Degradation of the resin-dentin bonds after simulated and inhibited cariogenic challenge in an in situ model

The aim of this study was to evaluate the resindentin bonds of two simplified etch-and-rinse adhesive after simulated cariogenic and inhibited cariogenic challenge in situ. Dental cavities (4 mm wide, 4 mm long, and 1.5 mm deep) were prepared in 60 bovine teeth with enamel margins. Restorations were bonded with either adhesive Adper Single Bond 2 (3MESPE) or Optibond Solo Plus (Kerr). Forty restorations were included in an intra-oral palatal appliance that was used for 10 adult volunteers while the remaining 20 dental blocks were not submitted to any cariogenic challenge [NC group] and tested immediately. For the simulated cariogenic challenge [C+DA], each volunteer dropped 20% sucrose solution onto all blocks four times a day during 14 days and distilled water twice a day. In the inhibited cariogenic challenge group [C + FA], the same procedure was done, but slurry of fluoride dentifrice (1.100 ppm) was applied instead of water. The restored bovine blocks were sectioned to obtain a slice for cross-sectional Vickers microhardness evaluation and resindentin bonded sticks (0.8 mm2) for resindentin microtensile evaluation. Data were evaluated by two-way ANOVA and Tukey's tests (a = 0.05). Statistically lower microhardness values and degradation of the resindentin bonds were only found in the C + DW group for both adhesives. The in situ model seems to be a suitable short-term methodology to investigate the degradation of the resindentin bonds under a more realistic condition. (c) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 100B: 14661471, 2012.

Six-month evaluation of a resin/dentin interface created by methacrylate and silorane-based materials

Objectives: This study aimed to compare the micro-tensile bond strength of methacrylate resin systems to a silorane-based restorative system on dentin after 24 hours and six months water storage. Material and Methods: The restorative systems Adper Single Bond 2/Filtek Z350 (ASB), Clearfil SE Bond/Z350 (CF), Adper SE Plus/Z350 (ASEP) and P90 Adhesive System/Filtek P90 (P90) were applied on flat dentin surfaces of 20 third molars (n=5). The restored teeth were sectioned perpendicularly to the bonding interface to obtain sticks (0.8 mm2) to be tested after 24 hours (24 h) and 6 months (6 m) of water storage, in a universal testing machine at 0.5 mm/min. The data was analyzed via two-way Analysis of Variance/Bonferroni post hoc tests at 5% global significance. Results: Overall outcomes did not indicate a statistical difference for the resin systems (p=0.26) nor time (p=0.62). No interaction between material × time was detected (p=0.28). Mean standard-deviation in MPa at 24 h and 6 m were: ASB 31.38 (4.53) and 30.06 (1.95), CF 34.26 (3.47) and 32.75 (4.18), ASEP 29.54 (4.14) and 33.47 (2.47), P90 30.27 (2.03) and 31.34 (2.19). Conclusions: The silorane-based system showed a similar performance to methacrylate-based materials on dentin. All systems were stable in terms of bond strength up to 6 month of water storage.

Bonded structures for enhanced damage tolerant pressurized fuselages

Adhesive bonding provides solutions to realize cost effective and low weight aircraft fuselage structures, in particular where the Damage Tolerance (DT) is the design criterion. Bonded structures that combine Metal Laminates (MLs) and eventually Selective Reinforcements can guarantee slow crack propagation, crack arrest and large damage capability. To optimize the design exploiting the benefit of bonded structures incorporating selective reinforcement requires reliable analysis tools. The effect of bonded doublers / selective reinforcements is very difficult to be predicted numerically or analytically due to the complexity of the underlying mechanisms and failures modes acting. Reliable predictions of crack growth and residual strength can only be based on sound empirical and phenomenological considerations strictly related to the specific structural concept. Large flat stiffened panels that combine MLs and selective reinforcements have been tested with the purpose of investigating solutions applicable to pressurized fuselages. The large test campaign (for a total of 35 stiffened panels) has quantitatively investigated the role of the different metallic skin concepts (monolithic vs. MLs) of the aluminum, titanium and glass-fiber reinforcements, of the stringers material and cross sections and of the geometry and location of doublers / selective reinforcements. Bonded doublers and selective reinforcements confirmed to be outstanding tools to improve the DT properties of structural elements with a minor weight increase. However the choice of proper materials for the skin and the stringers must be not underestimated since they play an important role as well. A fuselage structural concept has been developed to exploit the benefit of a metal laminate design concept in terms of high Fatigue and Damage Tolerance (F&DT) performances. The structure used laminated skin (0.8mm thick), bonded stringers, two different splicing solutions and selective reinforcements (glass prepreg embedded in the laminate) under the circumferential frames. To validate the design concept a curved panel was manufactured and tested under loading conditions representative of a single aisle fuselage: cyclic internal pressurization plus longitudinal loads. The geometry of the panel, design and loading conditions were tailored for the requirements of the upper front fuselage. The curved panel has been fatigue tested for 60 000 cycles before the introduction of artificial damages (cracks in longitudinal and circumferential directions). The crack growth of the artificial damages has been investigated for about 85 000 cycles. At the end a residual strength test has been performed with a “2 bay over broken frame” longitudinal crack. The reparability of this innovative concept has been taken into account during design and demonstrated with the use of an external riveted repair. The F&DT curved panel test has confirmed that a long fatigue life and high damage tolerance can be achieved with a hybrid metal laminate low weight configuration. The superior fatigue life from metal laminates and the high damage tolerance characteristics provided by integrated selective reinforcements are the key concepts that provided the excellent performances. The weight comparison between the innovative bonded concept and a conventional monolithic riveted design solution showed a significant potential weight saving but the weight advantages shall be traded off with the additional costs.

