Influence of the rotary and/or oscillatory reciprocating systems in the morphological changes of narrow and curved molar root canals anatomy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Topography of four different endodontic rotary systems, before and after being used for the 12th time

Root canal preparation may damage NiTi instruments resulting in wear and deformation. The aim of this study was to make a comparative evaluation of the surface topography of the cervical third of four different rotary systems, before and after being used twelve times, in 1.440 resin blocks with simulated root canals with standardized 45 degrees curvatures, and analyzed by atomic force microscopy AFM. The blocks were divided into four groups and prepared according to the manufacturers recommendations: Group 1 - K3 (R); Group 2 - Protaper Universal (R); Group 3 - Twisted Files (R) and Group 4 - Biorace (R). After each preparation, the instruments were washed and autoclaved. A total of 240 instruments were selected, being 30 new instruments and 30 after having been used for the 12th time, from each group. These instruments were analyzed by AFM and for quantitative evaluation, the mean RMS (Root mean square) values of the cervical third of the specimens from the four groups were used. The result showed that all the rotary files used for the 12th time suffered wear with change in the topography of the cervical region of the active portion of the file (ANOVA p < 0.01). Classifying the specimens in increasing order, from the least to the greatest wear suffered, Group 3 (2.8993 nm) presented the least wear, followed by Group 4 (12.2520 nm), Group 1 (36.0043 nm) and lastly, Group 2 (59.8750 nm) with the largest amount of cervical surface wear. Microsc. Res. Tech. 75:97-102, 2012. (c) 2011 Wiley Periodicals, Inc.

Efficacy of NiTi rotary instruments in removing calcium hydroxide dressing residues from root canal walls

The aim of this study was to evaluate the efficacy of three rotary instrument systems (K3, Pro Taper and Twisted File) in removing calcium hydroxide residues from root canal walls. Thirty-four human mandibular incisors were instrumented with the Pro Taper System up to the F2 instrument, irrigated with 2.5% NaOCl followed by 17% EDTA, and filled with a calcium hydroxide intracanal dressing. After 7 days, the calcium hydroxide dressing was removed using the following rotary instruments: G1. - NiTi size 25, 0.06 taper, of the K3 System; G2 - NiTi F2, of the Pro Taper System; or G3 - NiTi size 25, 0.06 taper, of the Twisted File System. The teeth were longitudinally grooved on the buccal and lingual root surfaces, split along their long axis, and their apical and cervical canal thirds were evaluated by SEM (x1000). The images were scored and the data were statistically analyzed using the Kruskall Wallis test. None of the instruments removed the calcium hydroxide dressing completely, either in the apical or cervical thirds, and no significant differences were observed among the rotary instruments tested (p > 0.05).

Effect of Nitrogen Ion Implantation on the Flexibility of Rotary Nickel-Titanium Instruments

Introduction: The aim of this study was to assess the effect of nitrogen ion implantation on the flexibility of rotary nickel-titanium (NiTi) instruments as measured by the load required to bend implanted and nonimplanted instruments at a 30 degrees angle. Methods: Thirty K3 files, size #40, 0.02 taper and 25-mm length, were allocated into 2 groups as follows: group A, 15 files exposed to nitrogen ion implantation at a dose of 2.5 x 10(17) ions/cm(2), voltage 200 KeV, current density 1 mu A/cm(2), temperature 130 degrees C, and vacuum conditions of 10 x 10(-6) mm Hg for 6 hours; and group B, 15 nonimplanted files. One extra file was used for process control. All instruments were subjected to bend testing on a modified troptometer, with measurement of the load required for flexure to an angle of 30 degrees. The Mann-Whitney U test was used for statistical analysis. Findings with P <.05 were considered significant. Results: The mean load required to bend instruments at a 30 degrees angle was 376.26 g for implanted instruments and 383.78 g for nonimplanted instruments. The difference was not statistically significant. Conclusions: Our findings show that nitrogen ion implantation has no appreciable effect on the flexibility of NiTi instruments. (J Endod 2012;38:673-675)

