RESUMEN

Biomechanical studies in sauropod dinosaurs are mainly focused on neck posture and feeding strategy. Few works investigate other aspects such as tail movement and function, especially in the clade Titanosauria, the most diverse within Neosauropoda. This study applied biomechanical concepts of neutral pose (cartilaginous neutral pose) and range of motion to verify the shape and direction of the caudal region of the advanced titanosaurs Adamantisaurus mezzalirai and Baurutitan britoi, in addition to comparing it with other titanosaurs (e.g., Arrudatitan maximus, Lirainosaurus astibiae, and Trigonosaurus pricei). As a result, the tails analyzed have a sigmoidal-convex shape, probably close to the ground (but not touching it). The sigmoidal-convex shape could increase the moment arm for the M. caudofemoralis longus, making it possible to use the tail as a fifth stabilizing member. This work expands our knowledge about sauropod dinosaurs by exposing a diversity of shapes for the tails of titanosaur sauropods and brings new possibilities for how these dinosaurs could use their tails.

RESUMEN

A diketopyrrolopyrrole (DPP) and perylene diimide (PDI)-based molecule, denoted as PDI-DPP-PDI, was investigated as an electron acceptor material in bulk heterojunction (BHJ) solar cells, with poly[[4,8-bis [5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl] [2-(2-ethyl-1-oxohexyl)thieno[3,4-b]thiophenediyl]] (PBDTTT-CT) as an electron donor. The donor polymer and the acceptor molecule have complementary absorption spectra, which is an essential feature for energy collection in organic solar cells. However, AFM images indicated the presence of isolated and microsized PDI-DPP-PDI domains along the surface of the films, which reduced the power conversion efficiency. Therefore, to improve the homogenization of the acceptor along the film, a post-deposition treatment, denoted as solvent vapor annealing (SVA), was performed in a saturated atmosphere containing the vapour of an organic solvent for 3-10 minutes. This procedure changed the optical and morphological properties of the PBDTTT-CT : PDI-DPP-PDI active layer, resulting in increased power conversion efficiency values by more than 2.5 times (reaching 5.1%). Theoretical simulation pointed out that the experimental absorbance band localized at 580 nm, which appeared after SVA treatment, is possibly related to an intense simulated band with a maximum at 572 nm, resulting from a pair of transitions starting in the copolymer and ending in PDI-DPP-PDI, in regions where both are stacked at about 3 Å. The most significant natural transition orbitals (NTOs) related to these transitions indicated charge transfer character. Moreover, analyses carried out by power spectrum density (PDS) of images acquired from the SVA-treated film indicated that in the region of larger frequencies, across the length scale at around 30-70 nm, an additional fractal region appeared with a Ds of 0.95, indicating a flattened region, possibly related to changes in the overall conformation after SVA treatment. This indicates an improvement in the molecular packing, a feature not observed in the as-cast film. The analyses by force curve spectroscopy pointed out increased adhesion forces and adhesion energy in the PBDTTT-CT : PDI-DPP-PDI film after SVA treatment; this feature enhanced the interfacial interaction with the top electrodes, reflecting improved charge extraction in the photovoltaic device.

RESUMEN

The Continental African abelisauroid theropod dinosaur fossil record from the Jurassic-Cretaceous periods is becoming increasingly better understood, and offers great insight into the evolution and biogeography of this long-lived group of carnivores. Abelisauroidea is among the most familiar groups of theropod dinosaurs from Gondwana, with fossil records in South America, Australia, India and Africa, along with Europe. The objective of the present study is to review the fossil record of abelisauroids in continental Africa. Based on the literature and records from the online databases "The Paleobiology Database" and "The Theropod Database", we review the distribution of these theropods in Africa and comment on their evolution. The African continent is a major region of importance when it comes to 26 Abelisauroidea fossil findings, including records of both major subdivisions of the clade: the Abelisauridae and Noasauridae families. The oldest Abelisauroidea fossil record found in Africa dates from the Late Jurassic, while the final records date from the end of the Cretaceous. This indicates that clade was the longest surviving lineage of the large theropods of Africa, and they filled a variety of ecological roles, including apex predators, at the end of the Cretaceous, when tyrannosaurids occupied similar niches in the northern continents.

