Dehydrodipeptide hydrogelators containing naproxen N‑Capped tryptophan: self-assembly, hydrogel characterization, and evaluation as potential drug nanocarriers

In this work, we introduce dipeptides containing tryptophan N-capped with the nonsteroidal anti-inflammatory drug naproxen and C-terminal dehydroamino acids, dehydrophenylalanine (ΔPhe), dehydroaminobutyric acid (ΔAbu), and dehydroalanine (ΔAla) as efficacious protease resistant hydrogelators. Optimized conditions for gel formation are reported. Transmission electron microscopy experiments revealed that the hydrogels consist of networks of micro/nanosized fibers formed by peptide self-assembly. Fluorescence and circular dichroism spectroscopy indicate that the self-assembly process is driven by stacking interactions of the aromatic groups. The naphthalene groups of the naproxen moieties are highly organized in the fibers through chiral stacking. Rheological experiments demonstrated that the most hydrophobic peptide (containing C-terminal ΔPhe) formed more elastic gels at lower critical gelation concentrations. This gel revealed irreversible breakup, while the C-terminal ΔAbu and ΔAla gels, although less elastic, exhibited structural recovery and partial healing of the elastic properties. A potential antitumor thieno[3,2-b]pyridine derivative was incorporated (noncovalently) into the gel formed by the hydrogelator containing C-terminal ΔPhe residue. Fluorescence and Förster resonance energy transfer measurements indicate that the drug is located in a hydrophobic environment, near/associated with the peptide fibers, establishing this type of hydrogel as a good drug-nanocarrier candidate.

Effective interaction between monolayers of block copolymer compatiblizer in a polymer blend

The stability of ternary blends of two immiscible homopolymers and a block copolymer compatiblizer depends crucially on the effective interaction between the copolymermonolayers that form between the unlike homopolymer domains. Here, the interaction is calculated for blends involving A and B homopolymers of equal size with ABABdiblock copolymers of symmetric composition using both self-consistent field theory (SCFT) and strong-segregation theory (SST). If the homopolymers are larger than the copolymer molecules, an attractive interaction is predicted which would destroy the blend. This conclusion coupled with considerations regarding the elastic properties of the monolayer suggests that the optimum size of the homopolymer molecules is about 80% that of the copolymer molecule. A detailed examination of the theory demonstrates that the attraction results from the configurational entropy loss of the homopolymer molecules trapped between the copolymermonolayers. We conclude by suggesting how the monolayers can be altered in order to suppress this attraction and thus improve compatiblization.

Analysis of spherical indentation of superelastic shape memory alloys

Dimensional analysis and the finite element method are applied in this paper to study spherical indentation of superelastic shape memory alloys. The scaling relationships derived from dimensional analysis bridge the indentation response and the mechanical properties of a superelastic shape memory alloy. Several key variables of a superelastic indentation curve are revealed and examined. We prove that the bifurcation force in a superelastic indentation curve only relies on the forward transformation stress and the elastic properties of the initial austenite; and the return force in a superelastic indentation curve only relies on the reverse transformation stress and the elastic properties of the initial austenite. Furthermore, the dimensionless functions to determine the bifurcation force and the return force are proved to be identical. These results not only enhance our understanding of spherical indentation of superelastic shape memory alloys, but also provide the theoretical basis for developing a practicable method to calibrate the mechanical properties of a superelastic material from the spherical indentation test.

Determination of plastic yield stress from spherical indentation slope curve

The indentation slope curve from a spherical indentation on elastic-plastic materials is examined. By comparing it with that of an linear elastic material of the same elastic properties, we found that the start point of plastic yielding for an elastic-plastic material can be easily located from the indentation slope curve. Based on this analysis, a simple but effective method is proposed to measure the plastic yield stress of very small samples from a spherical nano-indentation slope curve.

The configuration evolution and macroscopic elasticity of fluid-filled closed cell composites : micromechanics and multiscale homogenization modelling

For fluid-filled closed cell composites widely distributed in nature, the configuration evolution and effective elastic properties are investigated using a micromechanical model and a multiscale homogenization theory, in which the effect of initial fluid pressure is considered. Based on the configuration evolution of the composite, we present a novel micromechanics model to examine the interactions between the initial fluid pressure and the macroscopic elasticity of the material. In this model, the initial fluid pressure of the closed cells and the corresponding configuration can be produced by applying an eigenstrain at the introduced fictitious stress-free configuration, and the pressure-induced initial microscopic strain is derived. Through a configuration analysis, we find the initial fluid pressure has a prominent effect on the effective elastic properties of freestanding materials containing pressurized fluid pores, and a new explicit expression of effective moduli is then given in terms of the initial fluid pressure. Meanwhile, the classical multiscale homogenization theory for calculating the effective moduli of a periodical heterogeneous material is generalized to include the pressurized fluid "inclusion" effect. Considering the coupling between matrix deformation and fluid pressure in closed cells, the multiscale homogenization method is utilized to numerically determine the macroscopic elastic properties of such composites at the unit cell level with specific boundary conditions. The present micromechanical model and multiscale homogenization method are illustrated by several numerical examples for validation purposes, and good agreements are achieved. The results show that the initial pressure of the fluid phase can strengthen overall effective bulk modulus but has no contribution to the shear modulus of fluid-filled closed cell composites.

