La composition chimique de la résine sandaraque et de son composant principal l’acide communique a été étudiée par chromatographie en phase gazeuse – spectrométrie de masse (GC-MS), MALDI-TOF (désorption-ionisation laser assistée par matrice - temps de vol), ESI (ionisation par électronébuliseur) - Orbitrap, FTIR/ATR (spectroscopie infrarouge à transformée de Fourier/réflectance totale atténuée), spectroscopie de RMN (résonance magnétique nucléaire) à l'état solide et liquide. Six composés avec des squelettes labdane et pimarane ont été identifiés dans la résine commerciale. Les spectres de masse obtenus ont été interprétés et le comportement en spectrométrie de masse de ces diterpénoïdes dans les conditions de l’impact électronique a été décrit. L'analyse quantitative par la méthode de l'étalon interne a révélé que les diterpénoïdes identifiés ne représentaient que 10 à 30% de l'échantillon analysé. La complexité de la fraction réticulée de la résine commerciale sandaraque est bien reflétée par les spectres de masse MALDI-TOF et ESI-Orbitrap. En conséquence, les spectres de masse de MALDI-TOF comprenaient trois clusters de pics dans la gamme m/z de 300-900, et ceux d’ESI-Orbitrap contenaient cinq clusters de pics dans la gamme m/z de 300-1100. Les pics dans les clusters correspondent aux dérivés oxygénés des diterpénoïdes. Les résultats obtenus à partir des expériences RMN par IRCP (Inversion Recovery Cross-Polarization) ont révélé le caractère rigide des échantillons de la résine sandaraque analysés et justifiaient l'hypothèse que le reste de l'échantillon, qui ne pouvait être quantifié par la méthode de l'étalon interne, aurait un caractère polymère. / The chemical composition of sandarac resin and its principal component communic acid was investigated by gas chromatography-mass spectrometry (GC-MS), MALDI-TOF (Matrix Assisted Laser Desorption Ionization - Time of Flight), ESI (Electrospray ionization)-Orbitrap, FTIR/ATR (Fourier transform infrared spectroscopy/Attenuated total reflectance), liquid- and solid state NMR (Nuclear magnetic resonance) spectroscopy. Six compounds with labdane and pimarane skeletons were identified in the commercial resin. The obtained mass spectra were interpreted and the mass spectrometric behaviour of these diterpenoids under EI conditions was described. Quantitative analysis by the method of internal standard revealed that identified diterpenoids represent only 10–30% of the analysed sample. The complexity of the reticulated fraction of the commercial sandarac resin was well reflected by the MALDI-TOF and ESI-Orbitrap mass spectra. As a result, MALDI-TOF mass spectra comprised three clusters of peaks in the m/z range of 300–900, and for the ESI-Orbitrap mass spectra contained five clusters of peaks in the m/z range of 300–1100. The peaks in the clusters corresponded to the oxygenated derivatives of the diterpenoids. The results obtained from the IRCP (Inversion Recovery Cross-Polarization) experiments revealed the rigid character of the sandarac resin samples analyzed and justified the hypothesis that the rest of the sample, which could not be quantified by the method of internal standard, would have a polymeric nature.

This diploma thesis deals with the issue of the degree of damage done to the vehicle‘s body paint varnish by bird droppings; with respect to the influence of the pollution time on the thickness of the layer of lacquer. The first chapter deals with the importance of varnish and other layers of body protection, types of body varnish damage, painting technology, lacquer defects, bird droppings and its effects on the varnish of the vehicle‘s body. The second chapter is dedicated exclusively to the description, planning and measurement of the coated layers on the vehicle’s body contaminated with bird feces.

This work consider with monitoring components of komplex permittivity at frequency section of electro-insulation material in process of wetting by dielectric relaxation spectroscopy.

This master's thesis focuses on composite systems based on varnish combined with different filler ratios of micronized mica. The aim is to analyse impact of the filler on dielectric properties of the varnish, i.e. relative permittivity and loss factor as functions of frequency as well as charging and discharging currents as functions of time. Dielectric mixture formulas are applied on relative permittivity values. Calculated and measured values are compared.