Asunto(s)

RESUMEN

We present a complete theoretical protocol to partition infrared intensities into terms owing to individual atoms by two different but related approaches: the atomic contributions (ACs) show how the entire molecular vibrational motion affects the electronic structure of a single atom and the total infrared intensity. On the other hand, the dynamic contributions (DCs) show how the displacement of a single atom alters the electronic structure of the entire molecule and the total intensity. The two analyses are complementary ways of partitioning the same total intensity and conserve most of the features of the total intensity itself. Combined, they are called the AC/DC analysis. These can be further partitioned following the CCTDP (or CCT) models according to the population analysis chosen by the researcher. The main conceptual features of the equations are highlighted, and representative numerical results are shown to support the interpretation of the equations. The results are invariant to rotation and translation and can readily be extended to molecules of any size, shape, or symmetry. Although the AC/DC analysis requires the choice of a charge model, all charge models that correctly reproduce the total molecular dipole moment can be used. A fully automated protocol managed by the Placzek program is made available, free of charge and with input examples.

RESUMEN

Titanosaurs are one of the most common dinosaurs found in Cretaceous outcrops, especially in Brazil. In this article we describe a proximal portion of an ulna (Paleo-UFG/V-0039) which was found isolated Paleo-UFG/V-0039 comes from a sandstone outcrop, with fine to medium granulation, of the Marília Formation (Bauru Group) that appears irregularly in the municipality of Gurinhatã, state of Minas Gerais, Brazil. The occurrence described here is the first dinosaur osteological remains documented in this municipality. Although incomplete, Paleo-UFG/V-0039 could be identified as an indeterminate lithostrotian titanosaur whose morphology is similar to some appendicular elements of European species than South American ones. However, the incompleteness of the specimen has difficult complex interpretations. Finally, Paleo-UFG/V-0039 highlights the importance of the Gurinhatã outcrops and other sites in this region for future discoveries.(AU)

Asunto(s)

RESUMEN

Abstract Titanosaurs are one of the most common dinosaurs found in Cretaceous outcrops, especially in Brazil. In this article we describe a proximal portion of an ulna (Paleo-UFG/V-0039) which was found isolated Paleo-UFG/V-0039 comes from a sandstone outcrop, with fine to medium granulation, of the Marília Formation (Bauru Group) that appears irregularly in the municipality of Gurinhatã, state of Minas Gerais, Brazil. The occurrence described here is the first dinosaur osteological remains documented in this municipality. Although incomplete, Paleo-UFG/V-0039 could be identified as an indeterminate lithostrotian titanosaur whose morphology is similar to some appendicular elements of European species than South American ones. However, the incompleteness of the specimen has difficult complex interpretations. Finally, Paleo-UFG/V-0039 highlights the importance of the Gurinhatã outcrops and other sites in this region for future discoveries.

RESUMEN

Abstract Titanosaurs are one of the most common dinosaurs found in Cretaceous outcrops, especially in Brazil. In this article we describe a proximal portion of an ulna (Paleo-UFG/V-0039) which was found isolated Paleo-UFG/V-0039 comes from a sandstone outcrop, with fine to medium granulation, of the Marília Formation (Bauru Group) that appears irregularly in the municipality of Gurinhatã, state of Minas Gerais, Brazil. The occurrence described here is the first dinosaur osteological remains documented in this municipality. Although incomplete, Paleo-UFG/V-0039 could be identified as an indeterminate lithostrotian titanosaur whose morphology is similar to some appendicular elements of European species than South American ones. However, the incompleteness of the specimen has difficult complex interpretations. Finally, Paleo-UFG/V-0039 highlights the importance of the Gurinhatã outcrops and other sites in this region for future discoveries.

RESUMEN

Noasaurines form an enigmatic group of small-bodied predatory theropod dinosaurs known from the Late Cretaceous of Gondwana. They are relatively rare, with notable records in Argentina and Madagascar, and possible remains reported for Brazil, India, and continental Africa. In south-central Brazil, the deposits of the Bauru Basin have yielded a rich tetrapod fauna, which is concentrated in the Bauru Group. The mainly aeolian deposits of the Caiuá Group, on the contrary, bear a scarce fossil record composed only of lizards, turtles, and pterosaurs. Here, we describe the first dinosaur of the Caiuá Group, which also represents the best-preserved theropod of the entire Bauru Basin known to date. The recovered skeletal parts (vertebrae, girdles, limbs, and scarce cranial elements) show that the new taxon was just over 1 m long, with a unique anatomy among theropods. The shafts of its metatarsals II and IV are very lateromedially compressed, as are the blade-like ungual phalanges of the respective digits. This implies that the new taxon could have been functionally monodactyl, with a main central weight-bearing digit, flanked by neighbouring elements positioned very close to digit III or even held free of the ground. Such anatomical adaptation is formerly unrecorded among archosaurs, but has been previously inferred from footprints of the same stratigraphic unit that yielded the new dinosaur. A phylogenetic analysis nests the new taxon within the Noasaurinae clade, which is unresolved because of the multiple alternative positions that Noasaurus leali can acquire in the optimal trees. The exclusion of the latter form results in positioning the new dinosaur as the sister-taxon of the Argentinean Velocisaurus unicus.