Atomically resolved tomography to directly inform simulations for structure-property relationships

Microscopy encompasses a wide variety of forms and scales. So too does the array of simulation techniques developed that correlate to and build upon microstructural information. Nevertheless, a true nexus between microscopy and atomistic simulations is lacking. Atom probe has emerged as a potential means of achieving this goal. Atom probe generates three-dimensional atomistic images in a format almost identical to many atomistic simulations. However, this data is imperfect, preventing input into computational algorithms to predict material properties. Here we describe a methodology to overcome these limitations, based on a hybrid data format, blending atom probe and predictive Monte Carlo simulations. We create atomically complete and lattice-bound models of material specimens. This hybrid data can then be used as direct input into density functional theory simulations to calculate local energetics and elastic properties. This research demonstrates the role that atom probe combined with theoretical approaches can play in modern materials engineering.

Novas fases amorfas de carbono produzidas por irradiação iônica de filmes de C/sub 60/, [alfa]-C e [alfa]-C:H

Neste trabalho estuda-se a formação de novas fases de carbono amorfo através da irradiação iônica de filmes de fulereno, a-C e a-C:H polimérico. Os efeitos da irradiação iônica na modificação das propriedades ópticas e mecânicas dos filmes de carbono irradiados são analisados de forma correlacionada com as alterações estruturais a nivel atômico. O estudo envolve tanto a análise dos danos induzidos no fulereno pela irradiação iônica a baixas fluências, correspondendo a baixas densidades de energia depositada, quanto a investigação das propriedades físico-químicas das fases amorfas obtidas após irradiações dos filmes de fulereno, a-C e a-C:H com altas densidades de energia depositada. As propriedades ópticas, mecânicas e estruturais das amostras são analisadas através de técnicas de espectroscopia Raman e infravermelho, espectrofotometria UV-VIS-NIR, microscopias ópticas e de força atômica, nanoindentação e técnicas de análise por feixe de íons, tais como retroespalhamento Rutherford e análises por reação nuclear. As irradiações produzem profundas modificações nas amostras de fulereno, a-C e a-C:H, e por conseqüência significativas alterações em suas propriedades ópticas e mecânicas. Após máximas fluências de irradiação fases amorfas rígidas (com dureza de 14 e 17 GPa) e com baixos gaps ópticos (0,2 e 0,5 eV) são formadas. Estas estruturas não usuais correspondem a arranjos atômicos com 90 a 100% de estados sp2. Em geral fases sp2 são planares e apresentam baixa dureza, como predito pelo modelo de “cluster”. Entretanto, os resultados experimentais mostram que as propriedades elásticas das novas fases formadas são alcançadas através da criação de uma estrutura sp2 tridimensional. A indução de altas distorções angulares, através da irradiação iônica, possibilita a formação de anéis de carbono não hexagonais, tais como pentágonos e heptágonos, permitindo assim a curvatura da estrutura. Utilizando um modelo de contagem de vínculos é feita uma análise comparativa entre a topologia (estrutura geométrica) de ligações C-sp2 e as propriedades nanomecânicas. São comparados os efeitos de estruturas sp2 planares e tridimensionais (aleatórias) no processo de contagem de vínculos e, conseqüentemente, nas propriedades elásticas de cada sistema. Os resultados mostram que as boas propriedades mecânicas das novas fases de carbono formadas seguem as predições do modelo de vínculos para uma rede atômica sp2 tridimensional. A formação de uma fase amorfa dura e 100% sp2 representa uma importante conquista na procura de novas estruturas rígidas de carbono. A síntese da estrutura desordenada sp2 tridimensional e vinculada aqui apresentada é bastante incomum na literatura. O presente trabalho mostra que o processo de não-equilíbrio de deposição de energia durante a irradiação iônica permite a formação de distorções angulares nas ligações sp2-C, possibilitando a criação de estruturas grafíticas tridimensionais.