Karies muss nicht zwangsweise durch invasives Bohren und anschließendes Restaurieren des Zahns behandelt werden. Beginnenden Entmineralisierungen der Zahnhartsubstanz kann heutzutage in verschiedener Weise substanz¬schonend entgegengewirkt werden. Ziel der vorliegenden In-vitro-Studie war es das Remineralisationspotential diverser neuartiger, zahnärztlicher Fluoridlacke auf initialen Schmelzläsionen zu untersuchen. Hierfür wurden aus gesunden, bovinen Zähnen Probenblöcke (n= 276) hergestellt und zufällig in zwölf Versuchsgruppen eingeteilt. Nach dem Erzeugen einer künstlichen Schmelzkaries durch 21-tägiges Lagern der Proben in einer Demineralisationslösung, wurden den Herstellerangaben folgend verschiedene Fluoridlacke appliziert: a) Natriumfluorid (Duraphat, 22.600 ppm F), b) Natriumfluorid in Kombination mit Kalziumfluorid (Biophat, 45.200 ppm F-), c) Natriumfluorid in Kombination mit Trikalziumphosphat (Clinpro White Varnish Mint, 22.600 ppm F-), d) Natriumfluorid in Kombination mit Casein Phospho¬peptid - amorphem Kalziumphosphat (MI Varnish, 22.600 ppm F-) und e) Silber-Diamin-Fluorid (Cariestop 30%, 35.400 ppm F-). Zwei Gruppen erfuhren zur Kontrolle keine Behandlung mit einem Lack. Um eine realitätsgetreue Umgebungssituation ähnlich der Mundhöhle zu simulieren, lagerten die Proben 28 Tage in einem pH-Wechselbad (6x120 Min Demineralisation/Tag). Zweimal täglich sorgten in verdünnter fluoridhaltiger Zahnpasta (14500 ppm F-, bzw. 5000 ppm F- Zahnpasta) getränkte Bürsten für die Reinigung der Schmelzoberflächen für je 10 Sekunden. Alle Proben wurden nach der 21-tägigen Demineralisationsphase, sowie nach der Lackbehandlung fotografiert und hinsichtlich der Läsionstiefe und des Mineralverlustes analysiert. Hierfür wurde die Technik der Transversalen Mikroradiographie zur Hilfe genommen. Alle angewandten Fluoridlacke führten zu einem signifikant geringeren Mineralverlust, sowie einem geringeren Fortschreiten der Läsionstiefe nach pH-cycling im Vergleich zur Negativkontrolle N1/N5 ohne Lackbehandlung (p≤0,043; außer NaF5, CPP5, SDF5). Unter den gewählten Versuchsbedingungen wurde jedoch alleinig durch die Behandlung mit Natriumfluorid in Kombination mit Kalziumfluorid (CaF1/CaF5) eine Remineralisation der künstlichen Schmelzkaries erzielt. Ein signifikanter Unterschied zwischen der Verwendung von 5.000 ppm F- Zahnpasta zu 1.450 ppm F- Zahn¬pasta hin¬sichtlich einer Verbesserung der Remineralisationsparameter konnte nur bei den Negativ¬kontrollgruppen festgestellt werden. Hochfluoridhaltige Zahnpasta in Kombination mit zahnärztlichen Lacken erzeugte hingegen keinen zusätzlichen Effekt im Vergleich zu normalfluoridhaltiger Zahnpasta in Kombination mit zahnärztlichen Lacken.:Inhaltsverzeichnis Abkürzungsverzeichnis IV 1 Einleitung 1 2 Literaturübersicht 3 2.1 Zahnschmelz 3 2.1.1 Aufbau und Eigenschaften 3 2.1.2 Rinderzahnschmelz als Ersatzmaterial für In-vitro-Versuche 6 2.2 Karies 7 2.2.1 Grundzüge der Kariesätiologie 8 2.2.2 Demineralisation und Remineralisation 9 2.3 Fluoride 12 2.3.1 Wirkungsweisen 12 2.3.2 Fluoridierungsmaßnahmen 13 3 Zielsetzung 21 4 Material und Methoden 23 4.1 Stichprobenumfangsplanung 23 4.2 Probenherstellung 23 4.3 Erzeugen einer künstlichen Kariesläsion 26 4.4 Erstellen von Dünnschliffen 28 4.5 Kolorimetrische Analyse 30 4.5.1 Fotoaufnahmen der Probe 30 4.5.2 Farbanalyse 32 4.5.3 Gruppeneinteilung 32 4.6 Probenbehandlung 33 4.7 pH-cycling 35 4.8 Analysen 37 4.8.1 Transversale Mikroradiographische Analyse 37 4.8.2 Kolorimetrische Analyse 38 4.9 Digitalisierung