The Integrated European Project "GEHA - GEnetics of Healthy Aging": recruitment, health status assessment and survival of the Italian 90+ sibpairs

The present study is part of the EU Integrated Project “GEHA – Genetics of Healthy Aging” (Franceschi C et al., Ann N Y Acad Sci. 1100: 21-45, 2007), whose aim is to identify genes involved in healthy aging and longevity, which allow individuals to survive to advanced age in good cognitive and physical function and in the absence of major age-related diseases. Aims The major aims of this thesis were the following: 1. to outline the recruitment procedure of 90+ Italian siblings performed by the recruiting units of the University of Bologna (UNIBO) and Rome (ISS). The procedures related to the following items necessary to perform the study were described and commented: identification of the eligible area for recruitment, demographic aspects related to the need of getting census lists of 90+siblings, mail and phone contact with 90+ subjects and their families, bioethics aspects of the whole procedure, standardization of the recruitment methodology and set-up of a detailed flow chart to be followed by the European recruitment centres (obtainment of the informed consent form, anonimization of data by using a special code, how to perform the interview, how to collect the blood, how to enter data in the GEHA Phenotypic Data Base hosted at Odense). 2. to provide an overview of the phenotypic characteristics of 90+ Italian siblings recruited by the recruiting units of the University of Bologna (UNIBO) and Rome (ISS). The following items were addressed: socio-demographic characteristics, health status, cognitive assessment, physical conditions (handgrip strength test, chair-stand test, physical ability including ADL, vision and hearing ability, movement ability and doing light housework), life-style information (smoking and drinking habits) and subjective well-being (attitude towards life). Moreover, haematological parameters collected in the 90+ sibpairs as optional parameters by the Bologna and Rome recruiting units were used for a more comprehensive evaluation of the results obtained using the above mentioned phenotypic characteristics reported in the GEHA questionnaire. 3. to assess 90+ Italian siblings as far as their health/functional status is concerned on the basis of three classification methods proposed in previous studies on centenarians, which are based on: • actual functional capabilities (ADL, SMMSE, visual and hearing abilities) (Gondo et al., J Gerontol. 61A (3): 305-310, 2006); • actual functional capabilities and morbidity (ADL, ability to walk, SMMSE, presence of cancer, ictus, renal failure, anaemia, and liver diseases) (Franceschi et al., Aging Clin Exp Res, 12:77-84, 2000); • retrospectively collected data about past history of morbidity and age of disease onset (hypertension, heart disease, diabetes, stroke, cancer, osteopororis, neurological diseases, chronic obstructive pulmonary disease and ocular diseases) (Evert et al., J Gerontol A Biol Sci Med Sci. 58A (3): 232-237, 2003). Firstly these available models to define the health status of long-living subjects were applied to the sample and, since the classifications by Gondo and Franceschi are both based on the present functional status, they were compared in order to better recognize the healthy aging phenotype and to identify the best group of 90+ subjects out of the entire studied population. 4. to investigate the concordance of health and functional status among 90+ siblings in order to divide sibpairs in three categories: the best (both sibs are in good shape), the worst (both sibs are in bad shape) and an intermediate group (one sib is in good shape and the other is in bad shape). Moreover, the evaluation wanted to discover which variables are concordant among siblings; thus, concordant variables could be considered as familiar variables (determined by the environment or by genetics). 5. to perform a survival analysis by using mortality data at 1st January 2009 from the follow-up as the main outcome and selected functional and clinical parameters as explanatory variables. Methods A total of 765 90+ Italian subjects recruited by UNIBO (549 90+ siblings, belonging to 258 families) and ISS (216 90+ siblings, belonging to 106 families) recruiting units are included in the analysis. Each subject was interviewed according to a standardized questionnaire, comprising extensively utilized questions that have been validated in previous European studies on elderly subjects and covering demographic information, life style, living conditions, cognitive status (SMMSE), mood, health status and anthropometric measurements. Moreover, subjects were asked to perform some physical tests (Hand Grip Strength test and Chair Standing test) and a sample of about 24 mL of blood was collected and then processed according to a common protocol for the preparation and storage of DNA aliquots. Results From the analysis the main findings are the following: - a standardized protocol to assess cognitive status, physical performances and health status of European nonagenarian subjects was set up, in respect to ethical requirements, and it is available as a reference for other studies in this field; - GEHA families are enriched in long-living members and extreme survival, and represent an appropriate model for the identification of genes involved in healthy aging and longevity; - two simplified sets of criteria to classify 90+ sibling according to their health status were proposed, as operational tools for distinguishing healthy from non healthy subjects; - cognitive and functional parameters have a major role in categorizing 90+ siblings for the health status; - parameters such as education and good physical abilities (500 metres walking ability, going up and down the stairs ability, high scores at hand grip and chair stand tests) are associated with a good health status (defined as “cognitive unimpairment and absence of disability”); - male nonagenarians show a more homogeneous phenotype than females, and, though far fewer in number, tend to be healthier than females; - in males the good health status is not protective for survival, confirming the male-female health survival paradox; - survival after age 90 was dependent mainly on intact cognitive status and absence of functional disabilities; - haemoglobin and creatinine levels are both associated with longevity; - the most concordant items among 90+ siblings are related to the functional status, indicating that they contain a familiar component. It is still to be investigated at what level this familiar component is determined by genetics or by environment or by the interaction between genetics, environment and chance (and at what level). Conclusions In conclusion, we could state that this study, in accordance with the main objectives of the whole GEHA project, represents one of the first attempt to identify the biological and non biological determinants of successful/unsuccessful aging and longevity. Here, the analysis was performed on 90+ siblings recruited in Northern and Central Italy and it could be used as a reference for others studies in this field on Italian population. Moreover, it contributed to the definition of “successful” and “unsuccessful” aging and categorising a very large cohort of our most elderly subjects into “successful” and “unsuccessful” groups provided an unrivalled opportunity to detect some of the basic genetic/molecular mechanisms which underpin good health as opposed to chronic disability. Discoveries in the topic of the biological determinants of healthy aging represent a real possibility to identify new markers to be utilized for the identification of subgroups of old European citizens having a higher risk to develop age-related diseases and disabilities and to direct major preventive medicine strategies for the new epidemic of chronic disease in the 21st century.

