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Thesis (MSc Food Sc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Fresh produce irrigation water from Western Cape Rivers carries faecal coliforms (FC) (Escherichia coli) at concentrations which often exceed the suggested limit of 1 000 FC per 100 mL and presents a health risk to consumers. On-farm ultraviolet (UV) irradiation presents several advantages for water disinfection but is an uncommon practice in South Africa. The aim of this study was to investigate the use of UV irradiation for river water disinfection prior to irrigation. Escherichia coli (E. coli) strains were exposed to low-pressure (LP) UV (4 mJ.cm-2) and UV/Hydrogen peroxide (H2O2) (4 mJ.cm-2/20 mg.L-1) treatments in Sterile Saline Solution (SSS). Strain variation in reductions was observed and ranged from 1.58 to 3.68 and 1.34 to 3.60 log for the UV and UV/H2O2 treatments, respectively. The UV/H2O2 treatment (4 mJ.cm-2/20 mg.L-1) was more effective, compared to UV singly, against some of the E. coli strains. Selected strains showed increased sensitivity at higher UV doses (8, 10 and 13 mJ.cm-2) and H2O2 concentrations (100 and 200 mg.L-1 with 4 mJ.cm-2) but a 3 log target reduction was not always reached. For all UV and UV/H2O2 treatments maximum resistance was shown by an environmental strain. Reference strains should, therefore, not be used for the optimisation of UV based disinfection parameters. At 10 mJ.cm-2 an American Type Culture Collection (ATCC) reference strain and an environmental strain (ATCC 25922 and F11.2) were both significantly less inactivated in sterilised river water compared to SSS. Enhanced water quality allowed for improved inactivation of the ATCC strain. Also, the efficiency of LP UV (5, 7 and 10 mJ.cm-2) and medium-pressure (MP) UV (13, 17 and 24 mJ.cm-2) radiation was investigated using water from the Plankenburg River. Water was sampled and treated on three respective days (Trials 1 to 3). Physico-chemical and microbiological water quality was always poor. The FC concentration reached a maximum of 6.41 log cfu.100 mL-1 while UV transmission was always below 38%. For LP and MP UV irradiation increased doses resulted in increased disinfection but a 3 log reduction of FC was only attained when MP UV light was used in Trial 1. Disinfection efficiency was dependent on water quality and on the characteristics of the microbial population in the water. Since FC were never reduced to below 3 log cfu.100 mL-1, the water did not adhere to guidelines for produce irrigation. Photo-repair following irradiation was investigated in river water using MP UV doses of 13 and 24 mJ.cm-2 and 3.5 kLux reactivating light, initially. Ultraviolet transmission was close to 50% and total coliform (TC) reduction exceeded 3 log, even at 13 mJ.cm-2. However, TC were reactivated from below 1 000 cfu.100.mL-1 to 3.93 and 4.41 log cfu.100 mL-1 for the 13 and 24 mJ.cm-2 treatments, respectively. A higher MP dose (40 mJ.cm-2) and a different treatment regime (2 x 20 mJ.cm-2) inhibited photo-repair (compared to 13 and 24 mJ.cm-2) but TC were always recovered to a final concentration surpassing 3 log cfu.100 mL-1, even under lower light intensities (1.0 to 2.0 kLux). In the current study UV irradiation did not produce water of acceptable standards for produce irrigation, mainly as a result of extremely poor water quality. However, on farm-scale, UV efficiency could be enhanced by improving water quality before irradiation. Also, stronger lamps that deliver higher UV doses may result in adequate disinfection, irrespective of water quality. Higher UV doses and the use of combination treatments (such as UV/Chlorine and UV/Peracetic acid) should be further investigated also to determine its disinfection efficiency and possible capability to inhibit post-disinfection repair. / AFRIKAANSE OPSOMMING: Varsproduk besproeiingswater