Chemical and physiological aspects of isomers of conjugated fatty acids

Conjugated fatty acid (CFA) is the general term to describe the positional and geometric isomers of polyunsaturated fatty acids with conjugated double bonds. The CFAs of linoleic acid (CLAs) are found naturally in foods derived from ruminant animals, meat, or dairy products. The CFAs of α-linolenic acid (CLNAs) are found exclusively in various types of seed oils of plants. There are many investigations to assess the effects to health from CFAs consumption, which have been associated with physiological processes that are involved with non transmissible chronic diseases such as cancer, atherosclerosis, inflammation, and obesity. Conclusive studies about the CFAs effects in the body are still scarce and further research about their participation in physiological processes are necessary. This review aimed to discuss the influence of conjugated fatty acids on physiological processes in animal organism.

Docosahexaenoic acid ethyl esther (DHAEE) microcapsule production by spray-drying: optimization by experimental design

Docosahexaenoic acid is an essential polyunsaturated fatty acid with important metabolic activities. Its conjugated double bonds make it susceptible to decomposition. Its stability may be improved through fatty acid entrapment with a spray-drying technique; however, the many parameters involved in this technique must be considered to avoid affecting the final product quality. Therefore, this study aimed to evaluate the entrapment conditions and yields of fish oil enriched with docosahexaenoic acid ethyl ester. Microcapsules were obtained from Acacia gum using a spray-drying technique. The experimental samples were analyzed by chromatography and delineated by Statistica software, which found the following optimum entrapment conditions: an inlet temperature of 188 °C; 30% core material; an N2 flow rate of 55 mm; and a pump flow rate of 12.5 mL/minute. These conditions provided a 66% yield of docosahexaenoic acid ethyl ester in the oil, corresponding to 19.8% of entrapped docosahexaenoic acid ethyl ester (w/w). This result was considered significant since 30% corresponded to wall material.

Stigmastadiene and specific extitntion (270 nm) to evaluate the presence of refined oils in virgin olive oil commercialized in Brazil

The increased marketing of olive oil in Brazil has intensified legal requirements to ensure regulation of this product. The measurement of the specific extinction at 270 nm (E 270) and content of stigmastadiene can be used to assess the presence of refined oils in virgin olive oil. During the vegetable oil refining process, compounds with conjugated double bonds are generated from unsaturated fatty acids that absorb at 270 nm and sterols, such as stigmasta-3,5-diene. To compare these parameters, seven samples of extra virgin olive oil and three samples of olive oil (blend of virgin and refined) were analyzed. Among the samples analyzed, four extra virgin samples had levels of stigmastadiene and E 270 higher than expected, among which two were adulterated with seed oil (rich in linoleic acid) and the other two with olive pomace oil. The results demonstrate the higher sensitivity of stigmastadiene to determine the presence of the refined oil in virgin olive oil and good agreement with determining E 270. The latter technique is a simple, quick, and low cost method of determination that can be easily implemented in laboratories to assist in the screening and regulation of olive oils sold in Brazil.

Metal-Ion-Binding Oligonucleotides: High-Affinity Probes for Nucleic Acid Sequences

Small non-coding RNAs have numerous biological functions in cell and are divided into different classes such as: microRNA, snoRNA, snRNA and siRNA. MicroRNA (miRNA) is the most studied non-coding RNA to date and is found in plants, animals and some viruses. miRNA with short sequences is involved in suppressing translation of target genes by binding to their mRNA post-transcriptionally and silencing it. Their function besides silencing of the viral gene, can be oncogenic and therefore the cause of cancer. Hence, their roles are highlighted in human diseases, which increases the interest in using them as biomarkers and drug targets. One of the major problems to overcome is recognition of miRNA. Owing to a stable hairpin structure, chain invasion by conventional Watson-Crick base-pairing is difficult. One way to enhance the hybridization is exploitation of metal-ion mediated base-pairing, i. e. oligonucleotide probes that tightly bind a metal ions and are able to form a coordinative bonds between modified and natural nucleobases. This kind of metallo basepairs containing short modified oligonucleotides can also be useful for recognition of other RNA sequences containing hairpin-like structural motives, such as the TAR sequence of HIV. In addition, metal-ion-binding oligonucleotides will undoubtedly find applications in DNA-based nanotechnology. In this study, the 3,5-dimethylpyrazol-1-yl substituted purine derivatives were successfully incorporated within oligonucleotides, into either a terminal or non-terminal position. Among all of the modified oligonucleotides studied, a 2-(3,5-dimethylpyrazol-1-yl)-6-oxopurine base containing oligonucleotide was observed to bind most efficiently to their unmodified complementary sequences in the presence of both Cu2+ or Zn2+. The oligonucleotide incorporating 2,6-bis(3,5-dimethylpyrazol-1-yl)purine base also markedly increased the stability of duplexes in the presence of Cu2+ without losing the selectivity.

