in the chemo-enzymatic epoxidation of β-caryophyllene. Several experimental parameters, such as the use of different organic solvents including ionic liquids, time, temperature, and agitation rate were evaluated. The mono-epoxide was obtained as a single product. The best result was achieved using immobilized F-AP15 lipase, forming the corresponding β-caryophyllene epoxide at a conversion of 96% in an 8h reaction at 35 ��C.

Optimization of chromatographic conditions and comparison of extraction efficiencies of four different methods for determination and quantification of pesticide content in bovine milk by UFLC-MS/MS

This paper describes the optimization of a multiresidue chromatographic analysis for the identification and quantification of 20 pesticides in bovine milk, including three carbamates, a carbamate oxime, six organophosphates, two strobilurins, a pyrethroid, an oxazolidinedione, an aryloxyphenoxypropionate acid/ester, a neonicotinoid, a dicarboximide, and three triazoles. The influences of different chromatographic columns and gradients were evaluated. Furthermore, four different extraction methods were evaluated; each utilized both different solvents, including ethyl acetate, methanol, and acetonitrile, and different workup steps. The best results were obtained by a modified QuEChERS method that lacked a workup step, and that included freezing the sample for 2 hours at -20 ºC. The results were satisfactory, yielding coefficients of variation of less than 20%, with the exception of the 50 ��g L-1 sample of famoxadone, and recoveries between 70 and 120%, with the exception of acephate and bifenthrin; however, both analytes exhibited coefficients of variation of less than 20%.

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.

AN��LISE EXPLORAT��RIA DAS CONCENTRA����ES DOS METAIS NA, CA, MG, SR E FE EM EXTRATO AQUOSO DE PETR��LEO, DETERMINADOS POR ICP OES, AP��S OTIMIZA����O EMPREGANDO PLANEJAMENTO DE EXPERIMENTOS

AbstractThe purpose of this study was to evaluate the best operating conditions of ICP OES for the determination of Na, Ca, Mg, Sr and Fe in aqueous extract of crude oil obtained after hot extraction with organic solvents (ASTM D 6470-99 modified). Thus, the full factorial design and central composite design were used to optimize the best conditions for the flow of nebulization gas, the flow of auxiliary gas, and radio frequency power. After optimization of variables, a study to obtain correct classification of the 18 samples of aqueous extract of crude oils (E1 to E18) from three production and refining fields was carried out. Exploratory analysis of these extracts was performed by principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), using the original variables as the concentration of the metals Na, Ca, Mg, Sr and Fe determined by ICP OES.

BUSCAS DE INFORMA����ES TECNOL��GICAS COM BASE EM DADOS DE PATENTES: ESTUDO DE CASO DOS L��QUIDOS I��NICOS NO BRASIL

This study describes the application of the Art of Scientific and Technological Search to strategically analyze areas of technological and industrial development. Application of scientific search strategies such as the creation of Patent Landscape has been shown to be useful for writing research projects, earning grants, publishing papers, drafting patent applications, and analyzing the market and economic potentials of a previous determined subject. The Patent Landscape regards a simplified analysis of technologies concerning ionic liquids patents applied in Brazil and published by Instituto Nacional da Propriedade Industrial(INPI). A total of 93 patent applications using the keywords "ionic liquids" were found in the INPI database. Among these, 75% were nonresident applications and 25% were Brazilian resident applications. Interestingly, BASF, Chevron Industries, and the Universidade Federal do Rio Grande do Sul (UFRGS) were discovered as higher patent applicant assignees. Differences in the patent application areas were also observed between these applicants, with new solvents and petrochemical applications as the areas of focus for the industrial applications (BASF and Chevron Industries), and energy production, catalysis, and chemical reaction media as the focus for the university applications.

M��TODOS DE EXTRA����O DE POLI-HIDROXIALCANOATOS A PARTIR DE BIOMASSA BACTERIANA

Polyhydroxyalkanoates (PHAs) are biodegradable and biocompatible polyesters intracellularly accumulated by many bacteria as an energy reserve material and carbon source. These biopolymers may be extracted from cells after their production phase, and the extraction process involves various individual operations to ensure adequate removal of the biopolymer from the cells. During this process, the following aspects should be considered: reduction of product losses during different stages of the process to obtain a highly pure product, preservation of physical and thermal characteristics, and use of low toxicity chemicals to achieve sustainable production and avoid harming the environment. The impact of the costs of PHA extraction on the total cost of the production process may account for over 50% of the end-value of the product. Within this context, several methods of PHA extraction have been reported in the literature. These methods include the use of solvents, chemical digestion, enzymatic digestion, mechanical extraction with high-pressure homogenization and ultrasound, extraction using supercritical fluids, or a combination of these methods. The present review of the literature shows strategies for extraction processes of PHAs produced by bacteria involving cell destabilization and/or breakage, recovery, and purification of the biopolymer.