und Auswertung der Aufnahmen 38 4.9.1 Statistische Auswertung 40 5 Ergebnisse 42 5.1 Validierung des Stichprobenumfangs 42 5.2 TMR-Analyse - Ergebnisse des Mineralgehalts 43 5.2.1 ΔZDT 43 5.2.2 ΔZST 45 5.3 TMR-Analyse - Ergebnisse der Läsionstiefe 47 5.3.1 LDDT 47 5.3.2 LDST 48 5.4 Kolorimetrische Analyse 49 5.5 Graphische Auswertung des Läsionsverlaufs 51 6 Diskussion 54 6.1 Diskussion des In-vitro-Modells 54 6.2 Diskussion der Ergebnisse 56 7 Zusammenfassung 64 8 Summary 66 9 Verzeichnisse I 9.1 Abbildungsverzeichnis I 9.2 Tabellenverzeichnis II 9.3 Diagrammverzeichnis II 9.4 Literaturverzeichnis III 10 Erklärung über die eigenständige Abfassung der Arbeit IX 11 Lebenslauf X 12 Danksagung XI / The treatment of caries does not necessarily require invasive measures. Initial demineralization of the tooth substance can also be counteracted in various ways without sacrificing further substance losses. The aim of this study was to compare the caries preventive effect of different fluoride varnishes on sound enamel, as well as on artificial enamel caries-like lesions. For this purpose, bovine enamel specimens (n = 276) with one sound surface [ST] and one artificial caries lesion [DT] were prepared and randomly allocated to twelve groups. The interventions before pH-cycling were: application of a varnish containing NaF (Duraphat, 22.600 ppm F-, NaF1/NaF5), NaF plus calcium fluoride (Biophat, 45.200 ppm F-, CaF1/CaF5), NaF plus tricalcium phosphate (Clinpro White Varnish Mint, 22.600 ppm F-, TCP1/TCP5), NaF plus CPP-ACP (MI Varnish, 22.600 ppm F-, CPP1/CPP5) and silver diamine fluoride (Cariestop 30%, 35.400 ppm F-, SDF1/SDF5). One group got no intervention. During the pH-cycling (28 days, 6x120 min demineralization/day) the half of the specimens of every group were brushed (10 s; 2x/d) with either 1.450 ppm F- or 5.000 ppm F- dentifrice slurry. The differences in view of the mineral loss, lesion depth and the color gradient between the two states after initial demineralization and after pH-cycling were investigated by a transversal microradiograph and a colorimetric analysis. The treatments of all varnishes showed a significantly lower increase in mineral loss and lesion depth after pH-cycling in comparison to the negative control without an intervention (p ≤ 0.043; except NaF5, CPP5, SDF5). However under the conditions chosen, only NaF + CaF could remineralize artificial enamel caries-like lesions. A significant difference between the use of 5.000 ppm F- toothpaste and 1.450 ppm F- toothpaste in terms of an enhanced remineralization could only be observed in groups N1/N5. The applications of a varnish in combination with the highly fluoridated toothpaste did not result in a significant difference in comparison to a varnish in combination with normal fluoridated toothpaste.:Inhaltsverzeichnis Abkürzungsverzeichnis IV 1 Einleitung 1 2 Literaturübersicht 3 2.1 Zahnschmelz 3 2.1.1 Aufbau und Eigenschaften 3 2.1.2 Rinderzahnschmelz als Ersatzmaterial für In-vitro-Versuche 6 2.2 Karies 7 2.2.1 Grundzüge der Kariesätiologie 8 2.2.2 Demineralisation und Remineralisation 9 2.3 Fluoride 12 2.3.1 Wirkungsweisen 12 2.3.2 Fluoridierungsmaßnahmen 13 3 Zielsetzung 21 4 Material und Methoden 23 4.1 Stichprobenumfangsplanung 23 4.2 Probenherstellung 23 4.3 Erzeugen einer künstlichen Kariesläsion 26 4.4 Erstellen von Dünnschliffen 28 4.5 Kolorimetrische Analyse 30 4.5.1 Fotoaufnahmen der Probe 30 4.5.2 Farbanalyse 32 4.5.3 Gruppeneinteilung 32 4.6 Probenbehandlung 33 4.7 pH-cycling 35 4.8 Analysen 