Antimutagenic, antiproliferative, and antioxidant effect of extracts obtained from octopus (Paraoctopus limaculatus)

Abstract The search for chemopreventive/chemoprotective compounds in marine organism has been extensively reported; however, the presence of these compounds in octopus has been incipiently explored. In this research, the antimutagenic, antiproliferative, and antioxidant potential of three crude extracts (methanolic, acetonic, and hexanic) from Paroctopus limaculatus was investigated. Antimutagenic activity against aflatoxin B1 (AFB1) was evaluated through the Ames test using Salmonella typhimurium tester strains TA98 and 100. Antiproliferative activity was assessed using the standard MTT (3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide) assay on M12.C3.F6 murine cell line. Antioxidant activity was assessed using the DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) methods. Hexanic extract showed the highest antimutagenic and antiproliverative activities inhibiting 80 and 43% of mutagenicity induced by AFB1 for TA98 and TA100, respectively, and showing a high antiproliferative activity at 200 and 100 µg/mL. However, when the antioxidant activity was evaluated at a concentration of 50 mg/mL, the methanolic fraction exerted inhibition of 98 and 96 % ABTS and DPPH radicals, respectively. RP-HPLC and 1H-RMN analyses suggested the presence of double bonds with extended conjugation and oxygenated compounds such as alcohols, esters, ethers or ketones. These results suggested that hexanic and methanolic extract form octopus contained compounds with chemoprotective and antioxidant properties.

Multicultural Belonging. Individuals across cultures, languages and places

The article-based doctoral dissertation deals with adult individuals in Western societies who were born into multilingual and multicultural families and have parents of different nationalities. The study’s participants grew up outside their parents’ countries of origin and relate to a multitude of bonds that link them across various cultures, languages and places. The study explores the social dimension of cultural belonging and examines diverse approaches that enable the participants to create notions of belonging and identification despite possessing at times contradictory transnational allegiances. The works offers new perspectives on transnational belonging and makes a timely contribution to discussions in the fields of cultural heritage studies, ethnology and transnational studies. The dissertation combines qualitative research methods with an insider perspective. The empirical material is based on semi-structured interviews with fifteen participants, among which are also the author’s siblings. The study addresses the relevance of the author’s personal situatedness and her multi-faceted roles as well as ethical concerns related to the methodological approach of insider research. The social dimension of cultural identities affect both the participants’ identification with their multiple attachments and language use in everyday life. The key research findings present interrelated discussions of the participants’ notion of being a mixture, the importance of family bonds and multilingualism, a specific mixed family lifestyle, the notion of non-belonging and the study participants’ sense of otherness as a means of creating communality with others. The study discusses the participants’ various life strategies of flexible relativising, juggling with multiple affiliations, the approach of “blending in” and their sense of ironic nation-ness for constructing a coherent sense of belonging. The author argues that multicultural belonging is inextricably connected to an association with multiple languages, cultures and places. Multicultural belonging is relational and depends on the context, social relationships and locations. The study proposes that multicultural belonging creates a tolerant understanding of membership and enables experiences of cosmopolitanism and selected notions of allegiance.