The position effect of structural Eucalyptus round timber on the flexural modulus of elasticity

A madeira roliça possui grande emprego nas construções civis, desempenhando a função de vigas, colunas, fundações, postes para distribuição de energia elétrica, entre outras, apresentando a vantagem de não ser processada, como é o caso da madeira serrada. O projeto envolvendo elementos roliços requer, além de outras variáveis estruturais, o conhecimento do módulo de elasticidade. No Brasil, os documentos normativos que tratam da determinação das propriedades de rigidez e resistência para peças roliças de madeira estão em vigência há mais de vinte anos sem revisão técnica. A madeira roliça, por geralmente possuir eixo com curvatura não nula, pode apresentar, segundo a posição da peça no ensaio de flexão, valores diferentes do módulo de elasticidade. Este trabalho tem como objetivo analisara influência da posição de peças roliças de madeira de Eucalyptus grandis na determinação do módulo de elasticidade na flexão. O ensaio de flexão utilizado é o de três pontos, sendo cada peça avaliada em duas posições distintas, definidas mediante o giro da seção transversal em torno do eixo. Os resultados encontrados indicam a necessidade do ensaio de flexão em, pelo menos, duas posições distintas da peça.

Diffusion of Interstitial Elements in Ti Alloys used as Biomaterials

Titanium alloys are excellent implant materials for orthopedic applications due to their desirable properties, such as good corrosion resistance, low elasticity modulus, and excellent biocompatibility. The presence of interstitial elements (such as oxygen and nitrogen) causes strong changes in the material's mechanical properties, mainly in its elastic properties. Study of the interaction among interstitial elements present in metals began with Snoek's postulate, that a stress-induced ordering of interstitials gives rise to a peak in the mechanical relaxation (internal friction) spectra. In the mechanical relaxation spectra, each species of interstitial solute atom gives rise to a distinct Snoek's peak, whose temperature and position depend on the measurement frequency. This effect is very interesting because its peculiar parameters are directly related to the diffusion coefficient (D) for the interstitial solute. This paper presents a study of diffusion of heavy interstitial elements in Ti-35Nb-7Zr-5Ta alloys using mechanical spectroscopy. Pre-exponential factors and activation energies are calculated for oxygen and nitrogen in theses alloys.

Processing and hygrothermal effects on viscoelastic behavior of glass fiber/epoxy composites

Fiber reinforced epoxy composites are used in a wide variety of applications in the aerospace field. These materials have high specific moduli, high specific strength and their properties can be tailored to application requirements. In order to screening optimum materials behavior, the effects of external environments on the mechanical properties during usage must be clearly understood. The environmental action, such as high moisture concentration, high temperatures, corrosive fluids or ultraviolet radiation (UV), can affect the performance of advanced composites during service. These factors can limit the applications of composites by deteriorating the mechanical properties over a period of time. Properties determination is attributed to the chemical and/or physical damages caused in the polymer matrix, loss of adhesion of fiber/resin interface, and/or reduction of fiber strength and stiffness. The dynamic elastic properties are important characteristics of glass fiber reinforced composites (GRFC). They control the damping behavior of composite structures and are also an ideal tool for monitoring the development of GFRC's mechanical properties during their processing or service. One of the most used tests is the vibration damping. In this work, the measurement consisted of recording the vibration decay of a rectangular plate excited by a controlled mechanism to identify the elastic and damping properties of the material under test. The frequency amplitude were measured by accelerometers and calculated by using a digital method. The present studies have been performed to explore relations between the dynamic mechanical properties, damping test and the influence of high moisture concentration of glass fiber reinforced composites (plain weave). The results show that the E' decreased with the increase in the exposed time for glass fiber/epoxy composites specimens exposed at 80 degrees C and 90% RH. The E' values found were: 26.7, 26.7, 25.4, 24.7 and 24.7 GPa for 0, 15, 30, 45 and 60 days of exposure, respectively. (c) 2005 Springer Science + Business Media, Inc.

Hygrothermal effects on damping behavior of metal/glass fiber/epoxy hybrid composites

Continuous fiber/metal laminates (FML) offer significant improvements over current available materials for aircraft structures due to their excellent fatigue endurance and low density. Glass fibers/epoxy laminae and aluminum foil (Glare) are commonly used to obtain these hybrid composites. The environmental factors can limit the applications of composites by deteriorating the mechanical properties during service. Usually, epoxy resins absorb moisture when exposed to humid environments and metals are prone to surface corrosion. Therefore, the combination of the two materials in Glare (polymeric composite and metal). can lead to differences that often turn out to be beneficial in terms of mechanical properties and resistance to environmental influences. In this work. The viscoelastic properties. such as storage modulus (E') and loss modulus (E'), were obtained for glass fiber/epoxy composite, aluminum 2024-T3 alloy and for a glass fiber/epoxy/aluminum laminate (Glare). It was found that the glass fiber/epoxy (G/E) composites decrease the E' modulus during hygrothermal conditioning up to saturation point (6 weeks). However, for Glare laminates the E' modulus remains unchanged (49GPa) during the cycle of hygrothermal conditioning. The outer aluminum sheets in the Glare laminate shield the G/E composite laminae from moisture absorption. which in turn prevent, in a certain extent, the material from hygrothermal degradation effects. (c) 2005 Elsevier B.V. All rights reserved.