Infinite dimensional Lie algebra associated with conformal transformations of the two-point velocity correlation tensor from isotropic turbulence

We deal with homogeneous isotropic turbulence and use the two-point velocity correlation tensor field (parametrized by the time variable t) of the velocity fluctuations to equip an affine space K3 of the correlation vectors by a family of metrics. It was shown in Grebenev and Oberlack (J Nonlinear Math Phys 18:109–120, 2011) that a special form of this tensor field generates the so-called semi-reducible pseudo-Riemannian metrics ds2(t) in K3. This construction presents the template for embedding the couple (K3, ds2(t)) into the Euclidean space R3 with the standard metric. This allows to introduce into the consideration the function of length between the fluid particles, and the accompanying important problem to address is to find out which transformations leave the statistic of length to be invariant that presents a basic interest of the paper. Also we classify the geometry of the particles configuration at least locally for a positive Gaussian curvature of this configuration and comment the case of a negative Gaussian curvature.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Optimization of RNA-based transgene expression by targeting Protein Kinase R

The aim of this thesis was to establish a method for repeated transfection of in vitro transcribed RNA (IVT-RNA) leading to a sustained protein expression lasting for days or even weeks. Once transfected cells recognize IVT-RNA as "non-self" and initiate defense pathways leading to an upregulated interferon (IFN) response and stalled translation. In this work Protein Kinase R (PKR) was identified as the main effector molecule mediating this cellular response. We assessed four strategies to inhibit PKR and the IFN response: A small molecule PKR inhibitor enhanced protein expression and hampered the induction of IFN-transcripts, but had to be excluded due to cytotoxicity. A siRNA mediated PKR knockdown and the overexpression of a kinase inactive PKR mutant elevated the protein expression, but the down-regulation of the IFN response was insufficient. The co-transfer of the viral inhibitors of PKR and the IFN response was most successful. The use of E3, K3 and B18R co-transfection enabled repeated IVT-RNA-based transfection of human fibroblasts. Thus, the developed protocol allows a continuous IVT-RNA encoded protein expression of proteins, which could be the basis for the generation of induced pluripotent stem cells (iPS) for several therapeutic applications in regenerative medicine or drug research.

Deposizione elettrochimica di esacianoferrato di rame tramite un metodo "a due step"; caratterizzazione e valutazione delle prestazioni

In this thesis we have identified two electrochemical procedures for preparing two compounds of copper hexacyanoferrate (CuHCF) films with different compositions and structures. The deposition were carried out using a “two steps” method consisting in electrochemical oxidation of previously deposited metallic copper on carbon substrates (glassy carbon and graphite foil electrodes) in K3[Fe(CN)6] solution. Both films, CuHCF-methodA and CuHCF-methodB, were characterized by cyclic voltammetry (GC) and their study using XANES spectroscopy revealed evidence of different structures. Additionally, insertion and extraction of different cations (Na+, K+, Mg2+, Al3+ and Cs+) were performed and the results indicate that CuHCF-methodA has slightly better performances and operational stability than CuHCF-methodB. Data from galvanostatic charge-discharge tests confirme the latter observation. An application for amperometric detection of H2O2 and SEM micrographs are also reported for both films (method A and B). Comparing these results with a previous work of our research group, seems that the deposition of two different compounds using methodA and methodB is due to the different stoichiometry of ions Cu2+ e [Fe(CN)6]3– created near electrode surface during the dissolution step.

