989 resultados para MOLAR
Resumo:
We provide a taxonomic redescription of the Fawn Antechinus, Antechinus bellus (Thomas). A. bellus is the only member of its genus to occur in Australia’s Northern Territory, where it can be found in savannah woodlands of the Top End. It is perhaps the most distinctive antechinus, and clearly distinguishable from the other 10 extant species of antechinus found in Australia: externally, A. bellus has pale body fur, white feet and large ears; A. bellus skulls have large auditory bullae and narrow interorbital width, while broadening abruptly at the molar row; mitochondrial and nuclear genes clearly dis-tinguish A. bellus from all congeners, phylogenetically positioning the Fawn Antechinus as sister to Queensland’s A. leo Van Dyck, 1980, with which it shares a curled supratragus of the external ear and a similar tropical latitudinal range.
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Antechinus argentus sp. nov. is currently only known from the plateau at the eastern escarpment of Kroombit Tops National Park, about 400km NNW of Brisbane and 60km SSW of Gladstone, south-east Queensland, Australia. Antechinus flavipes (Waterhouse) is also known from Kroombit Tops NP, 4.5km W of the nearest known population of A. argentus; A. mysticus Baker, Mutton and Van Dyck has yet to be found within Kroombit Tops, but is known from museum specimens taken at Bulburin NP, just 40km ESE, as well as extant populations about 400km to both the south-east and north-west of Kroombit NP. A. argentus can be easily distinguished in the field, having an overall silvery/grey appearance with much paler silver feet and drabber deep greyish-olive rump than A. flavipes, which has distinctive yellow-orange toned feet, rump and tail-base; A. argentus fur is also less coarse than that of A. flavipes. A. argentus has a striking silver-grey head, neck and shoulders, with pale, slightly broken eye-rings, which distinguish it from A. mysticus which has a more subtle greyish-brown head, pale buff dabs of eyeliner and more colourful brownish-yellow rump. Features of the dentary can also be used for identification: A. argentus differs from A. flavipes in having smaller molar teeth, as well as a narrower and smaller skull and from A. mysticus in having on average a narrower snout, smaller skull and dentary lengths and smaller posterior palatal vacuities in the skull. A. argentus is strongly divergent genetically (at mtDNA) from both A. flavipes (9.0–11.2%) and A. mysticus (7.2–7.5%), and forms a very strongly supported clade to the exclusion of all other antechinus species, in both mtDNA and combined (mtDNA and nDNA) phylogenies inferred here. We are yet to make detailed surveys in search of A. argentus from forested areas to the immediate east and north of Kroombit Tops. However, A. mysticus has only been found at these sites in low densities in decades past and not at all in several recent trapping expeditions conducted by the authors. With similar habitat types in close geographic proximity, it is plausible that A. argentus may be found outside Kroombit. Nevertheless, it is striking that from a range of surveys conducted at Kroombit Tops in the last 15 years and intensive surveys by the authors in the last 3 years, totalling more than 5 080 trap nights, just 13 A. argentus have been captured from two sites less than 6 km apart. If this is even close to the true geographic extent of the species, it would possess one of the smallest distributions of an Australian mammal species. With several threats identified, we tentatively recommend that A. argentus be listed as Endangered, pending an exhaustive trapping survey of Kroombit and surrounds.
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The synthesis of thiophene-containing second (G2) and third generation (G3) dendronized macromonomers with methacrylate polymerizable units as well as their corresponding dendronized polymers is reported. The dendrons are prepared from branched thiophene oligomers and are decorated with straight alkyl chains for solubility reasons. The polymerization reactions were done with AIBN as initiator and the polymers were characterized by NMR spectroscopy, elemental analysis and GPC. Molar masses are in the range of 2.2-5.4 × 105 g mol-1 (G2) and 1.3-3.0 × 104 g mol-1 (G3) for different runs. These polymers are investigated by cyclic voltammetry and optical spectroscopy.