vanuit Wes-Kaapse riviere bevat fekale kolivorme (FK) (Escherichia coli) in konsentrasies wat dikwels die voorgestelde limiet van 1 000 FK per 100 mL oorskry en hou `n gesondheidsrisiko vir verbruikers in. Plaasvlak ultraviolet (UV) bestraling bied verskeie voordele met verwysing na water dekontaminering, maar word selde aangewend in Suid-Afrika. Die doel van hierdie studie was om die gebruik van UV bestraling vir die dekontaminering van rivierwater, voor besproeiing, te ondersoek. Escherichia coli (E. coli) isolate is blootgestel aan lae-druk (LD) UV (4 mJ.cm-2) en UV/Waterstofperoksied (H2O2) (4 mJ.cm-2/20 mg.L-1) behandelings in Steriele Sout Oplossing (SSO). Isolaat variasie in reduksies is waargeneem en het gewissel tussen 1.58 tot 3.68 en 1.34 tot 3.60 log vir die UV en UV/H2O2 behandelings, onderskeidelik. In vergelyking met UV bestraling alleen was die UV/H2O2 behandeling (4 mJ.cm-2/20 mg.L-1) meer effektief teen sommige E. coli isolate. Geselekteerde isolate was meer sensitief tot hoër UV dosisse (8, 10 en 13 mJ.cm-2) en H2O2 konsentrasies (100 en 200 mg.L-1 met 4 mJ.cm-2), maar `n 3 log teikenreduksie was nie altyd haalbaar nie. Vir alle UV en UV/H2O2 behandlinge was die meeste weerstand deur `n omgewingsisolaat gebied. Verwysingsisolate behoort daarom nie aangewend te word vir die optimisering van UV-gebaseerde behandelingsparameters nie. By 10 mJ.cm-2 was beide `n ATCC verwysingsisolaat en `n omgewingsisolaat (ATCC 25922 en F11.2) betekenisvol minder gedeaktiveer in rivierwater as in SSO. Verbeterde waterkwaliteit het verhoogde inaktivering van die ATCC isolaat toegelaat. Die doeltreffendheid van LD UV (5, 7 en 10 mJ.cm-2) en medium-druk (MD) UV (13, 17 en 24 mJ.cm-2) bestraling is ook ondersoek deur watermonsters vanuit die Plankenburg Rivier te gebruik. Watermonsters was getrek en behandel op drie verskillende dae (Proewe 1 tot 3). Fisies-chemiese en mikrobiologiese kwaliteit van die water was deurentyd swak. Die FK konsentrasie het `n maksimum van 6.41 log kve.100 mL-1 bereik terwyl UV transmissie altyd laer as 38% was. Vir beide LD en MD UV bestraling het verhoogde dosisse gelei tot verbeterde dekontaminering, maar `n 3 log reduksie is slegs bereik toe MD UV lig gebruik is in Proef 1. Die effektiwiteit van die behandelings was afhanklik van waterkwaliteit en die eienskappe van die mikrobiese populasie in die water. Aangesien FK nooit tot onder 3 log kve.100 mL-1 verminder is nie het die water nie voldoen aan riglyne vir varsproduk-besproeiing nie. Fotoherstel na bestraling was ondersoek in rivierwater deur aanvanklik gebruik te maak van MD UV dosisse van 13 en 24 mJ.cm-2 en 3.5 kLux heraktiverende lig. Ultraviolettransmissie het byna 50% bereik en reduksie van totale kolivorme (TK) het 3 log oorskry, selfs by 13 mJ.cm-2. Totale kolivorme was egter geheraktiveer van onder 1 000 kve.100.mL-1 tot 3.93 en 4.41 log kve.100 mL-1 vir die 13 en 24 mJ.cm-2 behandelings, onderskeidelik. In vergelyking met 13 en 24 mJ.cm-2 het `n hoër MD dosis (40 mJ.cm-2) en `n veranderde bestralingstegniek (2 x 20 mJ.cm-2) fotoherstel onderdruk, maar TK was in elke geval geheraktiveer tot `n finale konsentrasie hoër as 3 log kve.100 mL-1, selfs onder laer intensiteit lig (1.0 tot 2.0 kLux). In hierdie ondersoek het UV bestraling nie water van aanvaarbare standaarde vir varsproduk besproeiing gelewer nie, hoofsaaklik as gevolg van swak waterkwaliteit. Nietemin, op plaasvlak mag die effektiwiteit van UV bestraling verhoog word deur waterkwaliteit voor bestraling te verbeter. Die gebruik van sterker lampe, om hoër UV dosisse te produseer, mag verder bydra tot voldoende dekontaminasie, ongeag van waterkwaliteit. Hoër UV dosisse en die gebruik van kombinasie behandelinge (soos UV/Chloor en UV/Perasynsuur) moet ook verder ondersoek word om die dekontaminasie effektiwiteit, en vermoë daarvan om heraktivering na dekontaminering te onderdruk, vas te stel.