A NOVEL METHOD FOR THE DETERMINATION OF TRACE THORIUM BY DISPERSIVE LIQUID-LIQUID MICROEXTRACTION BASED ON SOLIDIFICATION OF FLOATING ORGANIC DROP

In this study, dispersive liquid-liquid microextraction based on the solidification of floating organic droplets was used for the preconcentration and determination of thorium in the water samples. In this method, acetone and 1-undecanol were used as disperser and extraction solvents, respectively, and the ligand 1-(2-thenoyl)-3,3,3-trifluoracetone reagent (TTA) and Aliquat 336 was used as a chelating agent and an ion-paring reagent, for the extraction of thorium, respectively. Inductively coupled plasma-optical emission spectrometry was applied for the quantitation of the analyte after preconcentration. The effect of various factors, such as the extraction and disperser solvent, sample pH, concentration of TTA and concentration of aliquat336 were investigated. Under the optimum conditions, the calibration graph was linear within the thorium content range of 1.0-250 ��g L-1 with a detection limit of 0.2 ��g L-1. The method was also successfully applied for the determination of thorium in the different water samples.

CROMATOGRAFIA POR INTERA����ES HIDROFILICAS (HILIC): ESTADO DA ARTE E APLICA����ES

Hydrophilic interaction liquid chromatography (HILIC) has been gaining increased attention for its effective separation of highly polar compounds, which include carbohydrates, amino acids, pharmaceutical compounds, proteins, glycoproteins, nucleosides, etc. Polar compounds are usually poorly retained on reverse-phase liquid chromatography (RP-HPLC) columns or have poor solubility in the apolar mobile phase of normal-phase high performance liquid chromatography (NP-HPLC). Since HILIC uses organic solvents such as ACN or MeOH ( > 70%), also used in RP-HPLC and polar stationary phases similar to NP-HPLC (bare silica, diol, amino, amide, saccharide, zwitterionic stationary phases, etc.), it represents a hybrid of the two separation modes. The high organic content in the MP leads to good compatibility with mass spectrometry (MS), increasing the detectivity. This review describes the fundamentals of HILIC and highlights some interesting applications.

Pinnoiteteollisuudessa syntyvien maalij��tteiden hy��tyk��ytt�� ja uudet liiketoimintamahdollisuudet

T��m��n diplomity��n tavoite on kartoittaa maalien ja lakkojen valmistuksessa syntyvien sivuvirtojen hy��tyk��ytt���� ja hy��tyk��ytt��potentiaalia nykyisell����n. Ty��n tarkoitus on toimia esiselvityksen�� pinnoiteteollisuuden sivuvirtojen hy��tyk��ytt����n liittyvien liiketoimintamahdollisuuksien syvemm��lle analyysille. Teollisuuden sivuvirtoihin liittyv���� tietoa ker��t����n tilastoista ja olemassa olevista raporteista sek�� haastattelemalla teollisuus- ja palveluyritysten edustajia sek�� alan asiantuntijoita. Sivuvirtojen teknisten hy��tyk��ytt��mahdollisuuksien ja liiketoiminnallisten mahdollisuuksien tarkastelua varten j��rjestet����n ty��pajoja asiantuntijoille Apila Group Oy Ab:n asiantuntijaverkostossa. Nelj��ss�� haastatellussa tuotantolaitoksissa syntyi vuonna 2008 yhteens�� 6 662 tonnia kiinte���� j��tett�� ja lietteit��. 68 % n��ist�� sivuvirroista hy��tyk��ytettiin energiana tai polttoaineen valmistuksessa. Materiaalina sivuvirtoja hy��tyk��ytettiin 16 % sivuvirroista, p����asiassa pahvia, paperia, metalleja sek�� tynnyreit�� ja kontteja. My��s merkitt��v�� osa liuottimista otettiin talteen uudelleenhy��dynt��mist�� varten. T��ss�� diplomity��ss�� hy��tyk��ytt��mahdollisuuksien tarkempaa tarkastelua varten valittiin tavanomaisiksi j��tteiksi luokiteltuja maalisivuvirtoja, joita haastatelluissa tuotantolaitoksissa syntyi noin 1 500 tonnia. Maalisivuvirtojen t��rkeimm��t materiaaliominaisuudet liittyv��t niiden sis��lt��miin t��yte- ja sideaineisiin, jotka muodostavat merkitt��v��n osan maalien koostumuksesta. Selvityksen mukaan n��m�� ominaisuudet voidaan ottaa hy��tyk��ytt����n erilaisissa yhdistelm��materiaaleissa, esimerkiksi ekstruusiopuristetuissa tai ahtopuristetuissa muovikuitukomposiiteissa. Komposiittien raaka-aineena k��ytet����n jo erilaisia sivuvirtoja ja lis��ksi erilaisten komposiittien markkinoiden ennustetaan kasvavan. T��m�� voi tarjota mahdollisuuksia uusille palvelu-, t&k- tai tuotteistusliiketoiminnoille. Kuivilla maalij��tteill�� on my��s hyv�� l��mp��arvo, jolloin energiahy��tyk��yt��n ja palamisj����nn��ksen materiaalihy��tyk��yt��n yhdist��minen mm. keramiikka- tai sementtiteollisuudessa voi tarjota mahdollisuuksia uusille liiketoiminnoille.