Physical and mineralogical changes of Hungarian monumental stones exposed to different conditions: stone-testing in-situ and under laboratory conditions

The Székesfehérvár Ruin Garden is a unique assemblage of monuments belonging to the cultural heritage of Hungary due to its important role in the Middle Ages as the coronation and burial church of the Kings of the Hungarian Christian Kingdom. It has been nominated for “National Monument” and as a consequence, its protection in the present and future is required. Moreover, it was reconstructed and expanded several times throughout Hungarian history. By a quick overview of the current state of the monument, the presence of several lithotypes can be found among the remained building and decorative stones. Therefore, the research related to the materials is crucial not only for the conservation of that specific monument but also for other historic structures in Central Europe. The current research is divided in three main parts: i) description of lithologies and their provenance, ii) physical properties testing of historic material and iii) durability tests of analogous stones obtained from active quarries. The survey of the National Monument of Székesfehérvár, focuses on the historical importance and the architecture of the monument, the different construction periods, the identification of the different building stones and their distribution in the remaining parts of the monument and it also included provenance analyses. The second one was the in situ and laboratory testing of physical properties of historic material. As a final phase samples were taken from local quarries with similar physical and mineralogical characteristics to the ones used in the monument. The three studied lithologies are: fine oolitic limestone, a coarse oolitic limestone and a red compact limestone. These stones were used for rock mechanical and durability tests under laboratory conditions. The following techniques were used: a) in-situ: Schmidt Hammer Values, moisture content measurements, DRMS, mapping (construction ages, lithotypes, weathering forms) b) laboratory: petrographic analysis, XRD, determination of real density by means of helium pycnometer and bulk density by means of mercury pycnometer, pore size distribution by mercury intrusion porosimetry and by nitrogen adsorption, water absorption, determination of open porosity, DRMS, frost resistance, ultrasonic pulse velocity test, uniaxial compressive strength test and dynamic modulus of elasticity. The results show that initial uniaxial compressive strength is not necessarily a clear indicator of the stone durability. Bedding and other lithological heterogeneities can influence the strength and durability of individual specimens. In addition, long-term behaviour is influenced by exposure conditions, fabric and, especially, the pore size distribution of each sample. Therefore, a statistic evaluation of the results is highly recommended and they should be evaluated in combination with other investigations on internal structure and micro-scale heterogeneities of the material, such as petrographic observation, ultrasound pulse velocity and porosimetry. Laboratory tests used to estimate the durability of natural stone may give a good guidance to its short-term performance but they should not be taken as an ultimate indication of the long-term behaviour of the stone. The interdisciplinary study of the results confirms that stones in the monument show deterioration in terms of mineralogy, fabric and physical properties in comparison with quarried stones. Moreover stone-testing proves compatibility between quarried and historical stones. Good correlation is observed between the non-destructive-techniques and laboratory tests results which allow us to minimize sampling and assessing the condition of the materials. Concluding, this research can contribute to the diagnostic knowledge for further studies that are needed in order to evaluate the effect of recent and future protective measures.

Oxidierte Kohlenwasserstoffe in der oberen Troposphäre: Kinetische Untersuchungen zum Abbau und Einfluss auf HO x und Ozon-Chemie