The present study examined adverse effects of sunlight exposure (mimicked by intradermal cis-urocanic acid, cUCA) on local and systemic immune responses, with or without co-exposure to the immunotoxic insecticide permethrin. A single exposure to cUCA caused diminished splenic macrophage phagocytosis that was persistent up to 30 days post-exposure. Five-day exposure to cUCA subtly increased splenocyte proliferation in response to the T cell mitogen Concanavalin A. Four-week exposure to cUCA caused increased splenic lymphocyte cellularity, thymic hypocellularity, and enhanced hydrogen peroxide production by splenic leukocytes. Single exposure to topical permethrin resulted in decreased thymic and splenic weight and cellularity, and inhibited antibody production by splenic B cells. cUCA worsened the negative effect of permethrin on both thymic weight and cellularity, and depressed splenocyte blastogenesis, hydrogen peroxide production, and antibody production. Five-day exposure to either cUCA or permethrin also caused persistent decreased contact hypersensitivity responses, an effect that became more than additive when the chemicals were administered concurrently. Defects in antigen processing and presentation by cutaneous Langerhans cells were evaluated as possible contributing mechanisms to the cutaneous immunosuppression, using mice with deleted genes. Vehicle-exposed IFNg knockout mice displayed approximately a 22.1% depression in the ear swelling response as compared to control C57BL/6N mice, suggesting that this cytokine may be required for mounting a control-level hypersensitivity response. Ear swelling in cUCA-exposed IFNg knockout mice displayed a 21.4% depressed response as compared to cUCA-exposed wild-type C57BL/6N mice, again suggesting that IFNg is an important cytokine in the contact hypersensitivity (CH) response. TNFaR knockout mice exposed to cUCA displayed 33.9% greater ear swelling than cUCA-exposed wild-type C57BL/6N mice, suggesting that increased TNFa may be involved in inhibited CH by cUCA. TNFaR knockout mice exposed to permethrin displayed 33.9% greater ear swelling than permethrin-exposed C57BL/6N mice, suggesting that increased TNFa may also be involved in inhibited CH by permethrin. C57BL/6N mice exposed to cUCA + permethrin displayed severe reduction of the CH response to 8.7% of the control level. IFNg knockout mice exposed to permethrin + cUCA showed essentially identical depression of the CH response as IFNg knockout mice exposed to either permethrin or cUCA alone. These results suggest that IFNg is required for the greater than additive immunotoxic effect that occurred when these two agents were co-administered. TNFaR knockout mice exposed to cUCA + permethrin displayed 8.7 fold greater ear swelling than similarly exposed C57BL/6N mice, again suggesting that increased TNFa is involved in inhibited CH by both cUCA and permethrin. / Ph. D.

