Structure and ontogeny of Swartzia langsdorffii (Leguminosae) pericarp

In order to elucidate the position of the Swartzieae in Leguminosae, Swartzia langsdorffii was chosen as a representative of this tribe type genus and subjected to structural studies of immature ovaries (in the floral bud and flowers) and developing and mature fruits. The external epidermis of the ovary is characterized by one layer of thin-walled polyhedral cells with a thin cuticle. Parenchyma cells have a large quantity of tannin-containing idioblasts located inside a procambial ring. The one-layered inner epidermis consists of flattened cells. In fruits the one-layered exocarp is covered by a thick cuticle. The mesocarp consists of three distinct regions, the middle region being a sclerenchymatous layer. The one-layered endocarp shows cells with little cohesion. The occurrence of canals consisting of a net of resinous cells was also observed in the mesocarp. Secretion was of an elaborate composition. Differentiation of the secretory structures begin in the floral bud ovary, where they appear as idioblasts containing tannin. The taxonomic position of this tribe, as well as the function of the mesocarp secreting canals, are discussed.

Theoretical study of molecular and electronic structures of 5(1) knot systems: two-layered ONIOM calculations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Least-cost Disjoint Paths with Dependent Cost Structure in Wavelength Continuous Optical WDM Networks

One of the important issues in establishing a fault tolerant connection in a wavelength division multiplexing optical network is computing a pair of disjoint working and protection paths and a free wavelength along the paths. While most of the earlier research focused only on computing disjoint paths, in this work we consider computing both disjoint paths and a free wavelength along the paths. The concept of dependent cost structure (DCS) of protection paths to enhance their resource sharing ability was proposed in our earlier work. In this work we extend the concept of DCS of protection paths to wavelength continuous networks. We formalize the problem of computing disjoint paths with DCS in wavelength continuous networks and prove that it is NP-complete. We present an iterative heuristic that uses a layered graph model to compute disjoint paths with DCS and identify a free wavelength.

Layered Clustering Communication Protocol for Wireless Sensor Networks

In this paper, we propose a Layered Clustering Hierarchy (LCH) communication protocol for Wireless Sensor Networks (WSNs). The design of LCH has two goals: scalability and energy-efficiency. In LCH, the sensor nodes are organized as a layered clustering structure. Each layer runs a distributed clustering protocol. By randomizing the rotation of cluster heads in each layer, the energy load is distributed evenly across sensors in the network. Our simulations show that LCH is effective in densely deployed sensor networks. On average, 70% of live sensor nodes are involved directly in the clustering communication hierarchy. Moreover, the simulations also show that the energy load and dead nodes are distributed evenly over the network. As studies prove that the performance of LCH depends mainly on the distributed clustering protocol, the location of cluster heads and cluster size are two critical factors in the design of LCH.

Percolated non-Newtonian flow for silicone obtained from exfoliated bioinorganic layered double hydroxide intercalated with amino acid

A simple and scalable procedure was used to obtain thin, stable, homogeneous, and easy-to-handle films composed of silicone derived from dimethicones containing dispersed hydrotalcite-type materials previously organo-modified with amino acids. The absence of the typical X-ray pattern of the bioinorganic LDH filler suggested an exfoliation process that was further indirectly evidenced by a drastic change in the rheological behavior, which turned from a quasi-Newtonian behavior for the silicone free of LDH filler to an extensive developed gel-like structure for the nanocomposite derivatives. Visualized by the shear-thinning exponent of the complex viscosity in the low-frequency range, the percolation threshold was evident for filler loading as low as <5 w/W%, suggesting the presence of a largely developed interface between the filler and the polymer. The increase of more than one order of magnitude in viscosity was explained by the rather strong attrition phenomenon between the tethered amino acid anions and the silicone chains. UVB radiation absorption profiles make such bioinorganic polymer nanocomposites potentially applicable in skin protection. Thermo-gravimetric analysis revealed significant improvement in the thermal stability, especially in the final step of the polymer combustion, thus underlining the role of the hybrid material as a thermal retardant agent. (C) 2011 Elsevier B.V. All rights reserved.