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In recent years, the beauty leaf plant (Calophyllum Inophyllum) is being considered as a potential 2nd generation biodiesel source due to high seed oil content, high fruit production rate, simple cultivation and ability to grow in a wide range of climate conditions. However, however, due to the high free fatty acid (FFA) content in this oil, the potential of this biodiesel feedstock is still unrealized, and little research has been undertaken on it. In this study, transesterification of beauty leaf oil to produce biodiesel has been investigated. A two-step biodiesel conversion method consisting of acid catalysed pre-esterification and alkali catalysed transesterification has been utilized. The three main factors that drive the biodiesel (fatty acid methyl ester (FAME)) conversion from vegetable oil (triglycerides) were studied using response surface methodology (RSM) based on a Box-Behnken experimental design. The factors considered in this study were catalyst concentration, methanol to oil molar ratio and reaction temperature. Linear and full quadratic regression models were developed to predict FFA and FAME concentration and to optimize the reaction conditions. The significance of these factors and their interaction in both stages was determined using analysis of variance (ANOVA). The reaction conditions for the largest reduction in FFA concentration for acid catalysed pre-esterification was 30:1 methanol to oil molar ratio, 10% (w/w) sulfuric acid catalyst loading and 75 °C reaction temperature. In the alkali catalysed transesterification process 7.5:1 methanol to oil molar ratio, 1% (w/w) sodium methoxide catalyst loading and 55 °C reaction temperature were found to result in the highest FAME conversion. The good agreement between model outputs and experimental results demonstrated that this methodology may be useful for industrial process optimization for biodiesel production from beauty leaf oil and possibly other industrial processes as well.
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The effects of estrogen deficiency on bone characteristics are site-dependent, with the most commonly studied sites being appendicular long bones (proximal femur and tibia) and axial bones (vertebra). The effect on the maxillary and mandibular bones is still inconsistent and requires further investigation. This study was designed to evaluate bone quality in the posterior maxilla of ovariectomized rats in order to validate this site as an appropriate model to study the effect of osteoporotic changes. Methods: Forty-eight 3-month-old female Sprague-Dawley rats were randomly divided into two groups: an ovariectomized group (OVX, n=24) and Sham-operated group (SHAM, n=24). Six rats were randomly sacrificed from both groups at time points 8, 12, 16 and 20 weeks. The samples from tibia and maxilla were collected for Micro CT and histological analysis. For the maxilla, the volume of interest (VOI) area focused on the furcation areas of the first and second molar. Trabecular bone volume fraction (BV/TV, %), trabecular thickness (Tb.Th.), trabecular number (Tb.N.), trabecular separation (Tb.Sp.), and connectivity density (Conn.Dens) were analysed after Micro CT scanning. Results: At 8 weeks the indices BV/TV, Tb.Sp, Tb.N and Conn.Dens showed significant differences (P<0.05) between the OVX and SHAM groups in the tibia. Compared with the tibia, the maxilla developed osteoporosis at a later stage, with significant changes in maxillary bone density only occurring after 12 weeks. Compared with the SHAM group, both the first and second molars of the OVX group showed significantly decreased BV/TV values from 12 weeks, and these changes were sustained through 16 and 20 weeks. For Tb.Sp, there were significant increases in bone values for the OVX group compared with the SHAM group at 12, 16 and 20 weeks. Histological changes were highly consistent with Micro CT results. Conclusion: This study established a method to quantify the changes of intra-radicular alveolar bone in the posterior maxilla in an accepted rat osteoporosis model. The degree of the osteoporotic changes to trabecular bone architecture is site-dependent and at least 3 months are required for the osteoporotic effects to be apparent in the posterior maxilla following rat OVX.
Hydrolysis of genotoxic methyl-substituted oxiranes : Experimental kinetic and semiempirical studies
Resumo:
The kinetics of acid-catalyzed hydrolysis of seven methylated aliphatic epoxides - R1R2C(O)CR3R4 (A: R1=R2=R3=R4=H; B: R1=R2=R3=H, R4=Me; C: R1=R2=H, R3=R4=Me; D: R1=R3=H, R2=R4=Me(trans); E: R1=R3=H, R2=R4=Me(cis); F: R1=R3=R4=Me, R2=H; G: R1=R2=R3=R4=Me) - has been studied at 36 ± 1.5°C. Compounds with two methyl groups at the same carbon atom of the oxirane ring exhibit highest rate constants (k(eff) in reciprocal molar concentration per second: 11.0 ± 1.3 for C, 10.7 ± 2.1 for F, and 8.7 ± 0.7 for G as opposed to 0.124 ± 0.003 for B, 0.305 ± 0.003 for D, and 0.635 ± 0.036 for E). Ethylene oxide (A) displays the lowest rate of hydrolysis (0.027 M-1 s-1). The results are consistent with literature data available for compounds A, B, and C. To model the reactivities we have employed quantum chemical calculations (MNDO, AM1, PM3, and MINDO/3) of the main reaction species. There is a correlation of the logarithm k(eff) with the total energy of epoxide ring opening. The best correlation coefficients (r) were obtained using the AM1 and MNDO methods (0.966 and 0.957, respectively). However, unlike MNDO, AM1 predicts approximately zero energy barriers for the oxirane ring opening of compounds B, C, E and G, which is not consistent with published kinetic data. Thus, the MNDO method provides a preferential means of modeling the acidic hydrolysis of the series of methylated oxiranes. The general ranking of mutagenicity in vitro, A > B > C, is in line with the concept that this sequence also gradually leaves the expoxide reactivity optimal for genotoxicity toward reactivities leading to higher biological detoxifications.