Formamide is a solvent of great interest to prebiotic chemists because it is liquid over a wide range, it is less volatile than either water or HCN, and it possesses a versatile reactivity. When formamide is heated in the presence of minerals or inorganic catalysts, a variety of products including purine nucleobases are generated. Irradiation of formamide reaction solutions with ultraviolet light increases the yield and diversity of products, and eliminates the need for a mineral catalyst. We have also performed formamide reactions in the presence of pyrite, a mineral which is likely to have been available on the primordial Earth, under a variety of atmospheric conditions. Our results indicate the greatest yield and diversity of products result from the combination of a pyrite mineral catalyst, heat, UV irradiation, and a carbon dioxide atmosphere. Purine nucleobases are simple to synthesize in model reactions and they stack well in aqueous solution; it has been hypothesized that the first nucleic acids were composed of only purine bases, and that water-soluble, cationic, aromatic molecules with large stacking surfaces (“”molecular midwives””) may have aided the assembly of the earliest nucleic acid analogs. We have characterized the interactions of various intercalators with a standard DNA duplex as well as with an antiparallel homopurine DNA duplex and have determined that molecules which possess four or more rings and a curved shape interact selectively with all-purine DNA; such molecules can serve as models for putative prebiotic midwives.

O envelhecimento dos ligantes asfálticos possui uma grande influência sobre as propriedades mecânicas das misturas asfálticas. As especificações atuais limitam determinados índices ou parâmetros de envelhecimento, visando contornar o endurecimento excessivo do ligante asfáltico, porém, não levam em conta o efeito da radiação ultravioleta (UV). O objetivo deste trabalho é avaliar o efeito dos envelhecimentos termo-oxidativo e foto-oxidativo sobre as propriedades reológicas de um CAP puro e 11 ligantes asfálticos modificados, incluindo polímeros elastoméricos e plastoméricos, borracha moída de pneus e ácido polifosfórico, incluindo também combinações destes aditivos. Os ligantes asfálticos, com classificação por grau de desempenho PG 76-XX, preparados com base em um CAP 50-70 com classificação PG 64-22, foram previamente envelhecidos a curto prazo na estufa RTFO e posteriormente submetidos ao envelhecimento foto-oxidativo em uma estufa UV sob dois níveis de radiação, 0,68 W/m² e 1,00 W/m², por um período de 240 h. Para efeitos de comparação dos resultados, as mesmas amostras foram submetidas ao envelhecimento termo-oxidativo na estufa PAV. As amostras virgens e envelhecidas a curto prazo foram caracterizadas por meio de ensaios empíricos. Os resíduos obtidos nos envelhecimentos foram submetidos a ensaios no reômetro de cisalhamento dinâmico (DSR). Propriedades reológicas dos ligantes asfálticos foram analisadas por meio de curvas-mestre e do ensaio de fadiga LAS. Algumas amostras foram caracterizadas quimicamente por meio de espectroscopia no infravermelho (FTIR), cromatografia por permeação em gel (GPC) e do fracionamento SARA. Para a maioria das amostras os procedimentos PAV e UV a 0,68 W/m² apresentam certa equivalência, em termos da capacidade de alterar as propriedades reológicas analisadas. O ligante asfáltico que mostrou ser menos sensível ao envelhecimento PAV foi o CAP+SBR, o que demonstrou ser menos sensível ao envelhecimento UV a 0,68 W/m² foi o CAP+EVA, e o que demonstrou menor sensibilidade ao envelhecimento UV a 1,00 W/m² foi o CAP+SBS. O CAP+SBS+PPA foi a amostra que apresentou maior sensibilidade ao envelhecimento PAV e UV a 1,00 W/m². / Aging of the asphalt