Numerical combination for nonlinear analysis of structures coupled to layered soils

This paper presents an alternative coupling strategy between the Boundary Element Method (BEM) and the Finite Element Method (FEM) in order to create a computational code for the analysis of geometrical nonlinear 2D frames coupled to layered soils. The soil is modeled via BEM, considering multiple inclusions and internal load lines, through an alternative formulation to eliminate traction variables on subregions interfaces. A total Lagrangean formulation based on positions is adopted for the consideration of the geometric nonlinear behavior of frame structures with exact kinematics. The numerical coupling is performed by an algebraic strategy that extracts and condenses the equivalent soil's stiffness matrix and contact forces to be introduced into the frame structures hessian matrix and internal force vector, respectively. The formulation covers the analysis of shallow foundation structures and piles in any direction. Furthermore, the piles can pass through different layers. Numerical examples are shown in order to illustrate and confirm the accuracy and applicability of the proposed technique.

Structure and properties of composite polyolefin materials

This thesis is based on three main studies, all dealing with structure-property investigation of semicrystalline polyolefin-based composites. Low density poly(ethylene) (LDPE) and isotactic poly(propylene) (iPP) were chosen as parts of the composites materials and they were investigated either separately (as homoploymers), either in blend systems with the composition LDPE/iPP 80/20 or as filled matrix with layered silicate (montmorillonite). The beneficial influence of adding ethylene-co-propylene polymer of amorphous nature, to low density poly(ethylene)/isotactic poly(propylene) (80/20) blend is demonstrated. This effect is expressed by the major improvement of mechanical properties of ternary blends as examined at a macroscopic size scale by means of tensile measurements. The structure investigation also reveals a clear dependence of the morphology on adding ethylene-copropylene polymer. Both the nature and the content of ethylene-co-propylene polymer affect structure and properties. It is further demonstrated that the extent of improvement in mechanical properties is to be related to the molecular details of the compatibilizer. Combination of high molecular weight and high ethylene content is appropriate for the studied system where the poly(ethylene) plays the role of matrix. A new way to characterize semicrystalline systems by means of Brillouin spectroscopy is presented in this study. By this method based on inelastic light scattering, we were able to measure the high frequency elastic constant (c11) of the two microphases in the case where the spherulites size is exhibit size larger than the size of the probing phonon wavelength. In this considered case, the sample film is inhomogeneous over the relevant length scales and there is an access to the transverse phonon in the crystalline phase yielding the elastic constant c44 as well. Isotactic poly(propylene) is well suited for this type of investigation since its morphology can be tailored through different thermal treatment from the melt. Two distinctly different types of films were used; quenched (low crystallinity) and annealed (high crystallinity). The Brillouin scattering data are discussed with respect to the spherulites size, lamellae thickness, long period, crystallinity degree and well documented by AFM images. The structure and the properties of isotactic poly(propylene) matrix modified by inorganic layered silicate, montmorillonite, are discussed with respect to the clay content. Isotactic poly(propylene)-graft-maleic anhydride was used as compatibilizer. It is clearly demonstrated that the property enhancement is largely due to the ability of layered silicate to exfoliate. The intimate dispersion of the nanometer-thick silicate result from a delicate balance of the content ratio between the isotactic poly(propylene)-graft-maleic anhydride compatibilizer and the inorganic clay.

Synthesis and characterization of structurally well-defined polymer-layered silicate nanocomposites