Der erste Teil dieser Arbeit befasst sich mit der Kinetik der Reaktion des OH-Radikals mit Glykolaldehyd (HOCH2CHO). Die Geschwindigkeitskonstante k1 wurde für diese Reaktion temperaturabhängig bestimmt. Durch gepulste Photolyse wurden OH-Radikale erzeugt. Anschließend wurde die laserinduzierte Fluoreszenz der OH-Radikale bei 309 nm detektiert. Die ermittelte Geschwindigkeitskonstante k1 für die Reaktion von OH mit HOCH2CHO von (8,0 ± 0,8) x 10-12 cm3 Teilchen-1 s-1 erweist sich für den Temperaturbereich von 240 K < T < 362 K als temperaturunabhängig. Zwischen 60 und 250 Torr kann zudem keine Druckabhängigkeit für k1 beobachtet werden. Die unerwartet niedrigere Geschwindigkeitskonstante für die betrachtete Reaktion im Vergleich zur Reaktion von OH mit CH3CHO konnte anhand von Überlegungen zur Korrelation zwischen der C-H-Bindungsstärke und dem H-Abstraktionskanal erklärt werden. Im zweiten Teil dieser Arbeit wurde die Photochemie von Aceton (CH3C(O)CH3), Methylethylketon (C2H5C(O)CH3, MEK) und Acetylbromid (CH3C(O)Br) betrachtet. Für die Photolyse von Aceton (bei 248 nm und 266 nm), MEK (bei 248 nm) und Acetylbromid (bei 248 nm) wurden bei 298 ± 3 K druckabhängig zwischen 5 und 1600 Torr N2 Quantenausbeuten für die Methylbildung (Phi(CH3)) bestimmt. Nach gepulster Photolyse der betrachteten Moleküle wurden die transienten Absorptionssignale der Methylradikale bei 216,4 nm verfolgt. Die Quantenausbeuten wurden relativ zur Photolyse von Methyliodid (CH3I) unter gleichen Reaktionsbedingungen ermittelt. Die erhaltenen Quantenausbeuten für CH3-Radikale nehmen für die beiden Systeme Aceton / 248 nm (Phi(CH3, Aceton) = 1,42 – 0,99) und MEK / 248 nm (Phi(CH3, MEK) = 0,45 – 0,19) druckabhängig zu hohen Drücken ab. Die Druckabhängigkeit von Phi(CH3) wird auf die Konkurrenz zwischen Stoßrelaxation und Dissoziation der schwingungsangeregten Acetylradikale (CH3CO#) zurückgeführt. Für das System Aceton / 266 nm wird keine Druckabhängigkeit von Phi(CH3) = 0,93 ± 0,1 beobachtet. Dies wird damit erklärt, dass CH3CO# nicht genügend Energie besitzt, um die Barriere zur Dissoziation zu überschreiten. Bei der Photolyse von Acetylbromid bei 248 nm wird druckunabhängig Phi(CH3) = 0,92 ± 0,10 bestimmt. In diesem System dissoziieren die schwingungsangeregten Acetylradikale bei allen Drücken vollständig. Bei 266 nm wurde die Gesamtquantenausbeute für die Photodissoziation von Aceton (Phi(diss, 266nm)) bestimmt. Die nach Photolyse erhaltenen Methyl - und Acetylradikale wurden nach Titration mit Br2 durch die Resonanzfluoreszenz der Bromatome detektiert. Phi(diss, 266nm) wurde mit 0,92 ± 0,07 bestimmt.

Struktur-Dynamik-Beziehungen in amorphen festen Lösungen

Feste Lösungen homogen dispergierter Wirkstoffmoleküle in amorphen Polymermatrizen sind wichtige Materialien in vielen pharmazeutischen Anwendungen, bei denen eine kontrollierte Abgabe wasserunlöslicher Wirkstoffe in wässrige Systeme eine Rolle spielt. Die intermolekulare Bindungs-stärke zwischen Polymer- und Wirkstoffmolekülgruppen bestimmt die Stabilität der festen Lösung und steuert somit die biologische Aktivität der Wirkstoffmoleküle. In festen Lösungen, die aus acryl-säurehaltigen Copolymeren (Protonendonoren) und basischen Wirkstoffmolekülen (Protonenakzepto-ren) hergestellt werden, sind intermolekulare Wasserstoffbrücken zwischen den Systemkomponenten Triebkraft für die Bildung einer stabilen homogenen Dispersion und für die Entstehung struktureller Merkmale zwischen den Molekülgruppen der Systemkomponenten. Zudem ist die Bindungsstärke der Wasserstoffbrücken im Hinblick auf die kontrollierte Abgabe der Wirkstoffe von Bedeutung. Da dynamische chemische Gleichgewichte bei der Bildung der Wasserstoffbrücken eine wichtige Rolle spielen müssen neben strukturellen Parametern auch dynamische Faktoren beleuchtet werden. Ziel dieser Arbeit ist neben der Ermittlung von intermolekularen Bindungsstärken vor allem die Identifika-tion struktureller Verhältnisse zwischen den Systemkomponenten auf molekularer Ebene. Die Be-stimmung der Abhängigkeit dieser Parameter von der Struktur der verwendeten Polymere und einer Vielzahl weiterer Einflüsse wie z.B. Feuchtigkeit, Lagerdauer oder Wirkstoffkonzentration soll ein kontrolliertes Design fester Lösungen mit definierten anwendungsspezifischen Eigenschaften ermögli-chen. Temperaturabhängige 1H-Festkörper-MAS-NMR (Magic Angle Spinning Nuclear Magnetic Resonance) Experimente an festen Lösungen mit unterschiedlichen Copolymer-Zusammensetzungen weisen die Existenz dynamischer chemischer Gleichgewichte in den komplexen Wasserstoffbrücken-netzwerken nach. Veränderungen in der chemischen Verschiebung und in der Linienform der Reso-nanzlinien acider Protonen erlauben einen tiefen Einblick in die Architektur dieser Netzwerke und legen die Bindungsverhältnisse unter Berücksichtigung der Polymerchemie und der Mobilität der Systemkomponenten dar, wobei die Befunde mithilfe quantenchemischer Rechnungen untermauert werden können. Die Gegenwart acider Protonen ermöglicht einen einfachen 1H-2H-Austausch, wor-aufhin mithilfe rotorsynchronisierter temperaturabhängiger 2H-MAS-NMR Experimente die Wasser-stoffbrückenbindungsstärke bestimmt werden kann. Mit 1H-1H-Korrelationsexperimenten (Doppelquantenspektroskopie) stehen Methoden für die Bestimmung homonuklearer dipolarer 1H-1H-Kopplungen zur Verfügung, die strukturelle Aussagen aufgrund von bevorzugten räumlichen Kontak-ten bestimmter Molekülgruppen ermöglichen. Weiterhin können diese Experimente verwendet werden, um Wasserstoffbrücken zwischen Polymergruppen von Polymer-Wirkstoff-Wasserstoffbrücken zu unterscheiden, wodurch eine quantitative Beschreibung des Bindungsnetzwerks und der Konkurrenz-prozesse zwischen den einzelnen wasserstoffverbrückten Spezies ermöglicht wird. Eine Kristallisation der Wirkstoffmoleküle ist in vielen Anwendungen unerwünscht, da sie die biologische Verfügbarkeit des Wirkstoffs reduzieren. Mit 1H-Festkörper-MAS-NMR Experimenten können kristalline von amorph dispergierten Wirkstoffmolekülen unterschieden werden, wodurch eine Quantifizierung der Destabilisierungsprozesse ermöglicht wird, die durch Exposition der festen Lösungen mit Wasserdampf ausgelöst werden können. Die Zeit- und Konzentrationsabhängigkeit der Wasseraufnahme kann mit NMR-Experimenten verfolgt werden, wobei unterschiedlich mobile Was-serspezies an unterschiedlichen Bindungsorten identifiziert werden können, was zum molekularen Verständnis der Destabilisierungsprozesse beiträgt. Zusätzlich wird die Mobilität der Wirkstoffmole-küle bestimmt, die sich – wie auch die Wirkstoffkonzentration - als wichtige Größe in der Beschrei-bung der Destabilisierung erweist. Aufbauend auf den Beobachtungen wird ein Zusammenhang zwischen der Copolymerzusammensetzung und einer kritischen Wirkstoffkonzentration hergestellt, der für die Anwendungen amorpher fester Lösungen in biologischen Systemen von großer Bedeutung ist.