binders has a great influence on the mechanical properties of asphalt mixtures. The current specifications establish limits for some indexes or aging parameters in an attempt to avoid the excessive hardening of the asphalt binder; however, they do not take into account the effects of ultraviolet (UV) irradiation. The objective of this study is to analyze the impact of thermo-oxidative and UV aging methods on the rheological properties of a base asphalt cement (AC) and 11 formulations prepared with additives, i. e., elastomeric and plastomeric polymers, ground tire rubber and polyphosphoric acid. Combinations these additives were also included in the study. The modified asphalt binders are graded as PG-76 XX in the Superpave specification, whereas the 50-70 base AC is graded as PG 64-22 in the same specification. The materials were first aged in the rolling thin-film oven (RTFO), and then submitted to photo-oxidative aging in an UV oven at two irradiation levels (0.68 W/m² and 1.00 W/m²) for 240 h. For comparison purposes, these formulations were also subjected to thermo-oxidative aging in the pressurized aging vessel (PAV). The unaged and short-term aged samples were characterized by means of empirical tests. The residues obtained in the RTFOT, PAV e UV aging methods were tested in the dynamic shear rheometer (DSR). The rheological properties of asphalt binders were analyzed by means of master curves and the linear amplitude sweep (LAS) fatigue test. Some samples were chemically characterized by the Fourier transform infrared spectroscopy (FTIR), the gel permeation chromatography (GPC) and the SARA fractionation techniques. The PAV and the UV procedures at 0.68 W/m² show some similarities for many formulations in terms of the ability to change their rheological properties. The AC+SBR was found to be less sensitive to PAV aging than the other studied binders, whereas the AC+EVA was the less sensitive material to UV aging at 0.68 W/m² and the AC+SBS showed the lowest sensitivity to UV aging at 1.00 W/m². The AC+SBS+PPA was the most sensitive formulation to PAV and UV aging at 1.00 W/m².

Background: A mouse model of combined UVA/riboflavin irradiation to eliminate stromal cells and other antigen-presenting cells in the cornea provides the basis for a probably low risk of corneal transplantation. Methods: After abrasion of the epithelium, the central corneas of mouse eyes were treated with UVA/riboflavin in vitro. Histological studies of hematoxylin-eosin and immunohistochemical staining with caspase 3 were performed. Dissected mouse corneas were analyzed by Western blot. Results: Apoptotic cells were shown on the central corneal stroma; a cell-free zone was displayed in the cornea. Numbers of dead cells increased according to cultivation time. However, the endothelium survived due to the adjustment of the irradiation dose. Conclusions: A cell-free zone in the stroma of the mouse cornea was produced by UVA/riboflavin irradiation in vitro. The technique makes possible to prevent or reduce immunological reactions and the risk of graft rejection by pretreatment of the donor cornea, ultimately prolonging graft survival. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