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Synthesis of imines from amines and aliphatic alcohols (C1–C6) in the presence of base on supported palladium nanoparticles has been achieved for the first time. The catalytic system shows high activity and selectivity in open air at room temperature. As an example of the isostructural Ln3Sb3Co2O14 (Ln: La, Pr, Nd, Sm—Ho) series with an ordered pyrochlore structure, the La variant is prepared by a citrate complex method employing stoichiometric amounts of La(NO3)3, Co(NO3)2, and Sb tartrate together with citric acid with a metal/citrate molar ratio of 1:2
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A series of macro–mesoporous TiO2/Al2O3 nanocomposites with different morphologies were synthesized. The materials were calcined at 723 K and were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), X-ray photoelectron spectroscopy (XPS) and UV–visible spectroscopy (UV–visible). A modified approach was proposed for the synthesis of 1D (fibrous) nanocomposite with higher Ti/Al molar ratio (2:1) at lower temperature (<100 °C), which makes it possible to synthesize such materials on industrial scale. The performance–morphology relationship of as-synthesized TiO2/Al2O3 nanocomposites was investigated by the photocatalytic degradation of a model organic pollutant under UV irradiation. The samples with 1D (fibrous) morphology exhibited superior catalytic performance than the samples without, such as titania microspheres.
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Tooeleite is an unique ferric arsenite sulfate mineral, which has the potential significance of directly fixing As(III) as mineral trap. The tooeleite and various precipitates were hydrothermally synthesized under the different of initial As(III)/As(V) molar ratios and characterized by XRD, FTIR, XPS and SEM. The crystallinity of tooeleite decreases with the amount of As(V). The precipitate is free of any crystalline tooeleite at the level of that XRD could detect when the ratio of As(III)/As(V) of 7:3 and more. The characteristic bands of tooeleite are observed in 772, 340, 696 and 304 cm−1, which are assigned to the ν1, ν2, ν3 and ν4 vibrations of AsO33−. These intensities of bands gradually decreases with the presence of As(V) and its increasing. An obviously wide band is observed in 830 cm−1, which is the ν1 vibration of AsO4. The result of XPS reveals that the binding energies of As3d increase from 44.0 eV to 45.5 eV, which indicates that the amount of As(V) in the precipitates increases. The concentrations of arsenic released of these precipitates are 350–650 mg/L. The stability of tooeleite decreases by comparison when the presence of coexisting As(V) ions.