Perfluorattuja yhdisteitä sisältävien jätevesien puhdistus- ja analyysimenetelmät

Perfluoratut alkyyliyhdisteet eli PFAS-yhdisteet ovat synteettisiä orgaanisia yhdisteitä, joissa on fluorattu hiiliketju. Hiilen ja fluorin väliset vahvat sidokset ovat muodostuneet ongelmaksi jätevedenpuhdistamoilla, sillä yhdisteet eivät hajoa puhdistamoilla käytössä olevilla vedenpuhdistusmenetelmillä. Yhdisteitä kertyy luontoon jätevesien mukana. Kandidaatintyössä on vertailtu yhdisteitä sisältävien vesien käsittelymenetelmiä parhaiten soveltuvan menetelmän löytämiseksi. Menetelmien kustannuksia tai soveltuvuutta vedenpuhdistamomittakaavan prosessiksi ei ole arvioitu. Lisäksi työssä on koottu yhdisteitä sisältävien jätevesien analysointiin sopivia analyysimenetelmiä. Soveltuvat puhdistus- ja analyysimenetelmät on esitelty uusien tieteellisten artikkelien pohjalta. Mahdollisia erotusmenetelmiä ovat membraanierotus ja sorptio. Membraaneista soveltuvimpia ovat nanosuodatus- ja käänteisosmoosimembraanit, joilla erottuvat jopa 0,0001 μm:n kokoiset partikkelit. PFAS-yhdisteet voidaan erottaa sorptiolla muun muassa aktiivihiileen. Yhdisteiden rakenne hajoaa nykyaikaisilla hapetusmenetelmillä ja polttamalla lietteen mukana. Hapettaminen permanganaatin avulla ei tuottanut hyvää tulosta, mutta fotokemiallisella hapetuksella ja alhaisen lämpötilan plasmatekniikalla (NTP) yhdisteiden rakenne hajosi lähes kokonaan. Fotokemiallinen hapetus onnistui erityisesti perfluorokarboksyylihapoilla, joiden rakenne hajosi jopa kolmessa tunnissa. Yleisimmin käytetty analyysimenetelmä on nestekromatografin ja massaspektrometrin yhdistelmä (LC-MS/MS) ja matriisivaikutus minimoidaan tyypillisesti kiinteäfaasiuutolla (SPE). Työssä esitellyistä käsittelymenetelmistä parhaiten soveltuva on NTP-menetelmä, koska sillä saatiin tutkimusten mukaan hajotettua yhdisteiden rakenne muita menetelmiä lyhyemmässä ajassa ja se soveltuu parhaiten kaikille PFAS-yhdisteille. NTP-menetelmässä ei tarvita katalyyttiä tai lisäkemikaaleja. Voimakkaana hapettimena toimivat epästabiilit hydroksyyliradikaalit, jotka syntyvät koronapurkauksen kautta. Koronapurkauksessa muodostuu myös otsonia ja lisäksi vapaa happi voi tehostaa hapettumista. Menetelmässä muodostuvien hajoamistuotteiden hallinta vaatii lisätutkimusta. Mahdollinen hallintakeino voisi olla esimerkiksi hapettumisessa vapautuvien fluoridi-ionien saostaminen. Muodostuvien hajoamistuotteiden toksisuutta voitaisiin tarkkailla biosensorilla.

Matemática agradável

This paper suggests a reconsideration of the principle that public deficits should be financed by public debt. Two main reasons are offered. First, it is admitted that public debt is an economic variable whose time behaviour is better described by a first difference equation instead of an accounting identity. The convergence condition thus obtained requires either a nominal negative interest rate or that government bonds are used to raise tax income, hypotheses not theoretically granted. As a consequence, if primary surplus is not sufficient to match interests' payment, it will be observed an explosive trend in the public debt, the due interests and the money issuing. Therefore, it lacks support to the idea that public debt prevents inflation. Second, it is shown that financing public deficit through money issuing leads to a stable equilibrium money stock. The general conclusion is that, in order to simultaneously promote economic growth and inflation control, money issuing is preferable to public debt.