O envelhecimento dos ligantes asfálticos possui uma grande influência sobre as propriedades mecânicas das misturas asfálticas. As especificações atuais limitam determinados índices ou parâmetros de envelhecimento, visando contornar o endurecimento excessivo do ligante asfáltico, porém, não levam em conta o efeito da radiação ultravioleta (UV). O objetivo deste trabalho é avaliar o efeito dos envelhecimentos termo-oxidativo e foto-oxidativo sobre as propriedades reológicas de um CAP puro e 11 ligantes asfálticos modificados, incluindo polímeros elastoméricos e plastoméricos, borracha moída de pneus e ácido polifosfórico, incluindo também combinações destes aditivos. Os ligantes asfálticos, com classificação por grau de desempenho PG 76-XX, preparados com base em um CAP 50-70 com classificação PG 64-22, foram previamente envelhecidos a curto prazo na estufa RTFO e posteriormente submetidos ao envelhecimento foto-oxidativo em uma estufa UV sob dois níveis de radiação, 0,68 W/m² e 1,00 W/m², por um período de 240 h. Para efeitos de comparação dos resultados, as mesmas amostras foram submetidas ao envelhecimento termo-oxidativo na estufa PAV. As amostras virgens e envelhecidas a curto prazo foram caracterizadas por meio de ensaios empíricos. Os resíduos obtidos nos envelhecimentos foram submetidos a ensaios no reômetro de cisalhamento dinâmico (DSR). Propriedades reológicas dos ligantes asfálticos foram analisadas por meio de curvas-mestre e do ensaio de fadiga LAS. Algumas amostras foram caracterizadas quimicamente por meio de espectroscopia no infravermelho (FTIR), cromatografia por permeação em gel (GPC) e do fracionamento SARA. Para a maioria das amostras os procedimentos PAV e UV a 0,68 W/m² apresentam certa equivalência, em termos da capacidade de alterar as propriedades reológicas analisadas. O ligante asfáltico que mostrou ser menos sensível ao envelhecimento PAV foi o CAP+SBR, o que demonstrou ser menos sensível ao envelhecimento UV a 0,68 W/m² foi o CAP+EVA, e o que demonstrou menor sensibilidade ao envelhecimento UV a 1,00 W/m² foi o CAP+SBS. O CAP+SBS+PPA foi a amostra que apresentou maior sensibilidade ao envelhecimento PAV e UV a 1,00 W/m². / Aging of the asphalt binders has a great influence on the mechanical properties of asphalt mixtures. The current specifications establish limits for some indexes or aging parameters in an attempt to avoid the excessive hardening of the asphalt binder; however, they do not take into account the effects of ultraviolet (UV) irradiation. The objective of this study is to analyze the impact of thermo-oxidative and UV aging methods on the rheological properties of a base asphalt cement (AC) and 11 formulations prepared with additives, i. e., elastomeric and plastomeric polymers, ground tire rubber and polyphosphoric acid. Combinations these additives were also included in the study. The modified asphalt binders are graded as PG-76 XX in the Superpave specification, whereas the 50-70 base AC is graded as PG 64-22 in the same specification. The materials were first aged in the rolling thin-film oven (RTFO), and then submitted to photo-oxidative aging in an UV oven at two irradiation levels (0.68 W/m² and 1.00 W/m²) for 240 h. For comparison purposes, these formulations were also subjected to thermo-oxidative aging in the pressurized aging vessel (PAV). The unaged and short-term aged samples were characterized by means of empirical tests. The residues obtained in the RTFOT, PAV e UV aging methods were tested in the dynamic shear rheometer (DSR). The rheological properties of asphalt binders were analyzed by means of master curves and the linear amplitude sweep (LAS) fatigue test. Some samples were chemically characterized by the Fourier transform infrared spectroscopy (FTIR), the gel permeation chromatography (GPC) and the SARA fractionation techniques. The PAV and the UV procedures at 0.68 W/m² show some similarities for many formulations in terms of the ability to change their rheological properties. The AC+SBR was found to be less sensitive to PAV aging than the other studied binders, whereas the AC+EVA was the less sensitive material to UV aging at 0.68 W/m² and the AC+SBS showed the lowest sensitivity to UV aging at 1.00 W/m². The AC+SBS+PPA was the most sensitive formulation to PAV and UV aging at 1.00 W/m².