37 4.8.1 Transversale Mikroradiographische Analyse 37 4.8.2 Kolorimetrische Analyse 38 4.9 Digitalisierung und Auswertung der Aufnahmen 38 4.9.1 Statistische Auswertung 40 5 Ergebnisse 42 5.1 Validierung des Stichprobenumfangs 42 5.2 TMR-Analyse - Ergebnisse des Mineralgehalts 43 5.2.1 ΔZDT 43 5.2.2 ΔZST 45 5.3 TMR-Analyse - Ergebnisse der Läsionstiefe 47 5.3.1 LDDT 47 5.3.2 LDST 48 5.4 Kolorimetrische Analyse 49 5.5 Graphische Auswertung des Läsionsverlaufs 51 6 Diskussion 54 6.1 Diskussion des In-vitro-Modells 54 6.2 Diskussion der Ergebnisse 56 7 Zusammenfassung 64 8 Summary 66 9 Verzeichnisse I 9.1 Abbildungsverzeichnis I 9.2 Tabellenverzeichnis II 9.3 Diagrammverzeichnis II 9.4 Literaturverzeichnis III 10 Erklärung über die eigenständige Abfassung der Arbeit IX 11 Lebenslauf X 12 Danksagung XI

No description available.

Aim: The aim of this study was to investigate if there is a beneficial effect on the prevalence of white spot lesions (WSL) in the mandibular and maxillary teeth when the teeth in the maxilla are treated with fluoride varnish compared to a placebo group. The null hypothesis was that there is no difference between the test and placebo group in development of WSL. Material and Method: 182 patients from three clinics in Scania county (Sweden) undergoing treatment with fixed orthodontic appliances were selected to participate, in the end 149 patients were included in the study. The patients were divided into two groups, one receiving a varnish of 7700 ppm fluoride (Fluor Protector S, Ivoclar Vivadent AG, Schaan, Liechtenstein) and one a placebo varnish. Pre- and post-treatment photos were taken and WSL was graded according to Gorelick index by two independent observers.  Results: No significant difference could be seen between the test and placebo group, neither on surface nor individual level. The results were based on both t-test and percentual calculations.  Conclusion: The null hypothesis could be accepted since no significant difference could be seen between the test or placebo group. Due to the loss of a number of patients, mainly because of loss in the original study and new exclusion criteria set by the authors, the results may have been conflicted. More research is therefore needed to draw any conclusions. / Syfte: Syftet med studien var att undersöka om det finns en effekt på förekomsten av white spot lesions (WSL) hos under- och överkäkens tänder när tänderna i överkäken behandlas med fluoridvarnish. Nollhypotesen sattes till att det inte finns någon skillnad mellan test- och placebogruppen i prevalens av WSL. Material och metod: Patienter från tre olika kliniker i Skåne deltog i studien, 149 av 182 deltagare fullföljde studien. Patienterna delades in i två grupper, en som fick ett fluoridvarnish med 7700 ppm fluorid (Fluor Protector S, Ivoclar Vivadent AG, Schaan, Liechtenstein) och en med placebovarnish. Kliniska foton togs innan samt efter behandling med fast apparatur som graderades och bedömdes enligt Gorelick-skalan för WSL av två oberoende observatörer. Resultat: Det fanns ingen signifikant skillnad mellan testgruppen och placebogruppen varken på individ- eller ytnivå. Resultatet baserades på både t-test och procentberäkningar. Slutsats: Nollhypotesen accepterades då ingen signifikant skillnad fanns mellan test- och placebogrupp. På grund av bortfall av patienter, både i originalstudien men även med anledning av exklusionskriterier satta för denna studie, kan resultatet ha påverkats. Mer forskning behövs därför för att dra några slutsatser.