Arcabouço geofísico, isostasia e causas do magmatismo cenozóico da província Borborema e de sua margem continental (Nordeste do Brasil)

The Borborema Province (BP) is a geologic domain located in Northeastern Brazil. The BP is limited at the south by the São Francisco craton, at the west by the Parnaíba basin, and both at the north and east by coastal sedimentary basins. Nonetheless the BP surface geology is well known, several key aspects of its evolution are still open, notably: i)its tectonic compartmentalization established after the Brasiliano orogenesis, ii) the architecture of its cretaceous continental margin, iii) the elastic properties of its lithosphere, and iv) the causes of magmatism and uplifting which occurred in the Cenozoic. In this thesis, a regional coverage of geophysical data (elevation, gravity, magnetic, geoid height, and surface wave global tomography) were integrated with surface geologic information aiming to attain a better understanding of the above questions. In the Riacho do Pontal belt and in the western sector of the Sergipano belt, the neoproterozoic suture of the collision of the Sul domain of the BP with the Sanfranciscana plate (SFP) is correlated with an expressive dipolar gravity anomaly. The positive lobule of this anomaly is due to the BP lower continental crust uplifting whilst the negative lobule is due to the supracrustal nappes overthrusting the SFP. In the eastern sector of the Sergipano belt, this dipolar gravity anomaly does not exist. However the suture still can be identified at the southern sector of the Marancó complex arc, alongside of the Porto da Folha shear zone, where the SFP N-S geophysical alignments are truncated. The boundary associated to the collision of the Ceará domain of the BP with the West African craton is also correlated with a dipolar gravity anomaly. The positive lobule of this anomaly coincides with the Sobral-Pedro II shear zone whilst the negative lobule is associated with the Santa Quitéria magmatic arc. Judging by their geophysical signatures, the major BP internal boundaries are: i)the western sector of the Pernambuco shear zone and the eastern continuation of this shear zone as the Congo shear zone, ii) the Patos shear zone, and iii) the Jaguaribe shear zone and its southwestern continuation as the Tatajuba shear zone. These boundaries divide the BP in five tectonic domains in the geophysical criteria: Sul, Transversal, Rio Grande do Norte, Ceará, and Médio Coreaú. The Sul domain is characterized by geophysical signatures associated with the BP and SFP collision. The fact that Congo shear zone is now proposed as part of the Transversal domain boundary implies an important change in the original definition of this domain. The Rio Grande do Norte domain presents a highly magnetized crust resulted from the superposition of precambrian and phanerozoic events. The Ceará domain is divided by the Senador Pompeu shear zone in two subdomains: the eastern one corresponds to the Orós-Jaguaribe belt and the western one to the Ceará-Central subdomain. The latter subdomain exhibits a positive ENE-W SW gravity anomaly which was associated to a crustal discontinuity. This discontinuity would have acted as a rampart against to the N-S Brasiliano orogenic nappes. The Médio Coreaú domain also presents a dipolar gravity anomaly. Its positive lobule is due to granulitic rocks whereas the negative one is caused by supracrustal rocks. The boundary between Médio Coreaú and Ceará domains can be traced below the Parnaíba basin sediments by its geophysical signature. The joint analysis of free air anomalies, free air admittances, and effective elastic thickness estimates (Te) revealed that the Brazilian East and Equatorial continental margins have quite different elastic properties. In the first one 10 km < Te < 20 km whereas in the second one Te ≤ 10 km. The weakness of the Equatorial margin lithosphere was caused by the cenozoic magmatism. The BP continental margin presents segmentations; some of them have inheritance from precambrian structures and domains. The segmentations conform markedly with some sedimentary basin features which are below described from south to north. The limit between Sergipe and Alagoas subbasins coincides with the suture between BP and SFP. Te estimates indicates concordantly that in Sergipe subbasin Te is around 20 km while Alagoas subbasin has Te around 10 km, thus revealing that the lithosphere in the Sergipe subbasin has a greater rigidity than the lithosphere in the Alagoas subbasin. Additionally inside the crust beneath Sergipe subbasin occurs a very dense body (underplating or crustal heritage?) which is not present in the crust beneath Alagoas subbasin. The continental margin of the Pernambuco basin (15 < Te < 25 km) presents a very distinct free air edge effect displaying two anomalies. This fact indicates the existence in the Pernambuco plateau of a relatively thick crust. In the Paraíba basin the free air edge effect is quite uniform, Te ≈ 15 km, and the lower crust is abnormally dense probably due to its alteration by a magmatic underplating in the Cenozoic. The Potiguar basin segmentation in three parts was corroborated by the Te estimates: in the Potiguar rift Te ≅ 5 km, in the Aracati platform Te ≅ 25 km, and in the Touros platform Te ≅ 10 km. The observed weakness of the lithosphere in the Potiguar rift segment is due to the high heat flux while the relatively high strength of the lithosphere in the Touros platform may be due to the existence of an archaean crust. The Ceará basin, in the region of Mundaú and Icaraí subbasins, presents a quite uniform free air edge effect and Te ranges from 10 to 15 km. The analysis of the Bouguer admittance revealed that isostasy in BP can be explained with an isostatic model where combined surface and buried loadings are present. The estimated ratio of the buried loading relative to the surface loading is equal to 15. In addition, the lower crust in BP is abnormally dense. These affirmations are particularly adequate to the northern portion of BP where adherence of the observed data to the isostatic model is quite good. Using the same above described isostatic model to calculate the coherence function, it was obtained that a single Te estimate for the entire BP must be lower than 60 km; in addition, the BP north portion has Te around 20 km. Using the conventional elastic flexural model to isostasy, an inversion of crust thickness was performed. It was identified two regions in BP where the crust is thickened: one below the Borborema plateau (associated to an uplifting in the Cenozoic) and the other one in the Ceará domain beneath the Santa Quitéria magmatic arc (a residue associated to the Brasiliano orogenesis). On the other hand, along the Cariri-Potiguar trend, the crust is thinned due to an aborted rifting in the Cretaceous. Based on the interpretation of free air anomalies, it was inferred the existence of a large magmatism in the oceanic crust surrounding the BP, in contrast with the incipient magmatism in the continent as shown by surface geology. In BP a quite important positive geoid anomaly exists. This anomaly is spatially correlated with the Borborema plateau and the Macaú-Queimadas volcanic lineament. The integrated interpretation of geoid height anomaly data, global shear velocity model, and geologic data allow to propose that and Edge Driven Convection (EDC) may have caused the Cenozoic magmatism. The EDC is an instability that presumably occurs at the boundary between thick stable lithosphere and oceanic thin lithosphere. In the BP lithosphere, the EDC mechanism would have dragged the cold lithospheric mantle into the hot asthenospheric mantle thus causing a positive density contrast that would have generated the main component of the geoid height anomaly. In addition, the compatibility of the gravity data with the isostatic model, where combined surface and buried loadings are present, together with the temporal correlation between the Cenozoic magmatism and the Borborema plateau uplifting allow to propose that this uplifting would have been caused by the buoyancy effect of a crustal root generated by a magmatic underplating in the Cenozoic