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The objectives of this work were divided in two experiments phases. In the first phase, it was studied the presence of trans-resveratrol in temperate climate fruits and the variation of their concentration in these fruits during storage period, as well the amount of total phenols and total anthocyanins. It was evaluated total phenols, total anthocyanins and trans-resveratrol, before and after cold storage and under controlled atmosphere; and after five days shelf-life at 20°C in Bruno kiwifruit; Araza and Yvahe strawberries; Black mulberry; Galaxi , Gala and Fuji apples; persimmon Fuyu ; Bleugem blueberry, Isabel , Merlot and Niagara Pink grapes. It was detected trans-resveratrol in natura in flesh Bruno kiwifruit; Araza and Yvahe strawberries; Black mulberry. In other fruits, it was detected transresveratrol in natura in the skin. The cold storage stimulated trans-resveratrol synthesis in Bleugem blueberry, and Isabel and Merlot grapes. In the second phase, it was evaluated the induction of trans-resveratrol synthesis and its possible action as phytoalexin in Gala and Fuji apples stored in controlled atmosphere were evaluated. Experiments were with the application of abiotic elicitors: ultraviolet irradiation, phosphite and acibenzolar-S-methyl, applied before controlled atmosphere storage, and intermittent ozone applied during storage of to Gala and Fuji apples. Rot was controlled in another experiment with the same elicitors. In fruit bark it was analyzed trans-resveratrol; total phenols and total anthocyanins, as well as the diameter of injury after inoculation of Penicillium sp. The abiotic elicitors were induced in 'Fuji' apples trans-resveratrol synthesis in the following sequence: Acibenzolar-Smethyl > phosphite ³ UV-C irradiation ³ ozone, but it wasn t effective on 'Gala' apple. There was no correlation between the syntheses of trans-resveratrol and rotting control, with exception of phosphite was control of rot in 'Gala'. / Os objetivos deste trabalho foram alcançados em duas etapas. Na primeira etapa, o objetivo foi avaliar a presença de trans-resveratrol em frutos de clima temperado e a sua variação de concentração nesses frutos durante o período de armazenamento, assim como a evolução dos polifenóis totais e antocianinas totais. Avaliou-se o conteúdo de polifenóis totais, antocianinas totais e trans-resveratrol antes e após o armazenamento refrigerado e em atmosfera controlada, e após cinco dias de exposição a 20°C em kiwi Bruno , morangos Araza e Yvahe , amora (Morus nigra), maçãs Galaxi , Gala e Fuji , caqui Fuyu , mirtilo Bleugem , uvas Isabel , Merlot e Niágara Rosada . Detectou-se o trans-resveratrol in natura em polpa de kiwi Bruno , morangos Araza e Yvahe e amora Preta . Nos demais fruto, detectou-se in natura trans-resveratrol na casca. O armazenamento refrigerado estimulou a síntese de trans-resveratrol em mirtilo Bleugem , uvas Isabel e Merlot . Na segunda etapa, o objetivo foi avaliar a indução da síntese de trans-resveratrol e sua possível ação como fitoalexina em maçãs Gala e Fuji , armazenadas em atmosfera controlada. Realizaram-se experimentos com aplicação de elicitores abióticos: irradiação ultravioleta, fosfito e acibenzolar-S-metil, aplicados antes do armazenamento em atmosfera controlada, e ozônio aplicado de forma intermitente durante o armazenamento de maçãs Gala e Fuji . Realizou-se o controle de podridão em outro experimento com os mesmos elicitores. Na casca dos frutos analisaram-se trans-resveratrol, polifenóis totais e antocianinas totais, e o diâmetro de lesão após inoculação por Penicillium sp. Os elicitores abióticos induziram a síntese de trans-resveratrol em maçã Fuji na seguinte ordem: Acibenzolar-S-metil > Fosfito ³ irradiação UV-C ³ ozônio, mas não apresentaram efeito em maçãs Gala , durante o armazenamento em atmosfera controlada. Os elicitores abióticos não apresentaram efeito no controle de podridão, com exceção do fosfito que controlaram a podridão em maçã Gala . Não houve correlação entre a síntese de trans-resveratrol e o controle de podridão.