Resumo:
Background Ephrin-B2 is the sole physiologically-relevant ligand of the receptor tyrosine kinase EphB4, which is over-expressed in many epithelial cancers, including 66% of prostate cancers, and contributes to cancer cell survival, invasion and migration. Crucially, however, the cancer-promoting EphB4 signalling pathways are independent of interaction with its ligand ephrin-B2, as activation of ligand-dependent signalling causes tumour suppression. Ephrin-B2, however, is often found on the surface of endothelial cells of the tumour vasculature, where it can regulate angiogenesis to support tumour growth. Proteolytic cleavage of endothelial cell ephrin-B2 has previously been suggested as one mechanism whereby the interaction between tumour cell-expressed EphB4 and endothelial cell ephrin-B2 is regulated to support both cancer promotion and angiogenesis. Methods An in silico approach was used to search accessible surfaces of 3D protein models for cleavage sites for the key prostate cancer serine protease, KLK4, and this identified murine ephrin-B2 as a potential KLK4 substrate. Mouse ephrin-B2 was then confirmed as a KLK4 substrate by in vitro incubation of recombinant mouse ephrin-B2 with active recombinant human KLK4. Cleavage products were visualised by SDS-PAGE, silver staining and Western blot and confirmed by N-terminal sequencing. Results At low molar ratios, KLK4 cleaved murine ephrin-B2 but other prostate-specific KLK family members (KLK2 and KLK3/PSA) were less efficient, suggesting cleavage was KLK4-selective. The primary KLK4 cleavage site in murine ephrin-B2 was verified and shown to correspond to one of the in silico predicted sites between extracellular domain residues arginine 178 and asparagine 179. Surprisingly, the highly homologous human ephrin-B2 was poorly cleaved by KLK4 at these low molar ratios, likely due to the 3 amino acid differences at this primary cleavage site. Conclusion These data suggest that in in vivo mouse xenograft models, endogenous mouse ephrin-B2, but not human tumour ephrin-B2, may be a downstream target of cancer cell secreted human KLK4. This is a critical consideration when interpreting data from murine explants of human EphB4+/KLK4+ cancer cells, such as prostate cancer cells, where differential effects may be seen in mouse models as opposed to human clinical situations.
Resumo:
Background Osteocytes, the most abundant cells in bone, havemultiple functions, including acting as mechanosensors and regulating mineralization. It is clear that osteocytes influence bone remodeling by controlling the differentiation and activity of osteoblasts and osteoclasts. Determining the relationship between titanium implants and osteocytes may therefore benefit our understanding of the process of osseointegration. Purpose The aim of this study was to visualize the ultrastructural relationship between osteocytes and the titanium implant surface following osseointegration in vivo. Materials and Methods Titanium implants were placed in the maxillary molar regions of eight female Sprague Dawley rats, 3 months old. The animals were sacrificed 8 weeks after implantation, and undecalcified tissue sections were prepared. Resin-cast samples were subsequently acid-etched with 37% phosphoric acid prior to examination using scanning electron microscopy. Results Compared with mature bone, where the osteocytes were arranged in an ordered fashion, the osteocytes appeared less organized in the newly formed bone around the titanium implant. Further, a layer of mineralization with few organic components was observed on the implant surface. This study shows for the first time that osteocytes and their dendrites are directly connected with the implant surface. Conclusions: This study shows the direct anchorage of osteocytes via dendritic processes to a titanium implant surface in vivo. This suggests an important regulatory role for osteocytes and their lacunar-canalicular network in maintaining long-term osseointegration.
Resumo:
Everything revolves around desiring-machines and the production of desire… Schizoanalysis merely asks what are the machinic, social and technical indices on a socius that open to desiring-machines (Deleuze & Guattari, 1983, pp. 380-381). Achievement tests like NAPLAN are fairly recent, yet common, education policy initiatives in much of the Western world. They intersect with, use and change pre-existing logics of education, teaching and learning. There has been much written about the form and function of these tests, the ‘stakes’ involved and the effects of their practice. This paper adopts a different “angle of vision” to ask what ‘opens’ education to these regimes of testing(Roy, 2008)? This paper builds on previous analyses of NAPLAN as a modulating machine, or a machine characterised by the increased intensity of connections and couplings. One affect can be “an existential disquiet” as “disciplinary subjects attempt to force coherence onto a disintegrating narrative of self”(Thompson & Cook, 2012, p. 576). Desire operates at all levels of the education assemblage, however our argument is that achievement testing manifests desire as ‘lack’; seen in the desire for improved results, the desire for increased control, the desire for freedom, the desire for acceptance to name a few. For Deleuze and Guattari desire is irreducible to lack, instead desire is productive. As a productive assemblage, education machines operationalise and produce through desire; “Desire is a machine, and the object of the desire is another machine connected to it”(Deleuze & Guattari, 1983, p. 26). This intersection is complexified by the strata at which they occur, the molar and molecular connections and flows they make possible. Our argument is that when attention is paid to the macro and micro connections, the machines built and disassembled as a result of high-stakes testing, a map is constructed that outlines possibilities, desires and blockages within the education assemblage. This schizoanalytic cartography suggests a new analysis of these ‘axioms’ of testing and accountability. It follows the flows and disruptions made possible as different or altered connections are made and as new machines are brought online. Thinking of education machinically requires recognising that “every machine functions as a break in the flow in relation to the machine to which it is connected, but at the same time is also a flow itself, or the production of flow, in relation to the machine connected to it”(Deleuze & Guattari, 1983, p. 37). Through its potential to map desire, desire-production and the production of desire within those assemblages that have come to dominate our understanding of what is possible, Deleuze and Guattari’s method of schizoanalysis provides a provocative lens for grappling with the question of what one can do, and what lines of flight are possible.