Zusammenfassung Nanokomposite aus Polymeren und Schichtsilikaten werden zumeist auf der Basis natürlicher Tone wie Montmorillonit hergestellt. Für NMR- und EPR-Untersuchungen der Tensidschicht, die das Silikat mit dem Polymer kompatibilisiert, ist der Eisengehalt natürlicher Tone jedoch abträglich, weil er zu einer Verkürzung der Relaxationszeiten und zu einer Linienverbreiterung in den Spektren führt. Dieses Problem konnte überwunden werden, indem als Silikatkomponente eisenfreies, strukturell wohldefiniertes Magadiit hydrothermal synthetisiert und für die Kompositbildung eingesetzt wurde. Die Morphologie des Magadiits wurde durch Rasterelektronenmikroskopie charakterisiert und der Interkalationsgrad von schmelzinterkalierten Polymer-Nanokompositen wurde durch Weitwinkelröntgenstreuung bestimmt. Polymere mit Carbonylgruppen scheinen leichter zu interkalieren als solche ohne Carbonylgruppen. Polycaprolacton interkalierte sowohl in Oragnomagadiite auf der Basis von Ammoniumtensiden als auch in solche auf der Basis von Phosphoniumtensiden. Die Dynamik auf einer Nanosekundenzeitskala und die Struktur der Tensidschicht wurden mittels ortsspezifisch spinmarkierter Tensidsonden unter Nutzung von Dauerstrich- (CW) und Puls-Methoden der elektronenparamagnetischen Resonanzspektroskopie (EPR) untersucht. Zusätzlich wurde die statische 2H-Kernmagnetresonanz (NMR) an spezifisch deuterierten Tensiden angewendet, um die Tensiddynamik auf einer komplementären Zeitskala zwischen Mikrosekunden und Millisekunden zu erfassen. Sowohl die CW-EPR- als auch die 2H-NMR-Ergebnisse zeigen eine Beschleunigung der Tensiddynamik durch Interkalation von Polycaprolacton auf, während sich in den nichtinterkalierten Mikrokompositen mit Polystyrol die Tensiddynamik verlangsamt. Die Rotationskorrelationszeiten und Aktivierungsenergien offenbaren verschiedene Regime der Tensiddynamik. In Polystyrol-Mikrokompositen entspricht die Übergangstemperatur zwischen den Regimen der Glasübergangstemperatur von Polystyrol, während sie in Polycaprolacton-Nanokompositen bei der Schmelztemperatur von Polycaprolacton liegt. Durch die erhebliche Verlängerung der Elektronenspin-Relaxationszeiten bei Verwendung von eisenfreiem Magadiit können Messdaten hoher Qualität mit Puls-EPR-Experimenten erhalten werden. Insebsondere wurden die Vier-Puls-Elektron-Elektron-Doppelresonanz (DEER), die Elektronenspinechoenveloppenmodulation (ESEEM) und die Elektronen-Kern-Doppelresonanz (ENDOR) an spinmarkierten sowie spezifisch deuterierten Tensiden angewandt. Die ENDOR-Ergebnisse legen ein Model der Tensidschicht nahe, in dem zusätzlich zu den Oberflächenlagen auf dem Silikat eine wohldefinierte mittlere Lage existiert. Dieses Modell erklärt auch Verdünnungseffekte durch das Polymer in Kompositen mit Polycaprolacton und Polystyrol. Die umfangreiche Information aus den Magnetresonanztechniken ergänzt die Information aus konventionellen Charakterisierungstechniken wie Röntgendiffraktion und Transmissionselektronenmikroskopie und führt so zu einem detaillierteren Bild der Struktur und Dynamik der Tensidschicht in Nanokompositen aus Polymeren und Schichtsilikaten.

Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.

An in vivo study of a growth-factor enhanced, cell free, two-layered collagen-tricalcium phosphate in deep osteochondral defects

Focal osteochondral defects are still a challenging problem in joint surgery. We have developed a two-layered implant consisting of a basal porous beta-tricalcium phosphate (TCP) for bone reconstruction and a superficial fibrous collagen type I/III layer for cartilage regeneration. Fifty-four osteochondral defects in the trochlear groove of 27 Göttinger Minipigs were created and either left untreated, treated with the implant alone, or the implant augmented with an additional growth factor mixture, which was assumed to stimulate cell and tissue differentiation. Follow-up was 6, 12 and 52 weeks with n=6 for each group. The repair tissue was evaluated for its gross appearance and biomechanical properties. Histological sections were semi-quantitatively scored for their histomorphological structure. Treatment with the two-layered implant improved defect filling and subchondral bone repair at 6 and 12 weeks follow-up. The TCP was replaced by cancellous bone at 52 weeks. Cartilage repair tissue mainly consisted of fibrocartilage and showed a moderate cell density up to the joint surface. Growth factor treatment improved the mechanical and histomorphological properties of the cartilage repair tissue at 12, but not at 52 weeks postoperatively. In conclusion, the two-layered collagen-TCP implant augmented with chondroinductive growth factors seems a promising new option for the treatment of deep osteochondral defects in joint surgery.