Tucked within Pomona College’s campus in Claremont, California, sits Frary Hall, the home of Mexican muralist Jose Clemente Orozco’s first work in the United States. The mural, titled Prometheus (1930), has been subjected to many instances of vandalism over the years. Thus, in 1980, a protective coating was applied. Today, the coating, a highly-reflective varnish, has been noted as a hindrance of the fresco’s original matte surface. Using case studies and art historical analysis, this thesis examines the importance of the mural within the history of Mexican muralism and the pros and cons of removing the protective coating. In addition, this research looks at the potential of art conservation as a means of reactivating the mural and promoting discussions across campus about the preservation of this cultural landmark. The thesis is culminated by a detailed proposal for the continued conservation of the mural, using Prometheus as a starting point for further discussions about aesthetics and ethics within the discourses of art history, art conservation and art restoration.

O objetivo do presente estudo foi avaliar in situ o efeito da associação do verniz fluoretado ao laser de Er:YAG e ao laser Nd:YAG na permeabilidade da dentina radicular erodida. Quarenta e oito fragmentos de dentina radicular bovina, com dimensões 2x2x2 mm, foram submetidos a um desafio erosivo inicial com ácido cítrico (0,3%, pH 3,2), por duas horas, sob agitação e armazenados em saliva artificial por vinte e quatro horas. Posteriormente, os espécimes foram divididos em relação aos tratamentos: verniz fluoretado e não fluoretado e subdivididos conforme a irradiação: laser de Er:YAG (100mJ, 3Hz), laser de Nd:YAG (70mJ, 15 Hz) e não irradiado. Após um período de lead in (2 dias), os voluntários (n=8) utilizaram dispositivos palatinos contendo três espécimes que foram submetidos a desafios erosivos ex vivo, quatro vezes ao dia, com ácido cítrico (0,3%, pH 3,2), durante 90s, por cinco dias. Na primeira fase do experimento, metade dos voluntários utilizou dispositivos contendo fragmentos tratados com verniz fluoretado, verniz fluoretado + laser de Er:YAG e verniz fluoretado + laser de Nd:YAG. A outra metade utilizou verniz não fluoretado, verniz não fluoretado + laser de Er:YAG e verniz não fluoretado + laser de Nd:YAG. Depois de um período de wash-out (15 dias), os voluntários foram cruzados quanto aos tratamentos, caracterizando um experimento cross-over 2x2. Ao final de cada fase experimental, a permeabilidade dentinária foi avaliada. A ANOVA dois critérios e o teste complementar de Duncan revelaram uma diferença significativa entre os espécimes tratados com o verniz fluoretado (p=0,005), verniz fluoretado + laser de Er:YAG (p=0,014) e verniz fluoretado + laser de Nd:YAG (p=0,025), em comparação aos tratados com verniz não fluoretado. Observou-se que, independentemente da associação aos lasers (Er:YAG ou Nd:YAG), o verniz fluoretado foi capaz de promover a redução da permeabilidade da dentina radicular erodida. Não se observou efeito adicional com a associação dos tratamentos. / The present study aimed to evaluate in situ the effect of associating the fluoride varnish to Er:YAG or Nd:YAG laser at permeability of eroded root dentin. Forty-eight specimens of bovine root dentin (2x2x2mm) were subjected to initial erosive challenge with citric acid (0.3%, pH 3.2), for 2 hours under agitation and stored at artificial saliva, at 37&deg C, for 24 hours, followed by a remineralization period in artificial saliva. After that, specimens were divided according to the treatment: fluoride varnish and non-flouride varnish, and subdivided according to the irradiation: Er:YAG laser (100mJ, 3Hz), Nd:YAG laser (70mJ, 15Hz) and non-irradiated. After a lead-in period (2 days), 8 volunteers (n=8) wore a palatal device containing 3 specimens that was subjected to erosive challenges ex vivo, four times a day with citric acid (0.3%, pH3.2), for 90s, during 5 days. At the first experimental phase, half of volunteers wore devices containing specimens treated with fluoride varnish, fluoride varnish + Er:YAG laser and fluoride varnish + Nd:YAG laser, and the other half wore the specimens treated with non-fluoride varnish, non-fluoride varnish + Er:YAG laser and non-flouride varnish + Nd:YAG laser. After a wash-out period (15 days), volunteers were crossed to different treatment, characterizing a 2x2 cross-over experiment. At the end of each experimental phase, the dentinal permeability was evaluated. Two-way ANOVA and Duncans test revealed a significant difference between specimens treated with fluoride varnish (p=0,005), fluoride varnish + Er:YAG laser (p=0,014) and fluoride varnish + Nd:YAG (p=0,025) compared to specimens treated with no-fluoride varnish. It was observed that regardless of association to laser (Er:YAG or Nd:YAG), fluoride varnish was able to promote, in situ, the reduction of permeability of eroded root dentin, but no additional effect was observed when the treatments were associated.

