Pro-fragrant ionic liquids with stable hemiacetal motifs: water-triggered release of fragrances

Stable liquid and solid salts in the form of elusive hemiacetals, appended with fragrant alcohols, have been synthesised as pro-fragrances, and the controlled release of these fragrances, triggered by water, is demonstrated

Syntheses and Self-Assembling Characteristics of Amphiphilic Star Diblock Copolymers

Uusien polymeeripohjaisten teknologioiden ja materiaalien myötä räätälöityjen polymeerien tarve on kasvanut. Viime vuosituhannen lopussa kehitetyt kontrolloidut polymerointimenetelmät ovat avanneet uusia mahdollisuuksia paitsi monimutkaisten polymeerien synteesiin, myös itsejärjestyvyyteen perustuvien funktionaalisten nanorakenteiden suunnitteluun ja valmistukseen. Nämä voivat jäljitellä luonnossa esiintyviä rakenteita, joita muodostavat esimerkiksi lipidit ja proteiinit. Itsejärjestyvät molekyylit ovat usein amfifiilisiä eli ne koostuvat hydrofiilisistä ja hydrofobisista osista ja polymeereissä nämä osat voivat olla omina lohkoinaan, jolloin puhutaan amfifiilisistä lohko- tai blokkikopolymeereistä. Riippuen järjestyneiden rakenteiden koostumuksesta ja muodosta, amfifiilisiä blokkikopolymeerejä on tutkittu tai jo käytetty nanoteknologiassa, elastomeereissä, voiteluaineissa, pinta-aktiivisina aineina, lääkkeenannostelussa, maaleissa, sekä elektroniikka-, kosmetiikka- ja elintarviketeollisuudessa. Tavallisimmin käytetyt amfifiiliset blokkikopolymeerit ovat olleet lineaarisia, mutta viime aikoina tutkimus on suuntautunut kohti monimutkaisempia rakenteita. Tällaisia ovat esimerkiksi tähtipolymeerit. Tähtimäisissä polymeereissä miselleille tyypillinen ydin-kuori-rakenne säilyy hyvin alhaisissakin polymeerikonsentraatioissa, koska polymeeriketjut ovat kiinni toisissaan yhdessä pisteessä. Siten ne ovat erityisen kiinnostavia tutkimuskohteita erilaisten hydrofobisten orgaanisten yhdisteiden sitomiseksi ja vapauttamiseksi. Tässä työssä on tarkasteltu amfifiilisten tähtipolymeerien itsejärjestymistä vesiliuoksissa sekä kokeellisesti ja tietokonesimulaatioin. Työ koostuu kahdesta osasta: tähtipolymeerien synteesistä makrosyklisillä initiaattoreilla ja amfifiilisten tähtimäisten blokkikopolymeerien ominaisuuksien tutkimisesta.

Vivenciando lugares prenhes de significados e decifrando simbologias da rua Sacadura Cabral e Morro da Conceição (RJ), arenas de vida e de pertencimento

A cidade do Rio de Janeiro atravessa um momento de intensas metamorfoses. O porto da cidade, que outrora era conhecido com um túmulo de estrangeiros, hoje procura ostentar a alcunha de Porto Maravilha. Com base nos preceitos da Geografia Humanística - vertente que exploraos dramas, alegrias, entusiasmos e decepções ocorridos no mundo vivido, no âmbito das relações do homem com o espaço - procuramos investigar o poder da identidade e do pertencimento de moradores e frequentadores da Zona Portuária da cidade, marcadamente da rua Sacadura Cabral e do Morro da Conceição. Os lugares em tela atravessam um instigante processo de toporreabilitação, que transborda seus impactos no mundo vivido dos indivíduos, nos elos dos mesmos e para com seus lugares de significado, plenos de simbolismo. Neste contexto, o lugar deve ser visto como um contínuo dinâmico, pleno de nuances, fragrâncias, simbolismos e identidades. Afinados com princípios fenomenológicos, buscamos entender as relações dos indivíduos com seus lares, traduzindo assim a alma dos seus lugares, identidade e simbiose. Apoiado em depoimentos, que portam identidades e traduzem culturas pulsantes, procuramos elucidar a força das vivências e o poder do lugar face às transformações ocorridas nas localidades em destaque.