Vibro-acoustical analysis and design of a multiple-layer constrained viscoelastic damping structure

The goal of this research is to provide a framework for vibro-acoustical analysis and design of a multiple-layer constrained damping structure. The existing research on damping and viscoelastic damping mechanism is limited to the following four mainstream approaches: modeling techniques of damping treatments/materials; control through the electrical-mechanical effect using the piezoelectric layer; optimization by adjusting the parameters of the structure to meet the design requirements; and identification of the damping material’s properties through the response of the structure. This research proposes a systematic design methodology for the multiple-layer constrained damping beam giving consideration to vibro-acoustics. A modeling technique to study the vibro-acoustics of multiple-layered viscoelastic laminated beams using the Biot damping model is presented using a hybrid numerical model. The boundary element method (BEM) is used to model the acoustical cavity whereas the Finite Element Method (FEM) is the basis for vibration analysis of the multiple-layered beam structure. Through the proposed procedure, the analysis can easily be extended to other complex geometry with arbitrary boundary conditions. The nonlinear behavior of viscoelastic damping materials is represented by the Biot damping model taking into account the effects of frequency, temperature and different damping materials for individual layers. A curve-fitting procedure used to obtain the Biot constants for different damping materials for each temperature is explained. The results from structural vibration analysis for selected beams agree with published closed-form results and results for the radiated noise for a sample beam structure obtained using a commercial BEM software is compared with the acoustical results of the same beam with using the Biot damping model. The extension of the Biot damping model is demonstrated to study MDOF (Multiple Degrees of Freedom) dynamics equations of a discrete system in order to introduce different types of viscoelastic damping materials. The mechanical properties of viscoelastic damping materials such as shear modulus and loss factor change with respect to different ambient temperatures and frequencies. The application of multiple-layer treatment increases the damping characteristic of the structure significantly and thus helps to attenuate the vibration and noise for a broad range of frequency and temperature. The main contributions of this dissertation include the following three major tasks: 1) Study of the viscoelastic damping mechanism and the dynamics equation of a multilayer damped system incorporating the Biot damping model. 2) Building the Finite Element Method (FEM) model of the multiple-layer constrained viscoelastic damping beam and conducting the vibration analysis. 3) Extending the vibration problem to the Boundary Element Method (BEM) based acoustical problem and comparing the results with commercial simulation software.

The structure of the asteroid 4 Vesta as revealed by models of planet-scale collisions

Asteroid 4Vesta seems to be a major intact protoplanet, with a surface composition similar to that of the HED (howardite-eucrite-diogenite) meteorites. The southern hemisphere is dominated by a giant impact scar, but previous impact models have failed to reproduce the observed topography. The recent discovery that Vesta's southern hemisphere is dominated by two overlapping basins provides an opportunity to model Vesta's topography more accurately. Here we report three-dimensional simulations of Vesta's global evolution under two overlapping planet-scale collisions. We closely reproduce its observed shape, and provide maps of impact excavation and ejecta deposition. Spiral patterns observed in the younger basin Rheasilvia, about one billion years old, are attributed to Coriolis forces during crater collapse. Surface materials exposed in the north come from a depth of about 20kilometres, according to our models, whereas materials exposed inside the southern double-excavation come from depths of about 60-100kilometres. If Vesta began as a layered, completely differentiated protoplanet, then our model predicts large areas of pure diogenites and olivine-rich rocks. These are not seen, possibly implying that the outer 100kilometres or so of Vesta is composed mainly of a basaltic crust (eucrites) with ultramafic intrusions (diogenites).

Carbohydrate gluing, an architectural mechanism in the supramolecular structure of an annelid giant hemoglobin.