O objetivo do presente estudo foi avaliar in situ o efeito da associação do verniz fluoretado ao laser de Er:YAG e ao laser Nd:YAG na permeabilidade da dentina radicular erodida. Quarenta e oito fragmentos de dentina radicular bovina, com dimensões 2x2x2 mm, foram submetidos a um desafio erosivo inicial com ácido cítrico (0,3%, pH 3,2), por duas horas, sob agitação e armazenados em saliva artificial por vinte e quatro horas. Posteriormente, os espécimes foram divididos em relação aos tratamentos: verniz fluoretado e não fluoretado e subdivididos conforme a irradiação: laser de Er:YAG (100mJ, 3Hz), laser de Nd:YAG (70mJ, 15 Hz) e não irradiado. Após um período de lead in (2 dias), os voluntários (n=8) utilizaram dispositivos palatinos contendo três espécimes que foram submetidos a desafios erosivos ex vivo, quatro vezes ao dia, com ácido cítrico (0,3%, pH 3,2), durante 90s, por cinco dias. Na primeira fase do experimento, metade dos voluntários utilizou dispositivos contendo fragmentos tratados com verniz fluoretado, verniz fluoretado + laser de Er:YAG e verniz fluoretado + laser de Nd:YAG. A outra metade utilizou verniz não fluoretado, verniz não fluoretado + laser de Er:YAG e verniz não fluoretado + laser de Nd:YAG. Depois de um período de wash-out (15 dias), os voluntários foram cruzados quanto aos tratamentos, caracterizando um experimento cross-over 2x2. Ao final de cada fase experimental, a permeabilidade dentinária foi avaliada. A ANOVA dois critérios e o teste complementar de Duncan revelaram uma diferença significativa entre os espécimes tratados com o verniz fluoretado (p=0,005), verniz fluoretado + laser de Er:YAG (p=0,014) e verniz fluoretado + laser de Nd:YAG (p=0,025), em comparação aos tratados com verniz não fluoretado. Observou-se que, independentemente da associação aos lasers (Er:YAG ou Nd:YAG), o verniz fluoretado foi capaz de promover a redução da permeabilidade da dentina radicular erodida. Não se observou efeito adicional com a associação dos tratamentos. / The present study aimed to evaluate in situ the effect of associating the fluoride varnish to Er:YAG or Nd:YAG laser at permeability of eroded root dentin. Forty-eight specimens of bovine root dentin (2x2x2mm) were subjected to initial erosive challenge with citric acid (0.3%, pH 3.2), for 2 hours under agitation and stored at artificial saliva, at 37&deg C, for 24 hours, followed by a remineralization period in artificial saliva. After that, specimens were divided according to the treatment: fluoride varnish and non-flouride varnish, and subdivided according to the irradiation: Er:YAG laser (100mJ, 3Hz), Nd:YAG laser (70mJ, 15Hz) and non-irradiated. After a lead-in period (2 days), 8 volunteers (n=8) wore a palatal device containing 3 specimens that was subjected to erosive challenges ex vivo, four times a day with citric acid (0.3%, pH3.2), for 90s, during 5 days. At the first experimental phase, half of volunteers wore devices containing specimens treated with fluoride varnish, fluoride varnish + Er:YAG laser and fluoride varnish + Nd:YAG laser, and the other half wore the specimens treated with non-fluoride varnish, non-fluoride varnish + Er:YAG laser and non-flouride varnish + Nd:YAG laser. After a wash-out period (15 days), volunteers were crossed to different treatment, characterizing a 2x2 cross-over experiment. At the end of each experimental phase, the dentinal permeability was evaluated. Two-way ANOVA and Duncans test revealed a significant difference between specimens treated with fluoride varnish (p=0,005), fluoride varnish + Er:YAG laser (p=0,014) and fluoride varnish + Nd:YAG (p=0,025) compared to specimens treated with no-fluoride varnish. It was observed that regardless of association to laser (Er:YAG or Nd:YAG), fluoride varnish was able to promote, in situ, the reduction of permeability of eroded root dentin, but no additional effect was observed when the treatments were associated.