A Stellar Census of the Tucana-Horologium Moving Group

We report the selection and spectroscopic confirmation of 129 new late-type (SpT = K3-M6) members of the Tucana-Horologium moving group, a nearby (d similar to 40 pc), young (tau similar to 40 Myr) population of comoving stars. We also report observations for 13 of the 17 known Tuc-Hor members in this spectral type range, and that 62 additional candidates are likely to be unassociated field stars; the confirmation frequency for new candidates is therefore 129/191 = 67%. We have used radial velocities, Ha emission, and Li-6708 absorption to distinguish between contaminants and bona fide members. Our expanded census of Tuc-Hor increases the known population by a factor of similar to 3 in total and by a factor of similar to 8 for members with SpT >= K3, but even so, the K-M dwarf population of Tuc-Hor is still markedly incomplete. Our expanded census allows for a much more detailed study of Tuc-Hor than was previously feasible. The spatial distribution of members appears to trace a two-dimensional sheet, with a broad distribution in X and Y, but a very narrow distribution (+/- 5 pc) in Z. The corresponding velocity distribution is very small, with a scatter of +/- 1.1 km s(-1) about the mean UVW velocity for stars spanning the entire 50 pc extent of Tuc-Hor. We also show that the isochronal age (tau similar to 20-30 Myr) and the lithium depletion boundary age (tau similar to 40 Myr) disagree, following the trend in other pre-main-sequence populations for isochrones to yield systematically younger ages. The H alpha emission line strength follows a trend of increasing equivalent width with later spectral type, as is seen for young clusters. We find that moving group members have been depleted of measurable lithium for spectral types of K7.0-M4.5. None of our targets have significant infrared excesses in the WISE W3 band, yielding an upper limit on warm debris disks of F < 0.7%. Finally, our purely kinematic and color-magnitude selection procedure allows us to test the efficiency and completeness for activity-based selection of young stars. We find that 60% of K-M dwarfs in Tuc-Hor do not have ROSAT counterparts and would have been omitted in X-ray-selected samples. In contrast, GALEX UV-selected samples using a previously suggested criterion for youth achieve completeness of 77% and purity of 78%, and we suggest new SpT-dependent selection criteria that will yield > 95% completeness for tau similar to 40 Myr populations with GALEX data available.

Daily ozone cycle in the stratosphere: global, regional and seasonal behaviour modelled with the Whole Atmosphere Community Climate Model

The Whole Atmosphere Community Climate Model (WACCM) is utilised to study the daily ozone cycle and underlying photochemical and dynamical processes. The analysis is focused on the daily ozone cycle in the middle stratosphere at 5 hPa where satellite-based trend estimates of stratospheric ozone are most biased by diurnal sampling effects and drifting satellite orbits. The simulated ozone cycle shows a minimum after sunrise and a maximum in the late afternoon. Further, a seasonal variation of the daily ozone cycle in the stratosphere was found. Depending on season and latitude, the peak-to-valley difference of the daily ozone cycle varies mostly between 3 and 5% (0.4 ppmv) with respect to the midnight ozone volume mixing ratio. The maximal variation of 15% (0.8 ppmv) is found at the polar circle in summer. The global pattern of the strength of the daily ozone cycle is mainly governed by the solar zenith angle and the sunshine duration. In addition, we find synoptic-scale variations in the strength of the daily ozone cycle. These variations are often anti-correlated to regional temperature anomalies and are due to the temperature dependence of the rate coefficients k2 and k3 of the Chapman cycle reactions. Further, the NOx catalytic cycle counteracts the accumulation of ozone during daytime and leads to an anti-correlation between anomalies in NOx and the strength of the daily ozone cycle. Similarly, ozone recombines with atomic oxygen which leads to an anti-correlation between anomalies in ozone abundance and the strength of the daily ozone cycle. At higher latitudes, an increase of the westerly (easterly) wind cause a decrease (increase) in the sunshine duration of an air parcel leading to a weaker (stronger) daily ozone cycle.

Towards understanding thermal jet quenching via lattice simulations

After reviewing how simulations employing classical lattice gauge theory permit to test a conjectured Euclideanization property of a light-cone Wilson loop in a thermal non-Abelian plasma, we show how Euclidean data can in turn be used to estimate the transverse collision kernel, C(k⊥), characterizing the broadening of a high-energy jet. First results, based on data produced recently by Panero et al, suggest that C(k⊥) is enhanced over the known NLO result in a soft regime k⊥ < a few T. The shape of k3⊥ C(k⊥) is consistent with a Gaussian at small k⊥.