We report a carbohydrate-dependent supramolecular architecture in the extracellular giant hemoglobin (Hb) from the marine worm Perinereis aibuhitensis; we call this architectural mechanism carbohydrate gluing. This study is an extension of our accidental discovery of deterioration in the form of the Hb caused by a high concentration of glucose. The giant Hbs of annelids are natural supramolecules consisting of about 200 polypeptide chains that associate to form a double-layered hexagonal structure. This Hb has 0.5% (wt) carbohydrates, including mannose, xylose, fucose, galactose, glucose, N-acetylglucosamine (GlcNAc), and N-acetylgalactosamine (GalNAc). Using carbohydrate-staining assays, in conjunction with two-dimensional polyacrylamide gel electrophoresis, we found that two types of linker chains (L1 and L2; the nomenclature of the Hb subunits followed that for another marine worm, Tylorrhynchus heterochaetus) contained carbohydrates with both GlcNAc and GalNAc. Furthermore, two types of globins (a and A) have only GlcNAc-containing carbohydrates, whereas the other types of globins (b and B) had no carbohydrates. Monosaccharides including mannose, fucose, glucose, galactose, GlcNAc, and GalNAc reversibly dissociated the intact form of the Hb, but the removal of carbohydrate with N-glycanase resulted in irreversible dissociation. These results show that carbohydrate acts noncovalently to glue together the components to yield the complete quaternary supramolecular structure of the giant Hb. We suggest that this carbohydrate gluing may be mediated through lectin-like carbohydrate-binding by the associated structural chains ("linkers").

On the initiation of boudinage and folding instabilities in layered elasto-visco-plastic solids - Insights from natural microstructures and numerical simulations

The present understanding of the initiation of boudinage and folding structures is based on viscosity contrasts and stress exponents, considering an intrinsically unstable state of the layer. The criterion of localization is believed to be prescribed by geometry-material interactions, which are often encountered in natural structures. An alternative localization phenomenon has been established for ductile materials, in which instability emerges for critical material parameters and loading rates from homogeneous conditions. In this thesis, conditions are sought under which this type of instability prevails and whether localization in geological materials necessarily requires a trigger by geometric imperfections. The relevance of critical deformation conditions, material parameters and the spatial configuration of instabilities are discussed in a geological context. In order to analyze boudinage geometries, a numerical eigenmode analysis is introduced. This method allows determining natural frequencies and wavelengths of a structure and inducing perturbations on these frequencies. In the subsequent coupled thermo-mechanical simulations, using a grain size evolution and end-member flow laws, localization emerges when material softening through grain size sensitive viscous creep sets in. Pinch-and-swell structures evolve along slip lines through a positive feedback between the matrix response and material bifurcations inside the layer, independent from the mesh-discretization length scale. Since boudinage and folding are considered to express the same general instability, both structures should arise independently of the sign of the loading conditions and for identical material parameters. To this end, the link between material to energy instabilities is approached by means of bifurcation analyses of the field equations and finite element simulations of the coupled system of equations. Boudinage and folding structures develop at the same critical energy threshold, where dissipative work by temperature-sensitive creep overcomes the diffusive capacity of the layer. This finding provides basis for a unified theory for strain localization in layered ductile materials. The numerical simulations are compared to natural pinch-and-swell microstructures, tracing the adaption of grain sizes, textures and creep mechanisms in calcite veins. The switch from dislocation to diffusion creep relates to strain-rate weakening, which is induced by dissipated heat from grain size reduction, and marks the onset of continuous necking. The time-dependent sequence uncovers multiple steady states at different time intervals. Microstructurally and mechanically stable conditions are finally expressed in the pinch-and-swell end members. The major outcome of this study is that boudinage and folding can be described as the same coupled energy-mechanical bifurcation, or as one critical energy attractor. This finding allows the derivation of critical deformation conditions and fundamental material parameters directly from localized structures in the field.

The Microphysical Structure of Mesoscale Convective Systems

Thesis (Ph.D.)--University of Washington, 2016-05