Inovações financeiras e institucionais do sistema de financiamento residencial americano

This article has the gold of summarize the institutional modifications of the US housing finance system between the 60's and the end of the 90's. Those changes narrowed the bonds between this segment of the credit market and the securitized financial markets, encouraging the foundation and diffusion of financial innovations that are in the core of the current financial crises.

Revelações da crise: moeda fiduciária e as relações Tesouro/Banco Central

The current crisis shed a new light on issues that, previously, were not perceived as serious or important. It highlighted the close ties between fiat currency and government bonds denominated in it or, in other words, the relationship between Treasury and Central Bank. Two ill-conceived views of the "new consensus" on money that had turned into taboos were put in evidence. The first, derived from the quantitative theory, concerns the rejection of unsterilized monetary expansion; the second, directly related to the neoliberal ideology, prohibits or imposes strict limits on the role of central banks in the financing of public debts.

The Brazilian deindustrialization: financialization is not guilty

The financialization of the Brazilian economy is often criticized as being responsible of the slowdown of capital accumulation in this country. Indeed, very high interest rates are maintained in order to finance the public debt, and this fosters capitalists to get more Treasury bonds rather than to invest in the productive area. Nevertheless, the evolution of the profit rate in this area also explains the particular relation existing between capitalists, finance and productive investment, as Marx showed it more than a century ago.

Päättäväiset porvarskat. Turun johtavan porvariston naisten toimijuus vuosina 1623–1670

Turun 1600-luvun johtavan porvariston naiset toimivat aktiivisesti ja päättäväisesti omiin ja perheensä etuihin liittyvissä asioissa. He jatkoivat jo keskiajalla alkanutta traditiota, jossa myös porvarisvaimojen taloudellisen toiminnan merkitys korostui. He eivät kuitenkaan olleet perheestään, suvustaan tai Turun paikallisyhteisöstä erillään olevia yksilöitä, vaan tärkeä osa niitä. Siksi heidän toimijuuttaan ei voi eikä tule erottaa aikakautensa ja yhteisönsä kontekstista. Johtavan porvariston naiset ajoivat asioitaan Turun kaupungin oikeusasteissa kaikissa kolmessa siviilisäädyssä, naimattomina tyttärinä, aviovaimoina ja leskinä, aktiivisimmat heistä elämänsä aikana yli sata kertaa. Verrattuna muihin saman ajanjakson kaupunkeihin naimattomaksi jääneet turkulaiset porvaristyttäret esiintyivät korostuneen aktiivisesti valvomassa taloudellisia etujaan. Heidän toimintansa hyväksyttiin silloin, kun se ei ylittänyt porvariyhteisön sovinnaisuuden rajoja, joita he pyrkivät koettelemaan parantaakseen talouttaan. Leskinaisten oikeustoimikelpoisuus kertoo siitä, että naisia ei pidetty vaimoinakaan lähtökohtaisesti kyvyttöminä hoitamaan perheen asioita, vaan ainoastaan velvollisina alistumaan miehensä edusmiehisyyteen ja määräysvaltaan tämän eläessä. Talouden pää oli yleensä mies ja hänen velvollisuutenaan oli ajaa perheensä asioita. Siksi aviovaimot esiintyvät oikeudessa siviilisäädyistä harvimmin. Leskillä oli puolestaan oikeus hoitaa itse omaisuuttaan. Tämä tarkoitti myös velvollisuutta valvoa lasten perintöä. Turun johtava porvaristo koostui joistakin kymmenistä perheistä, joista suurin osa oli 1600-loppupuolelle tultaessa muodostanut avioliittojen kautta laajan sukulaisverkoston. Tätä verkostoa ei olisi voinut syntyä ilman porvarisnaisia, joiden avioliitot mahdollistivat omaisuuden siirtämisen uusille yrittäjille. Vaikka sukulaisuussuhteet olivat tärkeitä kaupankäynnissä, kokivat naiset ne myös uhkaksi itselleen. Sukulaismiehet pyrkivät usein saamaan naisten omaisuutta käyttöönsä vetoamalla näiden heikkoon kykyyn hallita omaisuutta. Porvarisnaiset kuitenkin puolustautuivat tällaisissa tilanteissa voimakkaasti ja hakivat turvaa porvariyhteisöä edustaneelta raadilta. He osasivat vedota asemaansa yhteisön jäseninä ja saivat yleensä raadin ja porvariyhteisön tuen. Aviomiehen kuoltua porvarisnaisen oli päätettävä, jatkoiko hän miehensä liiketoimintaa vai hankkiko hän elantonsa jollain muulla tavalla. Monet lesket järjestelivät taloudellisia asioitaan heti miehensä kuoltua ja jäivät sitten elämään esimerkiksi kaupunkitalonsa, maatilojensa ja pääomansa turvin. Osa naisista jatkoi yrittäjyyttä pienimuotoisesti esimerkiksi lainaamalla rahaa korkoa vastaan tai panemalla olutta. Muutamat johtavan porvariston naiset jatkoivat kuitenkin laajaa taloudellista toimintaa vuosikausia. Heidän menestyksensä osoittaa, että he olivat saaneet jo kotonaan perusteellisen koulutuksen porvarisammattiin. He olivat myös toimineet miehensä kumppaneina yrityksen toiminnassa, joten heillä oli hyvät edellytykset itsenäiseen asioiden hoitamiseen. Saamansa koulutuksen turvin porvarisnaiset siirsivät osaamisensa myös lapsilleen.