Cyanide Compounds

Chapter 4, “Cyanide Compounds,” illustrates an explosively developing research theme in which the cyanide ligand is used as a linking agent for the designed assembly of polynuclear metal complexes. Syntheses of several basic building blocks, such as K3[Cr(CN)6],Cr(Me3tacn)(CN)3,K4[Mo(CN)8],Na[W(CO)5CN],K[CpFe(CO)(CN)2],[NEt4][Cp*Rh(CN)3],[Fe4(bpy)8(μ-CN)4][PF6]4,. are given here. These units may be used in several ways to construct polynuclear compounds. One approach involves a hexacyanometalate core decorated with peripheral metal centers, e.g., [{Cu(tpa)(CN)}6Fe][ClO4]8. or [Cr{CNNi(tetren)}6][ClO4]9. An octacyanometalate unit can lead to higher nuclearity condensed compounds, as in [Co{Co(MeOH)3}8(μ-CN)30{Mo(CN)3}6]. Alternatively, a cluster core may be substituted with cyano complexes as ligands, as in [PPh4]2[Fe4S4{NCW(CO)5}4]. If there are two cis cyano ligands on the building block, then quadrilateral or square structures often result, as in {CpFe(CO(μ-CN)2Cu(PCy3)}2 and [Fe2Cu2(bpy)6(μ-CN)4][PF6]4 However, if there are three adjacent cyano ligands, then cubic cages may be constructed as in [(CpCo)4(Cp*Rh)4(μ-CN)12][PF6]4.

Comparative characterisation of two nitroreductases from Giardia lamblia as potential activators of nitro compounds

Giardia lamblia is a protozoan parasite that causes giardiasis, a diarrhoeal disease affecting humans and various animal species. Nitro drugs such as the nitroimidazole metronidazole and the nitrothiazolide nitazoxanide are used for treatment of giardiasis. Nitroreductases such as GlNR1 and GlNR2 may play a role in activation or inactivation of these drugs. The aim of this work is to characterise these two enzymes using functional assays. For respective analyses recombinant analogues from GlNR1 and GlNR2 were produced in Escherichia coli. E. coli expressing GlNR1 and GlNR2 alone or together were grown in the presence of nitro compounds. Furthermore, pull-down assays were performed using HA-tagged GlNR1 and GlNR2 as baits. As expected, E. coli expressing GlNR1 were more susceptible to metronidazole under aerobic and semi-aerobic and to nitazoxanide under semi-aerobic growth conditions whereas E. coli expressing GlNR2 were susceptible to neither drug. Interestingly, expression of both nitroreductases gave the same results as expression of GlNR2 alone. In functional assays, both nitroreductases had their strongest activities on the quinone menadione (vitamin K3) and FAD, but reduction of nitro compounds including the nitro drugs metronidazole and nitazoxanidewas clearly detected. Full reduction of 7-nitrocoumarin to 7-aminocoumarin was preferentially achieved with GlNR2. Pull-down assays revealed that GlNR1 and GlNR2 interacted in vivo forming a multienzyme complex. These findings suggest that both nitroreductases are multifunctional. Their main biological role may reside in the reduction of vitamin K analogues and FAD. Activation by GlNR1 or inactivation by GlNR2 of nitro drugs may be the consequence of a secondary enzymatic activity either yielding (GlNR1) or eliminating (GlNR2) toxic intermediates after reduction of these compounds. © 2015 The Authors. Published by Elsevier Ltd on behalf of Australian Society for Parasitology. This is an open access article under the CC BY-NC-ND license

Isaak Troki, ein Apologet des Judenthums am Ende des sechszehnten Jahrhunderts

von Abraham Geiger

Kanzelreden

von David Feuchtwang