Study of stress distribution with finite element method in a root with prefabricated threaded split shaft post - Part I

A finite element analysis was carried out to study the role of prefabricated threaded split shaft post (Flexi-Post) on dentinal stress in pulpless tooth. Three dimensional plane strain model of mesio-distal section of a human maxillary central incisor without restoration was analysed with the MSC/NASTRAN (MacNeal/ Schwendler) general purpose finite analysis program was executed on a microcomputer. The model as discretized into 48.954 axisymmetric finite elements defined by 10.355 nodes. Each element was assigned unique elastic properties to represent the materials modeled. Homogeneity, isotropy and linear elasticity were assume for all material. A simulation of static load of 100N was applied to the incisal edge of the post; vertical. Maximal principal stresses and von Mises equivalent stress were calculated. Using the element analysis model employed in this study, the following can be concluded concerning threaded split shaft post (Flexi-Post): Maximum principal stresses in dentin were located at cervical place and at the post apex. The apical threads of the post not redirecting stresses away from the root.

Evaluation by Free Vibration Method of Moisture Absorption Effects in Polyamide/Carbon Fiber Laminates

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

Interaction potential between vortex lines for uniaxial superconductors in the London approximation

Two distinct expressions of the interaction potential between arbitrarily oriented curved vortex lines with respect to the crystal c axis are derived within the London approximation. One of these expressions is used to compute the eigenvalues of the elasticity matrix. We examine the elastic properties of the vortex chain lattice, recently proposed, concerning shearing deformation.