A model for specific interactions of manganese-phthalocyanine in protic media

Extinction coefficients (e) changes of manganese phthalocyanine (Mn-Pc) were studied in different organic solvents and related to solvent polarity scales; (Kosower's values (Z), Dimroth's values (E T), donor numbers (DN) and linear solvation energy relationships (LSER) or linear free energy relationships (LFER));, theoretical molecular orbital calculations and ligand/solvent coordination processes in order to predict molecular interaction with the medium and identification of predominant intermolecular forces.

Puulevyst�� valmistettujen kalusteosien pintak��sittelyn kehitt��minen UV-telalinjalla

Diplomity�� tehtiin Kidex Oy:lle, joka on Kiteell�� sijaitseva Martela-konsernin tyt��ryhti��. Kidex Oy toimii sopimusvalmistajana Martelalle sek�� muille valituille levykalusteasiakkaille, ja tuotteet ovat p����asiassa toimisto- ja keitti��kalusteita. Kev��ttalvella 2008 yritykseen siirrettiin Nummelasta pintak��sittelyosasto, jolla on tehty petsaus- ja lakkaust��it��. N��iden lis��ksi tehtaalla on pohdittu mahdollisuuksia maalaust��ihin, jotta UV-telalinjan kapasiteetti saataisiin paremmin k��ytt����n Ty��ss�� selvitettiin, mit�� muutoksia UV-kovettuvilla aineilla maalaaminen vaatii linjaan ja luotiin edellytykset maalaustoiminnan aloittamiselle. Muutokset pyrittiin pit��m����n niin v��h��isin�� kuin mahdollista. Lis��ksi m����ritettiin maalattavien tuotteiden laadun kriteerit ja todennusmenetelm��t, jotka voidaan viesti�� asiakkaille v����rink��sitysten v��ltt��miseksi. Laadun todentamista varten valmistettiin sarja koekappaleita, joista mitattiin asiakkaan kannalta t��rkeimm��t maalikalvon ominaisuudet. Ty��ss�� tarkasteltiin my��s pintak��sittelylaitoksia koskevaa VOC-asetusta ja verrattiin liuottimien kulutusta asetuksen m����ritt��miin rajoihin. Puulevyst�� valmistettujen kalusteosien pintak��sittely UV-telalinjalla eroaa oleellisesti perinteisist�� menetelmist�� esimerkiksi tuotantonopeuden osalta, joka johtuu p����asiassa pinnoitekalvon hetkess�� tapahtuvasta kovettumisesta UV-valon vaikutuksesta. UV-aineet ovat k��yt��nn��ss�� t��ysin kiinteist�� aineista koostuvia, eiv��tk�� n��in sis��ll�� vaarallisia haihtuvia liuottimia. UV-kovettuvilla tuotteilla maalaaminen on viime vuosina runsaasti tutkittu alue, joka eroaa tietyilt�� osin my��s pintak��sittelyst�� UV-kirkaslakoilla. Pigmentoitujen kalvojen kovettuminen vaatii erilaista UV-s��teily�� ja levitysm����rien seuranta on huomattavasti tarkempaa.