On the effect of molecular structure and composition on the photofragmentation of biomolecules

The research on the interaction between radiation and biomolecules pro-vides valuable information for both radiobiology and molecular physics. While radiobiology is interested in the damage inflicted on the molecule upon irradiation, molecular physics exploits these studies to obtain infor-mation about the physical properties of the molecule and the quantum me-chanical processes involved in the interaction. This thesis work investigated how a small change in the structure or composition of a biomolecule changes the response of the molecule to ioniz-ing radiation. Altogether eight different biomolecules were studied: nucleo-sides uridine, 5-methyluridine and thymidine; amino acids alanine, cysteine and serine; and halogenated acetic acids chloro- and bromoacetic acids. The effect of ionizing radiation on these molecules was studied on molecular level, investigating the samples in gas phase. Synchrotron radiation of VUV or soft x-ray range was used to ionize sample molecules, and the subsequent fragmentation processes were investigated with ion mass spectroscopy and ion-ion-electron coincidence spectroscopy. The comparison between the three nucleosides revealed that adding or removing a single functional group can affect not only the bonds from which the molecule ruptures upon ionization but also the charge localiza-tion in the formed fragments. Studies on amino acids and halogenated acetic acids indicated that one simple substitution in the molecule can dramatical-ly change the extent of fragmentation. This thesis work also demonstrates that in order to steer the radiation-induced fragmentation of the molecules, it is not always necessary to alter the amount of energy deposited on the molecules but selecting a suitable substitution may suffice.

Investigation of single tryptophan proteins encapsulated in TEOS-derived sol-gel matrices by fluorescence spectroscopy /