Zirconia in dentistry

The above factors emphasize the scope of this thesis for further investigations on zirconia, the improvement of all-ceramic zirconia restorations, and especially the interaction of zirconia and veneering and its influence on the performance of the whole restoration. The introduction, chapter 1, gave a literature overview on zirconia ceramics. In chapter 2, the objective of the study was to evaluate the effect of abrading before and after sintering using alumina-based abrasives on the surface of yttria-tetragonal zirconia polycrystals. Particular attention was paid to the amount of surface stress–assisted phase transformation (tetragonal→monoclinic) and the presence of microcracks. Chapter 3 is based on the idea that the conventional sintering techniques for zirconia based materials, which are commonly used in dental reconstruction, may not provide a uniform heating, with consequent generation of microstructural flaws in the final component. As a consequence of the sintering system, using microwave heating, may represent a viable alternative. The purpose of the study was to compare the dimensional variations and physical and microstructural characteristics of commercial zirconia (Y-TZP), used as a dental restoration material, sintered in conventional and microwave furnaces. Chapter 4 described the effect of sandblasting before and after sintering on the surface roughness of zirconia and the microtensile bond strength of a pressable veneering ceramic to zirconia.

Two pre-treatments for bonding to non-carious cervical root dentin

Purpose: To investigate the effect of airborne-particle abrasion or diamond bur preparation as pretreatment steps of non-carious cervical root dentin regarding substance loss and bond strength. Methods: 45 dentin specimens produced from crowns of extracted human incisors by grinding the labial surfaces with silicon carbide papers (control) were treated with one of three adhesive systems (Group 1A-C; A: OptiBond FL, B: Clearfil SE Bond, or C: Scotchbond Universal; n=15/adhesive system). Another 135 dentin specimens (n=15/group) produced from the labial, non-carious cervical root part of extracted human incisors were treated with one of the adhesive systems after either no pre-treatment (Group 2A-C), pre-treatment with airborne-particle abrasion (CoJet Prep and 50 µm aluminum oxide powder; Group 3A-C), or pre-treatment with diamond bur preparation (40 µm grit size; Group 4A-C). Substance loss caused by the pre-treatment was measured in Groups 3 and 4. After treatment with the adhesive systems, resin composite was applied and all specimens were stored (37°C, 100% humidity, 24 hours) until measurement of microshear bond strength (µSBS). Data were analyzed with a nonparametric ANOVA followed by Kruskal-Wallis and Wilcoxon rank sum tests (level of significance: alpha=0.05). Results: Overall substance loss was significantly lower in Group 3 (median: 19 µm) than in Group 4 (median: 113 µm; p<0.0001). There were no significant differences in µSBS between the adhesive systems (A-C) in Group 1, Group 3, and Group 4 (p>=0.133). In Group 2, OptiBond FL (Group 2A) and Clearfil SE Bond (Group 2B) yielded significantly higher µSBS than Scotchbond Universal (Group 2C; p<=0.032). For OptiBond FL and Clearfil SE Bond, there were no significant differences in µSBS between the ground crown dentin and the non-carious cervical root dentin regardless of any pre-treatment of the latter (both p=0.661). For Scotchbond Universal, the µSBS to non-carious cervical root dentin without pre-treatment was significantly lower than to ground crown dentin and to non-carious cervical root dentin pre-treated with airborne-particle abrasion or diamond bur preparation p<=0.014).