Novos frascos, velhas fragrâncias: a institucionalização da Lei Maria da Penha em uma cidade fluminense

A presente tese se propõe descrever e analisar as relações interpessoais entre mulheres, homens e profissionais das áreas do direito, psicologia e serviço social envolvidos na institucionalização da Lei 11.340/06, conhecida como Lei Maria da Penha (LMP), que rege hoje no Brasil os crimes de violência doméstica e familiar contra a mulher. Inicialmente é apresentada uma concisa contextualização da LMP e do campo de debate em que se insere, além das principais mudanças introduzidas por ela em relação às antigas políticas. As controvérsias que a lei vem levantando e as modificações sofridas em pouco tempo de existência, apontam para as dificuldades em se estabelecer um consenso por parte dos operadores e formuladores da lei quanto à percepção da violência doméstica e familiar contra a mulher como um crime e quanto a sua justa punição. Não só os operadores, mas as feministas também se envolveram em controvérsias teóricas em torno da distinção entre as definições de violência contra a mulher e de crime de violência contra a mulher. O esforço de se avançar na análise dessas categorias se justifica pelas dificuldades e impasses que se observam nas práticas institucionais na implementação da LMP. Essas práticas são descritas e analisadas a partir da incursão etnográfica em dois campos. No Juizado de Violência Doméstica e Familiar contra a Mulher participei de encontros de um grupo de reflexão para homens autores de violência, assisti audiências, entrevistei profissionais e dezoito homens envolvidos com a LMP. Os sentidos em disputa que os vários atores sociais constroem relativos aos conflitos violentos da intimidade ali julgados e suas relações com o exercício da(s) masculinidade(s) são discutidos. As informações do outro campo, um Centro de Referência da Mulher, provêm das observações de cenas do cotidiano institucional, do acompanhamento de atendimentos às usuárias, da participação em grupos de reflexão para as mulheres vítimas de violência e de entrevistas com duas profissionais e dezessete mulheres. É enfatizado o caráter de intervenção pedagógica das instituições que objetivam promover mudanças em caracteres considerados como de gênero de homens (a agressividade) e mulheres (a passividade) que estariam influenciando o engendramento e manutenção das violências. Nas entrevistas é ressaltado o que ecoa, corrobora, complementa, destoa ou mesmo mostra novos ângulos do que é apreendido nos grupos (confronto entre os sentidos da violência e suas relações com o que é ser homem e o que é ser mulher) e nas audiências (tendência à vitimização e à relativização dos papéis de vítima e acusado). Independente dos embates e controvérsias suscitadas, pode-se afirmar que a violência contra a mulher ingressou no mundo da lei nacional trazendo com sua institucionalização uma intensa circulação de diferentes sentidos, lógicas e moralidades que (re)modelam convenções sobre as relações de gêneros e sua influência sobre a citada violência.

Analytical method development for the uptake study of different organic pollutants by crops cultivated in compost-amended soils

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Single mating in orchid bees (Euglossa, Apinae): implications for mate choice and social evolution

Neotropical orchid bees (Euglossini) are conspicuously different from other corbiculate bees (Apinae) in their lack of advanced sociality and in male use of acquired odors (fragrances) as pheromone-analogues. In both contexts, orchid bee mating systems, in particular the number of males a female mates with, are of great interest but are currently unknown. To assess female mating frequency in the genus Euglossa, we obtained nests from three species in Mexico and Panama and genotyped mothers and their brood at microsatellite DNA loci. In 26 out of 29 nests, genotypes of female brood were fully consistent with being descended from a singly mated mother. In nests with more than one adult female present, those adult females were frequently related, with genotypes being consistent with full sister-sister (r = 0.75) or mother-daughter (r = 0.5) relationships. Thus, our genetic data support the notions of female philopatry and nest-reuse in the genus Euglossa. Theoretically, single mating should promote the evolution of eusociality by maximizing the relatedness among individuals in a nest. However, in Euglossini this genetic incentive has not led to the formation of eusocial colonies as in other corbiculate bees, presumably due to differing ecological or physiological selective regimes. Finally, monandry in orchid bees is in agreement with the theory that females select a single best mate based on the male fragrance phenotype, which may contain information on male age, cognitive ability, and competitive strength.