In the work reported here, optically clear, ultrathin TEOS derived sol-gel slides which were suitable for studies of tryptophan (Trp) fluorescence from entrapped proteins were prepared by the sol-gel technique and characterized. The monitoring of intrinsic protein fluorescence provided information about the structure and environment of the entrapped protein, and about the kinetics of the interaction between the entrapped protein and extemal reagents. Initial studies concentrated on the single Trp protein monellin which was entrapped into the sol-gel matrices. Two types of sol-gel slides, termed "wet aged", in which the gels were aged in buffer and "dry-aged", in which the gels were aged in air , were studied in order to compare the effect of the sol-gel matrix on the structure of the protein at different aging stages. Fluorescence results suggested that the mobility of solvent inside the slides was substantially reduced. The interaction of the entrapped protein with both neutral and charged species was examined and indicated response times on the order of minutes. In the case of the neutral species the kinetics were diffusion limited in solution, but were best described by a sum of first order rate constants when the reactions occurred in the glass matrix. For charged species, interactions between the analytes and the negatively charged glass matrix caused the reaction kinetics to become complex, with the overall reaction rate depending on both the type of aging and the charge on the analyte. The stability and conformational flexibility of the entrapped monellin were also studied. These studies indicated that the encapsulation of monellin into dry-aged monoliths caused the thermal unfolding transition to broaden and shift upward by 14°C, and causedthe long-term stability to improve by 12-fold (compared to solution). Chemical stability studies also showed a broader transition for the unfolding of the protein in dry-aged monoliths, and suggested that the protein was present in a distribution of environments. Results indicated that the entrapped proteins had a smaller range of conformational motions compared to proteins in solution, and that entrapped proteins were not able to unfold completely. The restriction of conformational motion, along with the increased structural order of the internal environment of the gels, likely resulted in the improvements in themial and long-term stability that were observed. A second protein which was also studied in this work is the metal binding protein rat oncomodulin. Initially, the unfolding behavior of this protein in aqueous solution was examined. Several single tryptophan mutants of the metal-binding protein rat oncomodulin (OM) were examined; F102W, Y57W, Y65W and the engineered protein CDOM33 which had all 12 residues of the CD loop replaced with a higher affinity binding loop. Both the thermal and the chemical stability were improved upon binding of metal ions with the order apo < Ca^^ < Tb^"^. During thermal denaturation, the transition midpoints (Tun) of Y65W appeared to be the lowest, followed by Y57W and F102W. The placement of the Trp residue in the F-helix in F102W apparently made the protein slightly more thermostable, although the fluorescence response was readily affected by chemical denaturants, which probably acted through the disruption of hydrogen bonds at the Cterminal end of the F-helix. Under both thermal and chemical denaturation, the engineered protein showed the highest stability. This indicated that increasing the number of metal ligating oxygens in the binding site, either by using a metal ion with a higher coordinatenumber (i.e. Tb^*) which binds more carboxylate ligands, or by providing more ligating groups, as in the CDOM33 replacement, produces notable improvements in protein stability. Y57W and CE)OM33 OM were chosen for further studies when encapsulated into sol-gel derived matrices. The kinetics of interaction of terbium with the entrapped proteins, the ability of the entrapped protein to binding terbium, as well as thermal stability of these two entrapped protein were compared with different levels of Ca^"*^ present in the matrix and in solution. Results suggested that for both of the proteins, the response time and the ability to bind terbium could be adjusted by adding excess calcium to the matrix before gelation. However, the less stable protein Y57W only retained at most 45% of its binding ability in solution while the more stable protein CDOM33 was able to retain 100% binding ability. Themially induced denaturation also suggested that CDOM33 showed similar stability to the protein in solution while Y57W was destabilized. All these results suggested that "hard" proteins (i.e. very stable) can easily survive the sol-gel encapsulation process, but "soft" proteins with lower thermodynamic stability may not be able to withstand the sol-gel process. However, it is possible to control many parameters in order to successfully entrap biological molecules into the sol-gel matrices with maxunum retention of activity.

Study of colossal magnetoresistance and pressure effects in La2/3Ca1/3MnO2 thin films /

The main purpose of this thesis is to study properties of La2/3Cai/3Mn03, both polycrystalline ceramics and thin films. This material has striking related electrical and magnetic properties. Thin films show colossal negative magnetoresistance (CMR) near transition from an insulating to a metallic state accompanied closely by transition from a paramagnetic to a ferromagnetic state. The double exchange mechanism (DE) and the Jahn-Teller deformations play an important role in CMR effect. Applied pressure has a very similar effect as does an applied magnetic field, except, at low temperatures (Tbonds in applied pressure axe discussed. The fabrication of La2/3Cai/3Mn03 thin films by pulsed laser deposition was successfully developed. The films grown on (100) SrTiOs substrate are c-axis oriented and exhibit negative magnetoresistance Ap/p(H) of over 400% at 245°C and 4200% at 90 K.