Impact of Sn/F Pre-Treatments on the Durability of Protective Coatings against Dentine Erosion/Abrasion.

For preventing erosive wear in dentine, coating with adhesives has been suggested as an alternative to fluoridation. However, clinical studies have revealed limited efficacy. As there is first evidence that Sn(2+) increases bond strength of the adhesive Clearfil SE (Kuraray), the aim of the present study was to investigate whether pre-treatment with different Sn(2+)/F(-) solutions improves the durability of Clearfil SE coatings. Dentine samples (eight groups, n=16/group) were freed of smear layer (0.5% citric acid, 10 s), treated (15 s) either with no solution (control), aminefluoride (AmF, 500 ppm F(-), pH 4.5), SnCl2 (800/1600 ppm Sn(2+); pH 1.5), SnCl2/AmF (500 ppm F(-), 800 ppm Sn(2+), pH 1.5/3.0/4.5), or Elmex Erosion Protection Rinse (EP, 500 ppm F-, 800 ppm Sn(2+), pH 4.5; GABA International), then rinsed with water (15 s) and individually covered with Clearfil SE. Subsequently the specimens were subjected to an erosion/abrasion protocol consisting of 1320 cycles of immersion in 0.5% citric acid (5 °C/55 °C; 2 min) and automated brushing (15 s, 200 g, NaF-toothpaste, RDA 80). As the coatings proved stable up to 1320 cycles, 60 modified cycles (brushing time 30 min/cycle) were added. Wear was measured profilometrically. After SnCl2/AmF, pH 4.5 or EP pre-treatment all except one coating survived. In the other groups, almost all coatings were lost and there was no significant difference to the control group. Pre-treatment with a Sn(2+)/F(-) solution at pH 4.5 seems able to improve the durability of adhesive coatings, rendering these an attractive option in preventing erosive wear in dentine.

Plaster reinforcement with fibers by mineral wool obtained from the recycle of construction and demolition waste

The use of mineral wool is becoming more widespread due to increased acoustic and thermal demands of Spanish Technical Building Code. This increase affects both in rehabilitation and new construction projects. Therefore, waste generation of this type of insulating material is having more importance. The main objective of this research is to study the possibility of recycling fiber obtained from mineral wool of the C&DW as an alternative material to chopped glass fibers that are currently used as reinforcing elements in the prefabricated plaster. To achieve this objective, series are made of plaster E-35 additived with rock wool residue and glass wool residue at different rates of addition. These series are repeated by changing the additive by E fiberglass (length of 25mm) to make a comparative analysis with respect to the series additived with mineral wool waste. All the series are subjected to the test to determine Shore C surface hardness and mechanical testing to determine the compressive and flexural strength. From the results it can be concluded that: with rock wool residue, increases Shore C hardness up to 15% with respect to the glass fiber and 9% with respect to the glass wool, with a percentage of addition 2%. With rock wool residue, weight is decreased by 5% with respect to the glass fiber and 4% with respect to the glass wool waste, with an addition percentage of 4%. For an addition rate of 4%, results in the flexural strength test with fiberglass are 85% higher than those obtained with glass wool residue. However, for a percentage of 1% addition, the results obtained with glass wool residue are 35% higher than those obtained with fiberglass. For an addition rate of 3% results in the compressive strength test with fiberglass are 54% lower than those obtained with rock wool waste and 70% lower than those obtained with glass wool waste. Comparing the two mineral wools, it can be concluded that up to 3% of the addition, the glass wool series results obtained are 10% higher than those additived with rock wool. However, higher percentages of addition show that the results obtained with rock wool are 35% higher than those obtained with glass wool. The general conclusion is that the series additived with mineral wool from C&DW show better results in tests than the ones used nowadays as plaster reinforcement.

Evaluación del comportamiento mecánico de estructuras de hormigón armado utilizadas como elementos termoactivos