Langerhans cells protect from allergic contact dermatitis in mice by tolerizing CD8+ T cells and activating Foxp3+ regulatory T cells

Allergic contact dermatitis is the most frequent occupational disease in industrialized countries. It is caused by CD8(+) T cell-mediated contact hypersensitivity (CHS) reactions triggered at the site of contact by a variety of chemicals, also known as weak haptens, present in fragrances, dyes, metals, preservatives, and drugs. Despite the myriad of potentially allergenic substances that can penetrate the skin, sensitization is relatively rare and immune tolerance to the substance is often induced by as yet poorly understood mechanisms. Here we show, using the innocuous chemical 2,4-dinitrothiocyanobenzene (DNTB), that cutaneous immune tolerance in mice critically depends on epidermal Langerhans cells (LCs), which capture DNTB and migrate to lymph nodes for direct presentation to CD8(+) T cells. Depletion and adoptive transfer experiments revealed that LCs conferred protection from development of CHS by a mechanism involving both anergy and deletion of allergen-specific CD8(+) T cells and activation of a population of T cells identified as ICOS(+)CD4(+)Foxp3(+) Tregs. Our findings highlight the critical role of LCs in tolerance induction in mice to the prototype innocuous hapten DNTB and suggest that strategies targeting LCs might be valuable for prevention of cutaneous allergy.

Synthesis of , of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs’ catalysts

A series of alpha,beta-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (>= 90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids. 

The consumption of beauty products on famale young adults in Portugal. Recommenrations for the brand Lancôme to improve its store trafic

This project aims to explore the Portuguese Beauty and Cosmetics market, and to discuss the usage and purchase behaviour of young female adults, between 18 and 26 years old. After a market analysis based on secondary data, it evaluates the results of qualitative and quantitative research based on 9 interviews and 126 online questionnaires to explore the consumers’ reasoning when choosing products from this category – fragrances, skin care or make-up – as well as their attitude towards brands, with a special focus on the premium cosmetics brand Lancôme. Contrary to our expectations there was no statistically significant positive influence of the online touchpoints within this age segment’s purchase intention. However, results indicate that Lancôme is already being perceived by some as young and modern, but is still suffering the threat of Mass Market brands that are valued by this target, mainly due to a price sensitivity towards premium beauty brands.

Hazardous substances in frequently used professional cleaning products.

A growing number of studies have identified cleaners as a group at risk for adverse health effects of the skin and the respiratory tract. Chemical substances present in cleaning products could be responsible for these effects. Currently, only limited information is available about irritant and health hazardous chemical substances found in cleaning products. We hypothesized that chemical substances present in cleaning products are known health hazardous substances that might be involved in adverse health effects of the skin and the respiratory tract. We performed a systematic review of cleaning products used in the Swiss cleaning sector. We surveyed Swiss professional cleaning companies (n = 1476) to identify the most used products (n = 105) for inclusion. Safety data sheets (SDSs) were reviewed and hazardous substances present in cleaning products were tabulated with current European and global harmonized system hazard labels. Professional cleaning products are mixtures of substances (arithmetic mean 3.5 +/- 2.8), and more than 132 different chemical substances were identified in 105 products. The main groups of chemicals were fragrances, glycol ethers, surfactants, solvents; and to a lesser extent, phosphates, salts, detergents, pH-stabilizers, acids, and bases. Up to 75% of products contained irritant (Xi), 64% harmful (Xn) and 28% corrosive (C) labeled substances. Hazards for eyes (59%) and skin (50%), and hazards by ingestion (60%) were the most reported. Cleaning products potentially give rise to simultaneous exposures to different chemical substances. As professional cleaners represent a large workforce, and cleaning products are widely used, it is a major public health issue to better understand these exposures. The list of substances provided in this study contains important information for future occupational exposure assessment studies.