Les expériences de laboratoire ont montré que la photo-irradiation ultraviolette d'analogues de glaces astrophysiques suivie de leur réchauffement à température ambiante mène à la formation de résidus organiques réfractaires. Ces résidus, solubles dans l'eau, consistent en un riche mélange de composés organiques incluant entre autres des acides aminés, molécules potentiellement importantes pour la chimie prébiotique. Ces résidus sont considérés comme des analogues de la matière organique réfractaire que l'on pense être synthétisée sur les grains de poussière dans les nuages moléculaires et/ou dans les disques protoplanétaires, produit de l'évolution des glaces, et qui pourra être accrétée plus tard en comètes ou en astéroïdes et finalement délivrée sur la Terre primitive. Ainsi, l'étude de ces analogues, produits dans des conditions astrophysiques pertinentes, représente un outil efficace pour explorer les processus à l'origine de la formation des molécules organiques complexes dans le Système Solaire et en particulier la possible introduction d'excès énantiomériques dans les molécules chirales.Ce travail de thèse est consacré à l'étude de ces résidus organiques, leur caractérisation et les applications astrophysiques de ces résultats. Nous avons utilisé différentes techniques d'analyse comme la chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC MS, classique et multidimensionnelle), la spectrométrie de masse par résonnance cyclotronique ionique à transformée de Fourier (FT ICR MS) ou encore la spectroscopie infrarouge. Nous avons mesuré les excès énantiomériques induits dans cinq acides aminés par irradiation de nos analogues avec de la lumière UV polarisée circulairement (UV CPL) et insérons nos résultats dans le cadre d'un scénario astrophysique cohérent pour expliquer l'origine des excès énantiomériques observés dans les acides aminés météoritiques. Nous avons étudié le contenu en acides aminés de la météorite de "Paris" et montré des similarités avec la distribution en acides aminés de nos résidus organiques. Nous avons également produit des analogues plus réalistes de grains interstellaires en incluant une surface silicatée, afin de tester l’effet potentiel de cette surface sur la formation et la nature des résidus organiques. Enfin, nous effectuons une discussion générale à propos de la pertinence de ces résultats dans le contexte astrophysique et soulignons le possible lien entre astrochimie et chimie prébiotique. / Laboratory experiments have shown that ultraviolet photo-irradiation of astrophysical ice analogs and their following warm-up until room temperature lead to the formation of refractory organic residues. These residues consist of rich mixtures of organic compounds, including amino acids, which have a potential importance for prebiotic chemistry. They are considered as analogs of the organic refractory materials that are thought to be synthesized on dust grains in molecular clouds and/or in protoplanetary disks, as a product of ices evolution, and that could be later accreted into comets and asteroids and eventually be delivered to the early Earth. Hence, the study of these analogs, produced under astrophysically relevant conditions, represents a valid tool to investigate the processes at work for the origin of complex organic molecules in the Solar System and in particular the possible introduction of enantiomeric excesses in chiral molecules. This PhD work is devoted to the study of these laboratory organic residues, their characterization and the astrophysical applications of the results. We used different analytical techniques such as gas chromatography mass spectrometry (GC MS, classical and multidimensional), Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), and infrared spectroscopy. We measured the enantiomeric excesses induced in five chiral amino acids by UV circularly polarized light (UV CPL) irradiation of our analogs and insert our result in a coherent astrophysical scenario for the origin of the enantiomeric excesses observed in meteoritic amino acids. We studied the amino acid content of the Paris meteorite and evidence some similarities with the distribution of the amino acids in our organic residues. We also produced more realistic analogs of interstellar grains, including a silicate surface, to test the potential effect of such a surface on the formation and nature of organic residues. Finally, we discuss the significance of these results in the astrophysical context and the possible relationship between astrochemistry and prebiotic chemistry.

Background: A mouse model of combined UVA/riboflavin irradiation to eliminate stromal cells and other antigen-presenting cells in the cornea provides the basis for a probably low risk of corneal transplantation. Methods: After abrasion of the epithelium, the central corneas of mouse eyes were treated with UVA/riboflavin in vitro. Histological studies of hematoxylin-eosin and immunohistochemical staining with caspase 3 were performed. Dissected mouse corneas were analyzed by Western blot. Results: Apoptotic cells were shown on the central corneal stroma; a cell-free zone was displayed in the cornea. Numbers of dead cells increased according to cultivation time. However, the endothelium survived due to the adjustment of the irradiation dose. Conclusions: A cell-free zone in the stroma of the mouse cornea was produced by UVA/riboflavin irradiation in vitro. The technique makes possible to prevent or reduce immunological reactions and the risk of graft rejection by pretreatment of the donor cornea, ultimately prolonging graft survival. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.