El objetivo de este trabajo es conocer las posibles modificaciones que puede producir en el comportamiento de las estructuras de hormigón armado (EHA) el hecho de que sean utilizadas como estructuras termoactivas, ya sea como intercambiadores en contacto con el terreno, o como sistema de distribución de calor utilizando la inercia térmica de los elementos de hormigón del edificio, basándose en el uso de energías renovables. Las EHA termoactivas se caracterizan por la incorporación en su interior de tubos de polietileno por los que circulan fluidos a temperaturas medias, que pueden incidir en el comportamiento mecánico de los elementos estructurales debido a dos efectos fundamentales: el incremento de temperatura que se produce en el interior de la EHA y la perturbación provocada por la incorporación de los tubos de polietileno. Con este fin, se ha realizado una campaña experimental de probetas de hormigón, estudiando los dos efectos por separado, por un lado se ha evaluado el comportamiento de probetas de hormigón tipo H-25 y tipo H-30 sometidas a cuatro temperaturas diferentes: 20ºC, 40ºC, 70ºC y 100ºC, ensayando la resistencia a compresión y la resistencia a anclaje/adherencia mediante ensayo “pull-out”; y, por otro lado, se ha evaluado el comportamiento de probetas de hormigón tipo H-25 y tipo H-30, elaboradas con dos tipos de molde (cilíndrico y cúbico), en las que se ha colocado tubos de polietileno en su interior en distintas posiciones, ensayando su resistencia a compresión. Los resultados de los ensayos han puesto de manifiesto que aunque se produce una disminución en la resistencia a compresión, y a arrancamiento, del hormigón, al ser sometido a aumentos de temperatura, esta disminución de la propiedades mecánicas es inferior al 20% al no superar esta tecnología los 70ºC; y respecto a la variación de la resistencia a compresión de probetas cilíndricas y cúbicas, debidas a la incorporación de los tubos de polietileno, se observa que si la posición de los mismos es paralela a la dirección de la carga tampoco se ven comprometidas las propiedad mecánicas del hormigón en valores superiores al 20%. ABSTRACT The aim of this project is to study the effects of using concrete structures as thermo-active constructions, either as energy foundations or other kind of thermo-active ground structures, or as a thermally activated building structure utilizing its own thermal mass conductivity and storage capacity to heat and cool buildings, based on renewable or “free” energy sources. The pipes, filled with a heat carrier fluid, that are embedded into the building´s concrete elements may bring on two different adverse effects on concrete structures. In one hand, the consequence of thermal variations and, on the other hand, because of the fact that the pipes are inside of the concrete mortar and in direct contact with the reinforcing steel bars. For this reason, different types of specimens and testing procedures have been proposed to discuss the effects of temperature (20º, 40ºC, 70ºC y 100ºC) on the performance of two different hardened concrete: H-25 and H-30, and the effects of having the pipes embedded in different positions inside of specimens made of two types of concrete, H-25 and H-30, and with two kind of cast, cylindrical and cubical. The experimental program includes the use of compressive strength test and also pull-out test, in order to investigate the interfacial adhesion quality and interfacial properties between steel bar and concrete. The results of the mechanical test showed that the increase of temperature in hardened concrete specimens lower than 70ºC, and the introduction of embedded pipes placed in parallel to the load, in cylindrical or cubic specimens, does not jeopardize the mechanical properties of concrete with strength decreases higher than 20%.

Perfil antropométrico y respuesta psico-fisiológica en escalada deportiva en roca: Diferencias entre modalidades

En la literatura se ha descrito el perfil antropométrico y la respuesta psicofisiológica en escalada deportiva en roca, pero hasta la fecha, no se habían analizado las diferencias existentes entre sus principales modalidades. El objetivo de la presente tesis fue describir las características antropométricas del escalador de competición y comprobar la existencia de diferencias entre los participantes de distintas modalidades, así como analizar la respuesta psico-fisiológica durante la ejecución de un búlder y una vía, además de evaluar las diferencias entre su realización a vista o tras un ensayo. Para ello, efectuamos dos estudios diferentes: en el primero participaron voluntariamente 61 hombres y 18 mujeres, participantes en cuatro pruebas del circuito nacional de competición de escalada durante el año 2009, tres de ellas de la modalidad de dificultad a vista y una de búlder. Se realizaron mediciones antropométricas, prueba de fuerza de prensión manual antes y después de competir, y se cumplimentó un cuestionario donde se evaluaba la percepción del esfuerzo y la experiencia deportiva. En el segundo estudio, 23 escaladores, 15 hombres y 8 mujeres, divididos en tres grupos en función de su nivel de rendimiento, realizaron de manera voluntaria distintas pruebas durante tres días separados entre sí al menos 48 horas. El primer día rellenaron un cuestionario sobre su experiencia deportiva y nivel de rendimiento, fueron pesados, tallados y sometidos a un escáner de cuerpo completo en densitómetro con objeto de medir la composición corporal. El segundo día realizaron previo calentamiento, un búlder a vista y, tras un descanso de 15 minutos, escalaron una vía a vista acorde con su nivel. El tercer día, después de calentar y disponer de 20 minutos para ensayarlo, repitieron la escalada del búlder. Tras un descanso de 15 minutos y 20 minutos de ensayo, realizaron un segundo intento a la vía. Se registraron los valores en la respuesta cardiorrespiratoria, se obtuvieron muestras de lactato en sangre del lóbulo de la oreja y se realizaron pruebas de fuerza de prensión manual antes y después de la escalada. También se pasó un cuestionario para medir la ansiedad y autoconfianza así como el esfuerzo percibido. Los resultados no mostraron diferencias antropométricas significativas entre los participantes en competiciones de búlder y los que participaron en competiciones de escalada de dificultad a vista. Se dieron diferencias en la pérdida de fuerza antes y después de escalar entre dichos participantes. Las mujeres obtuvieron menor fuerza de prensión manual que los hombres pero la misma pérdida de fuerza entre el instante antes de competir y el posterior. La respuesta fisiológica durante la ejecución del búlder fue menor que la obtenida durante la ejecución de la vía. Hubo pérdida de fuerza de prensión manual entre el instante anterior y el posterior a ejecutar la vía, pero no al hacer el búlder. Sin embargo, no se dieron diferencias en la ansiedad y la autoestima provocada por ambas modalidades, por lo que deducimos que la ejecución de un búlder y una vía presentan una respuesta fisiológica distinta. Proponemos que la respuesta está relacionada, sobre todo, con las variables de ejecución, de tal manera que a mayor distancia y/o tiempo recorrido en la escalada, mayor será la contribución anaeróbica al esfuerzo y la fatiga manifestada como pérdida de fuerza que, en el caso del búlder, fue mínima o inexistente. En el segundo intento, tras un ensayo de 20 minutos en el búlder, se consiguió mejorar el rendimiento respecto al primer intento, que se manifestó con un aumento en la distancia recorrida. Sin embargo, en la vía no se dieron diferencias entre ambos intentos, ni en la ejecución, ni en la respuesta fisiológica, ni en la ansiedad, ni siquiera en la fuerza de prensión manual. ABSTRACT It has been described in the literature the anthropometric profile and psychophysiological response in rock climbing, but so far not been analyzed differences between its main modalities. The aim of this thesis was to describe the anthropometric characteristics of the climber competitor and check for differences between participants of different modalities and to analyze the psycho-physiological response during the execution of a boulder and a route also to assess differences between on sight and redpoint attempts. We made two different studies: in the first 61 men and 18 women who attended four competitions of national climbing circuit in 2009, three of them on-sight difficulty competitions and a boulder competition participated voluntarily. Anthropometric measurements, a hand grip strength test before and after competing were registered for each climber, and a questionnaire which assessed perception of effort and the climbing experience was fulfilled. In the second study, various tests were conducted on 23 volunteer climbers, 15 men and 8 women, during three days separated for, at least, 48 hours of resting, divided into three groups according to their performance. The first day, climbers completed a questionnaire on their experience and performance level. It was recorded weight, height and they underwent a full body scan densitometer in order to measure body composition. The second day, after previous warming-up, they climbed a boulder on sight and, after a break of 15 minutes, climbed a route on-sight according to their level. The third day, after warming-up and have 20 minutes to try it, they repeated the bouldering climbing. After a break of 15 minutes and 20 minutes of essaying, they made a second attempt at the route. Values in the cardiorespiratory response were recorded, blood lactate samples were obtained from earlobe, and hand grip strength was tested before and after the climb. They also filled a questionnaire to measure anxiety and self-confidence and perceived exertion. The results showed no significant anthropometric differences between participants in bouldering competitions and participants in competitions on-sight difficulty climbing. There were found differences in strength loss before and after climbing between those participants. Women had less hand grip strength than men but the same loss of strength between the records carried out before and after competing. The physiological response recorded for boulder climbing was lower than the obtained for the route. There was loss of hand grip strength between the time before and after running the route but not for bouldering. However, there were no differences in anxiety and self-esteem caused by both modalities, so we conclude that the implementation of a boulder and a route have different physiological responses. We think that this response is mainly related to performance variables, as a greater distance and/or travel time on the climb, the higher the anaerobic contribution to the effort and fatigue as manifested by loss of strength in the case of the boulder was minimal or nonexistent. In the second attempt after 20 minutes in the boulder better performance was achieved on the first attempt, which was manifested by an increment of climbing distance. However, there were the differences in the route between the two attempts, either in execution or in the physiological response, or anxiety, or even in hand grip strength.