Asunto(s)

RESUMEN

A study is presented on the resonance Raman (RR) spectrum based on fully anharmonic wave functions and energies obtained from ab initio multireference potential energy curves of diatomic systems. The vibrational problem is numerically solved using a variational stochastic method or the Cooley-Numerov method, as implemented in Le Roy's LEVEL program. Anharmonic Franck-Condon and Herzberg-Teller integrals are numerically evaluated, and the RR polarizability is calculated within the time-independent framework of the RR theory. At the harmonic level, the differential cross sections show faster convergence with respect to the number of intermediate vibrational states than what is obtained from anharmonic wave functions. Twice as many intermediate states are required to achieve the same convergence in the RR intensities as observed within the harmonic model. The anharmonic spectra evaluated for H2, C2, and O2 molecules show that RR intensities are strongly affected by anharmonic effects. They differ from their harmonic counterparts not only in the position of the peaks but also in the absolute and relative intensities.

RESUMEN

Over the last few decades, the systematics and evolution of carcharodontosaurids, a group of large predatory dinosaurs, from North Africa have been better understood mainly due the discovery of new species. We review this record here and discuss its importance for understanding the evolution and ecology of these dinosaurs. North Africa has one of the best records of carcharodontosaurid species. These species show dietary specializations and paleogeographic distributions similar to other top predatory theropods such as Abelisauridae and Spinosauridae. However, carcharodontosaurids have a wider distribution than other large theropods. The middle Cretaceous of North Africa was characterized by the niche overlap between large predators. This evidence increases our understanding of the evolution of Carcharodontosauridae in a highly competitive region, a conjuncture rarely reported for large top predators.

Asunto(s)

RESUMEN

Over the last few decades, the systematics and evolution of carcharodontosaurids, a group of large predatory dinosaurs, from North Africa have been better understood mainly due the discovery of new species. We review this record here and discuss its importance for understanding the evolution and ecology of these dinosaurs. North Africa has one of the best records of carcharodontosaurid species. These species show dietary specializations and paleogeographic distributions similar to other top predatory theropods such as Abelisauridae and Spinosauridae. However, carcharodontosaurids have a wider distribution than other large theropods. The middle Cretaceous of North Africa was characterized by the niche overlap between large predators. This evidence increases our understanding of the evolution of Carcharodontosauridae in a highly competitive region, a conjuncture rarely reported for large top predators.(AU)

Asunto(s)

RESUMEN

The monosignate character of resonance Raman optical activity (RROA) spectra has been often taken as granted in experimental and computational approaches, on the basis of basic theoretical approximations only considering resonance with a single electronic state of the molecule and the scattering process to be governed by the Franck-Condon mechanism. We show in this letter for the first time that, by resorting to a fully quantum mechanical (QM) methodology able to take into account all terms entering the general definition of RROA, and which considers excited state interference and Herzberg-Teller effects, sign alternation and at the same time intensity enhancement in RROA spectra is obtained. Such features constitute an important milestone toward the exploration of RROA of a wide range of chiral biological molecules.

RESUMEN

The experimental infrared fundamental intensities of gas phase carbonyl compounds obtained by the integration of spectral bands in the Pacific Northwest National Laboratory (PNNL) spectral database are in good agreement with the intensities reported by other laboratories having a root mean square error of 27 km mol(-1) or about 13% of the average intensity value. The Quantum Theory of Atoms in Molecules/Charge-Charge Transfer-Counterpolarization (QTAIM/CCTCP) model indicates that the large intensity variation from 61.7 to 415.4 km mol(-1) is largely due to static atomic charge contributions, whereas charge transfer and counterpolarization effects essentially cancel one another leaving only a small net effect. The Characteristic Substituent Shift Model estimates the atomic charge contributions to the carbonyl stretching intensities within 30 km mol(-1) or 10% of the average contribution. However, owing to the size of the 2 × C × CTCP interaction contribution, the total intensities cannot be estimated with this degree of accuracy. The dynamic intensity contributions of the carbon and oxygen atoms account for almost all of the total stretching intensities. These contributions vary over large ranges with the dynamic contributions of carbon being about twice the size of the oxygen ones for a large majority of carbonyls. Although the carbon monoxide molecule has an almost null dipole moment contrary to the very polar bond of the characteristic carbonyl group, its QTAIM/CCTCP model is very similar to those found for the carbonyl compounds.