Características del diseño de una relación estratégica comunitaria y marketing en emprendimiento en el sector de ambientadores y cosméticos

En nuestro país el sector de ambientadores y cosméticos ha presentado un crecimiento económico constante y notable, proyectando a Colombia para el año 2032 como un dirigente en la elaboración de cosméticos y productos de aseo. La biodiversidad colombiana ofrece múltiples recursos, incluyendo una gran diversidad de aromas naturales, es un importante mercado para producción de cosméticos sin la utilización de productos artificiales. El presente trabajo de investigación tiene por objetivo determinar las características del diseño de una relación estratégica comunitaria y marketing en la creación de una empresa de cosméticos y ambientadores. Ésta investigación se realiza bajo la recopilación de información del sector y principalmente de la organización, dentro de un estudio empírico-analítico descriptivo. Estableciendo resultados que finalmente dan respuesta a la utilidad de estrategias comunitarias en la actualidad. En el caso de estudio de la nueva empresa "Jolie Le Petit" en un sector en crecimiento, ofrece múltiples oportunidades de negocio y permite generar ideas innovadoras para la venta de productos. La facilidad de cambio y la inclusión en la comunidad posibilita el acercamiento a los clientes, asegurando la permanencia en el mercado indicado. Considerando la posibilidad que la inversión extranjera en el sector pueda afectar notablemente el mercado nacional. Mediante el análisis concluimos que la estrategia de mercadeo comunitaria es adecuada y aplicable a este tipo de empresa. "Jolie Le Petit" además de ser una unidad es también un actor social, estando inmersa en una comunidad en donde juega un papel vital el ser percibida como un buen vecino, ofreciendo a los clientes confianza compromiso y relación continua.

Fragrance release from the surface of branched poly(amide)s

Enzymes are powerful tools in organic synthesis that are able to catalyse a wide variety of selective chemical transformations under mild and environmentally friendly conditions. Enzymes such as the lipases have also found applications in the synthesis and degradation of polymeric materials. However, the use of these natural catalysts in the synthesis and the post-synthetic modification of dendrimers and hyperbranched molecules is an application of chemistry yet to be explored extensively. In this study the use of two hydrolytic enzymes, a lipase from Candida cylindracea and a cutinase from Fusarium solani pisii, were investigated in the selective cleavage of ester groups situated on the peripheral layer of two families of branched polyamides. These branched polyamides were conjugated to simple fragrances citronellol and L-menthol via ester linkages. Hydrolysis of the ester linkage between the fragrances and the branched polyamide support was carried out in aqueous buffered systems at slightly basic pH values under the optimum operative conditions for the enzymes used. These preliminary qualitative investigations revealed that partial cleavage of the ester functionalities from the branched polyamide support had occurred. However, the ability of the enzymes to interact with the substrates decreased considerably as the branching density, the rigidity of the structure and the bulkiness of the polyamide-fragrance conjugates increased.

Análise dos parâmetros cinéticos para produção de levana por Zymomonas mobilis utilizando fermentação submersa

Levan is an exopolysaccharide synthesized by several microorganisms during fermentation of a culture medium containing sucrose, yeast extract and minerals. This biopolymer has applications in the food segment as stabilizers, thickeners, as carriers for flavor and fragrances, as well as in the pharmaceutical segment as a hypocholesterolemic agent and for exhibiting antitumor activity. This work aimed to analyze the kinetic parameters for levan production. The microorganism used was Zymomonas mobilis CCT 4494, incubated in a synthetic medium containing 200.0 g L-1 of sucrose, in a rotary shaker at 200 rpm and 30°C. Samples were taken every 24h, during a period of 96h, in order to determine variations of pH, biomass, reducing sugar, total reducing sugar and levan formation. It was observed that yields of biomass and synthesized biopolymer in 24h were superior to those obtained in 48, 72 and 96h of fermentation.