Lipase-catalyzed Approaches towards Secondary Alcohols: Intermediates for Enantiopure Drugs

The use of enantiopure intermediates for drug synthesis is a trend in pharmaceutical industry. Different physiological effects are associated with the enantiomers of chiral molecules. Thus, the safety profile of a drug based on an enantiopure active pharmaceutical ingredient is more reliable. Biocatalysis is an important tool to access enantiopure molecules. In biocatalysis, the advantage of selectivity (chemo-, regio- and stereoselectivity) is combined with the benefits of a green synthesis strategy. Chemoenzymatic syntheses of drug molecules, obtained by combining biocatalysis with modern chemical synthesis steps usually consists of fewer reaction steps, reduced waste production and improved overall synthetic efficiency both in yields and enantio- and/or diastereoselectivities compared with classical chemical synthesis. The experimental work together with the literature review clearly indicates that lipase catalysis is highly applicable in the synthesis of enantiopure intermediates of drug molecules as the basis to infer the correct stereochemistry. By lipase catalysis, enantiopure secondary alcohols used as intermediates in the synthesis of Dorzolamide, an antiglaucoma drug, were obtained. Enantiopure _-hydroxy nitriles as potential intermediates for the synthesis of antidepressant drugs with 1-aryl-3- methylaminopropan-1-ol structure were also obtained with lipases. Kinetic resolution of racemates was the main biocatalytic approach applied. <i>Candida Antarctica</i> lipase B, <i>Burkholderia cepacia</i> lipase and <i> Thermomyces lanuginosus</i> lipase were applied for the acylation of alcohols and the alcoholysis of their esters in organic solvents, such as in diisopropyl ether and <i>tert-</i>butyl methyl ether. <i>Candida Antarctica</i> lipase B was used under solvent free conditions for the acylation of ethyl 3-hydroxybutanoate.

Membraanien kest��vyys ionisessa nesteess��

T��m��n diplomity��n tavoitteena oli etsi�� mahdollisimman hyvin ionista nestett�� kest��v�� yleisesti kaupallisesti saatavilla oleva nano- tai ultrasuodatusmembraani. Kirjallisuusosassa on perehdytty yleisesti membraanitekniikan ja ionisten nesteiden historiaan sek�� niiden ominaisuuksiin ja k��ytt��sovelluksiin. Membraaniprosesseista on lyhyesti k��yty l��pi mikro-, ultra- ja nanosuodatus sek�� k����nteisosmoosi ja pervaporaatio. Kokeellisessa osassa tutkittiin nelj��ntoista kaupallisesti saatavilla olevien nano- ja ultrasuodatusmembraanien kest��vyytt�� ionisessa nesteess��. Tutkimuksessa k��ytettyjen membraanien vesi- ja malliaineliuosvuon arvoja sek�� retentioita vertailtiin ennen ja j��lkeen ioniselle nesteelle altistusta. Tulokset osoittivat, ett�� polyamidista, polyeetterisulfonista ja sulfonoidusta polyeetterisulfonista valmistettujen membraanien suodatusominaisuudet muuttuivat niiden altistuessa ioniselle nesteelle. N��iden membraanien permeabiliteetit ja retentiot laskivat viikon altistuksen j��lkeen merkitt��v��sti. Erityisesti liuottimia kest��viksi suunnitellut membraanit s��ilyttiv��t erotusominaisuutensa paremmin.

Extractives and energetic properties of wood and charcoal

Charcoal production stands out as a raw material for the production of renewable energy. To assess wood quality in energy terms, studies have focused more on the holocellulose and lignin content than on the role of extractives. The objective of this study was to evaluate the relationship between the extractive content in cold water, in dichloromethane and total on energy properties of wood and charcoal, from six trees species. The extractives were removed with different solvents to be recorded and gross calorific value of wood was determined. The wood was carbonized at 1.67��C/min heating rate until maximum of 450��C and residence time of 30 min. The extractive content was correlated with the gravimetric yield, apparent relative density, ash, volatile matter, fixed carbon and gross calorific value of charcoal. The removal of total extractives and extractives soluble in dichloromethane reduced the gross calorific value of wood of most species evaluated. The extractives removed in cold water did not correlate with the parameters of carbonization. The extractives content in dichloromethane correlated with volatile matter, fixed carbon and gross calorific value. Total extractive content correlated with gravimetric yield, apparent relative density and gross calorific value of charcoal.