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Background: There are persistent concerns about litigation in the dental and medical professions. These concerns arise in a setting where general dentists are more frequently undertaking a wider range of oral surgery procedures, potentially increasing legal risk. Methods: Judicial cases dealing with medical negligence in the fields of general dentistry (oral surgery procedure) and Oral and Maxillofacial Surgery were located using the three main legal databases. Relevant cases were analysed to determine the procedures involved, the patients’ claims of injury, findings of negligence, and damages awarded. A thematic analysis of the cases was undertaken to determine trends. Results: Fifteen cases over a twenty-year period were located across almost all Australian jurisdictions (eight cases involved general dentists; seven cases involved Oral and Maxillofacial Surgeons). Eleven of the fifteen cases involved determinations of whether or not the practitioner had failed in their duty of care; negligence was found in six cases. Eleven of the fifteen cases related to molar extractions (eight specifically to third molar). Conclusions: Dental and medical practitioners wanting to manage legal risk should have regard to circumstances arising in judicial cases. Adequate warning of risks is critical, as is offering referral in appropriate cases. Pre-operative radiographs, good medical records, and processes to ensure appropriate follow-up are also important.
Resumo:
Two new star-burst compounds based on 1,3,5-triazine core and carbazole end-capped phenylene ethynylene arms (1a and 1b) were synthesized and characterized. Their photophysical properties were investigated systematically via spectroscopic and theoretical methods. Both compounds exhibit strong 1π–π⁎ transitions in the UV region and intense 1π–π⁎/intramolecular charge transfer (1ICT) absorption bands in the UV–vis region. Introducing the carbazole end-capped phenylene ethynylene arm on the 1,3,5-triazine core causes a slight bathochromic shift and enhanced molar extinction coefficient of the 1π–π⁎/1ICT transition band. Both compounds are emissive in solution at room temperature and 77 K, which exhibit pronounced positive solvatochromic effect. The emitting state could be ascribed to 1ICT state in more polar solvent, and 1π–π⁎ state in low-polarity solvent. The high emission quantum yields (Φem=0.90~1.0) of 1a and 1b (in hexane and toluene) make them potential candidates as efficient light-emitting materials. The spectroscopic studies and theoretical calculations indicate that the photophysical properties of these compounds can be tuned by the carbazole end-capped phenylene ethynylene arm, which would also be useful for rational design of photofunctional materials.
Resumo:
We find that visible light irradiation of gold–palladium alloy nanoparticles supported on photocatalytically inert ZrO2 significantly enhances their catalytic activity for oxidant-free dehydrogenation of aromatic alcohols to the corresponding aldehydes at ambient temperatures. Dehydrogenation is also the dominant process in the selective oxidation of the alcohols to the corresponding aldehydes with molecular oxygen. The alloy nanoparticles strongly absorb light and exhibit superior catalytic and photocatalytic activity when compared to either pure palladium or gold nanoparticles. Analysis with a free electron gas model for the bulk alloy structure reveals that the alloying increases the surface charge heterogeneity on the alloy particle surface, which enhances the interaction between the alcohol molecules and the metal NPs. The increased surface charge heterogeneity of the alloy particles is confirmed with density function theory applied to small alloy clusters. Optimal catalytic activity was observed with a Au : Pd molar ratio of 1 : 186, which is in good agreement with the theoretical analysis. The rate-determining step of the dehydrogenation is hydrogen abstraction. The conduction electrons of the nanoparticles are photo-excited by the incident light giving them the necessary energy to be injected into the adsorbed alcohol molecules, promoting the hydrogen abstraction. The strong chemical adsorption of alcohol molecules facilitates this electron transfer. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive the dehydrogenation. These findings provide useful insight into the design of catalysts that utilize light for various organic syntheses at ambient temperatures.