RESUMEN

Simple procedures for the location of proper and improper rotations and reflexion planes are presented. The search is performed with a molecule divided into subsets of symmetrically equivalent atoms (SEA) which are analyzed separately as if they were a single molecule. This approach is advantageous in many aspects. For instance, in those molecules that are symmetric rotors, the number of atoms and the inertia tensor of the SEA provide one straight way to find proper rotations of any order. The algorithms are invariant to the molecular orientation and their computational cost is low, because the main information required to find symmetry elements is interatomic distances and the principal moments of the SEA. For example, our Fortran implementation, running on a single processor, took only a few seconds to locate all 120 symmetry operations of the large and highly symmetrical fullerene C720, belonging to the Ih point group. Finally, we show how the interatomic distances matrix of a slightly unsymmetrical molecule is used to symmetrize its geometry.

Asunto(s)

Asunto(s)

Asunto(s)

RESUMEN

Stromal tissue regulates the development and differentiation of breast epithelial cells, with adipocytes being the main stromal cell type. The aim of the present study was to evaluate the effect of adipocyte differentiation on proliferation and migration, as well as to assess the activity of heparanase and metalloproteinase-9 (MMP-9), in normal (NMuMG) and tumoral (LM3) murine breast epithelial cells. NMuMG and LM3 cells were grown on irradiated 3T3-L1 cells (stromal support, SS) at various degrees of differentiation [preadipocytes (preA), poorly differentiated adipocytes (pDA) and mature adipocytes (MA)] and/or were incubated in the presence of conditioned medium (CM) derived from each of these three types of differentiated cells. Cells grown on a plastic support or in fresh medium served as the controls. Cell proliferation was measured with a commercial colorimetric kit, and the motility of the epithelial cells was evaluated by means of a wound-healing assay. Heparanase activity was assessed by quantifying heparin degradation, and the expression of MMP-9 was determined using Western blotting. The results indicate that cell proliferation was increased after 24 and 48 h in the NMuMG and LM3 cells grown on preA, pDA and MA SS. In the NMuMG cells cultured on SS in the presence of all three types of CM, proliferation was enhanced. LM3 cell migration was increased in the presence of all three types of CM and in cells grown on preA SS. Heparanase activity was increased in the NMuMG cells incubated with all three types of CM, and in the LM3 cells incubated with the CM from pDA and MA. Both the NMuMG and LM3 cell lines presented basal expression of MMP-9; however, a significant increase in MMP-9 expression was observed in the LM3 cells incubated with each of the three types of CM. In conclusion, adipocyte differentiation influences normal and tumoral breast epithelial cell proliferation and migration. Heparanase and MMP-9 appear to be involved in this regulation. The experimental model presented in this study is in keeping with the characteristics of the physiological environment of breast epithelial cells, in terms of both the soluble and insoluble factors present and the stromal structure per se.

RESUMEN

The molecular dipole moments, their derivatives, and the fundamental IR intensities of the X2CY (X = H, F, Cl; Y = O, S) molecules are determined from QTAIM atomic charges and dipoles and their fluxes at the MP2/6-311++G(3d,3p) level. Root-mean-square errors of +/-0.03 D and +/-1.4 km mol(-1) are found for the molecular dipole moments and fundamental IR intensities calculated using quantum theory of atoms in molecules (QTAIM) parameters when compared with those obtained directly from the MP2/6-311++G(3d,3p) calculations and +/-0.05 D and 51.2 km mol(-1) when compared with the experimental values. Charge (C), charge flux (CF), and dipole flux (DF) contributions are reported for all the normal vibrations of these molecules. A large negative correlation coefficient of -0.83 is calculated between the charge flux and dipole flux contributions and indicates that electronic charge transfer from one side of the molecule to the other during vibrations is accompanied by a relaxation effect with electron density polarization in the opposite direction. The characteristic substituent effect that has been observed for experimental infrared intensity parameters and core electron ionization energies has been applied to the CCFDF/QTAIM parameters of F2CO, Cl2CO, F2CS, and Cl2CS. The individual atomic charge, atomic charge flux, and atomic dipole flux contributions are seen to obey the characteristic substituent effect equation just as accurately as the total dipole moment derivative. The CH, CF, and CCl stretching normal modes of these molecules are shown to have characteristic sets of charge, charge flux, and dipole flux contributions.