Exploring the active site of chorismate mutase by combinatorial mutagenesis and selection: the importance of electrostatic catalysis.

Chorismate mutase (EC 5.4.99.5) catalyzes the intramolecular rearrangement of chorismate to prephenate. Arg-90 in the active site of the enzyme from Bacillus subtilis is in close proximity to the substrate's ether oxygen and may contribute to efficient catalysis by stabilizing the presumed dipolar transition state that would result upon scission of the C--O bond. To test this idea, we have developed a novel complementation system for chorismate mutase activity in Escherichia coli by reengineering parts of the aromatic amino acid biosynthetic pathway. The codon for Arg-90 was randomized, alone and in combination with that for Cys-88, and active clones were selected. The results show that a positively charged residue either at position 88 (Lys) or 90 (Arg or Lys) is essential. Our data provide strong support for the hypothesis that the positive charge is required for stabilization of the transition state of the enzymatic chorismate rearrangement. The new selection system, in conjunction with combinatorial mutagenesis, renders the mechanism of the natural enzyme(s) accessible to further exploration and opens avenues for the improvement of first generation catalytic antibodies with chorismate mutase activity.

Effects of plant functional traits on soil stability: intraspecific variability matters

This data set describes different vegetation, soil and plant functional traits (PFTs) of 15 plant species in 30 sampling plots of an agricultural landscape in the Haean-myun catchment in South Korea. We divided the data set into two main tables, the first one includes the PFTs data of the 15 studied plant species, and the second one includes the soil and vegetation characteristics of the 30 sampling plots. For a total of 150 individuals, we measures the maximum plant height (cm) and leaf size (cm**2), which means the leaf surface area for the aboveground compartment of each individual. For the belowground compartment, we measured root horizontal width, which is the maximum horizontal spread of the root, rooting length, which is the maximum rooting depth, root diameter, which is the average root diameter of a the whole root, specific root length (SRL), which is the root length divided by the root dry mass, and root/shoot ratio, which is the root dry mass divided by the shoot dry mass. At each of the 30 studied plots, we estimated three different variables describing the vegetation characteristics: vegetation cover (i.e. the percentage of ground covered by vegetation), species richness (i.e. the number of observed species) and root density (estimated using a 30 cm x 30 cm metallic frame divided into nine 10 cm x 10 cm grids placed on the soil profile), as we calculated the total number of roots that appear in each of the nine grids and then we converted it into percentage based on the root count, following. Moreover, in each plot we estimated six different soil variables: Bulk density (g/cm**3), clay % (i.e. percentage of clay), silt % (i.e. percentage of silt), soil aggregate stability, using mean weight diameter (MWD), penetration resistance (kg/cm**2), using pocket penetrometer and soil shear vane strength (kPa).