Polymeric fibers with tunable properties Lessons from spider silk

Making artificial fibers inspired in spider silks is considered as one of the milestones in the field of biomimetics. The interest is usually justified by the outstanding tensile properties of natural fibers, but it is usually overlooked that spider silk is endowed with a number of related properties – supercontraction, recovery and the existence of a ground state – that impart the material with additional desirable features, such as the possibility of tuning its mechanical behaviour. In this work we present a review on the experimental analysis and significance of these properties, stressing the contributions of our research group to the field. It is also demonstrated how the knowledge gained in the basic study of the natural material has been essential for the improvement of the properties exhibited by artificially processed bio-inspired silk fiber

The hidden link between supercontraction and mechanical behavior of spider silks

The remarkable properties of spider silks have stimulated an increasing interest in understanding the roles of their composition and processing, as well as in the mass-production of these fibers. Previously, the variability in the mechanical properties of natural silk fibers was a major drawback in the elucidation of their behavior, but the authors have found that supercontraction of these fibers allows one to characterize and reproduce the whole range of tensile properties in a consistent way. The purpose of this review is to summarize these findings. After a review of the pertinent mechanical properties, the role of supercontraction in recovering and tailoring the tensile properties is explained, together with an alignment parameter to characterize silk fibers. The concept of the existence of a mechanical ground state is also mentioned. These behaviors can be modeled, and two such models–at the molecular and macroscopic levels–are briefly outlined. Finally, the assessment of the existence of supercontraction in bio-inspired fibers is considered, as this property may have significant consequences in the design and production of artificial fibers

Propiedades mecánicas y resistencia de aortas ascendentes patológicas

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Relationship between fibre orientation and tensile strength of natural collagen membranes for heart valve leaflets

Heart valve prostheses are used to replace native heart valves which that are damaged because of congenital diseases or due to ageing. Biological prostheses made of bovine pericardium are similar to native valves and do not require any anticoagulation treatment, but are less durable than mechanical prostheses and usually fail by tearing. Researches are oriented in improving the resistance and durability of biological heart valve prostheses in order to increase their life expectancy. To understand the mechanical behaviour of bovine pericardium and relate it to its microstructure (mainly collagen fibres concentration and orientation) uniaxial tensile tests have been performed on a model material made of collagen fibres. Small Angle Light Scattering (SALS) has been also used to characterize the microstructure without damaging the material. Results with the model material allowed us to obtain the orientation of the fibres, relating the microstructure to mechanical performanc

Efecto de la Longitud de onda de la radiación UV sobre la seda de araña

En el presente trabajo se continúa el análisis de la influencia de la radiación UV sobre las propiedades mecánicas de las fibras de seda de araña. Para ello se ha empleado la seda producida por la glándula ampollácea mayor de la especie Argiope trifasciata y se ha estudiado el comportamiento en tracción simple de fibras de seda sometidas a diferentes tiempos de irradiación con luz UV de longitudes de onda de 254, 312 y 365 nm. Se ha encontrado que la radiación ultravioleta disminuye la tensión de rotura y la deformación de rotura modificando, en algunos casos, el aspecto general de las curvas tensión-deformación. Además se ha hecho uso de la radiación UV de longitud de onda de 254 nm para introducir daño en las fibras con objeto de realizar un análisis fractográfico sistemático. El estudio se complementa con la evaluación del efecto producido por la irradiación en el fenómeno de supercontracción

The variability and interdependence of spider viscid line tensile properties

True stress-true strain curves of naturally spun viscid line fibers retrieved directly from the spiral of orb-webs built by Argiope trifasciata spiders were measured using a novel methodology. This new procedure combines a method for removing the aqueous coating of the fibers and a technique that allows the accurate measurement of their cross sectional area. Comparison of the tensile behaviour of different samples indicates that naturally spun viscid lines show a large variability, comparable to that of other silks, such as major ampullate gland silk and silkworm silk. Nevertheless, application of a statistical analysis allowed identifying two independent parameters that underlie the variability and characterize the observed range of true stress-true strain curves. Combination of this result with previous mechanical and microstructural data suggested the assignment of these two independent effects to the degree of alignment of the protein chains and to the local relative humidity which, in turn, depends on the composition of the viscous coating and on the external environmental conditions

Efecto de la temperatura en la rotura por despegue de una placa de ateroma

Las placas de ateroma de las paredes arteriales son acumulaciones de lípidos y otras sustancias que modifican las propiedades de la pared vascular. El principal problema que presentan estas placas es su rotura y despegue de la pared, con la posibilidad de obstruir la circulación de la sangre. En este trabajo se analiza, mediante un modelo animal en conejos, el efecto que una variación de temperatura (por ejemplo en un proceso febril) puede tener en la aparición de tensiones tangenciales entre la placa y la pared. Para ello se han obtenido las propiedades termomecánicas de la pared arterial y de la placa de ateroma. Asimismo, se ha elaborado un modelo para estimar las tensiones generadas por un incremento de temperatura. Como ejemplo se muestra que un aumento de la temperatura de 4ºC, que correspondería a una fiebre de algo más de 40ºC, puede generar elevadas tensiones capaces de provocar el despegue de la placa. - Atheroma plaques are accumulations of lipids and other substances attached to the inner side of the artery walls, which modify the mechanical behaviour of the artery wall. Their main problem comes when the plaque breaks and incorporates to the blood flow, because it can eventually block blood circulation and damage to the surrounding tissues and organs. This work explores, by means of a rabbit model, the effect of temperature variation on the development of interfacial shear stresses between plaque and wall. The thermomechanical properties of arterial wall and atheroma plaques have been obtained. A simplified model has also been developed in order to estimate the stress level, which has shown that due to a moderate temperature increment of 4ºC interfacial shear stresses can reach high values, enough to provoke plaque rupture and detachment

Influencia de la radiación UV en las propiedades mecánicas y en el comportamiento en fractura de un polimero artificial bioinspirado en la seda de araña

En el presente trabajo se estudia la influencia de la radiación UV sobre las propiedades mecánicas y las superficies de fractura de un polímero artificial bioinspirado en la seda de araña. Las fibras de seda de araña constituyen un material enormemente atractivo ya que su elevada resistencia y deformabilidad lo convierten en el material con mayor trabajo hasta rotura de los conocidos hasta el momento. Además se ha encontrado que posee una elevada biocompatibilidad y un comportamiento biodegradable. Debido a estas excelentes propiedades se han dedicado importantes esfuerzos a intentar producir fibras inspiradas en la seda de araña. Fruto de estos esfuerzos es el polímero artificial estudiado en este trabajo. Dicho polímero presenta una secuencia de aminoácidos inspirada en la spidroína 1, que es una de las dos proteínas que conforman la seda de araña natural. Uno de los factores más perjudiciales para los polímeros es la radiación ultravioleta (UV), de presencia ubicua en aplicaciones al aire libre, ya que puede provocar la modificación de sus enlaces covalentes y, como consecuencia, modificar sus propiedades mecánicas. Para evaluar el efecto de la radiación UV sobre el material bioinspirado se ha estudiado el comportamiento a tracción simple de fibras sometidas a diferentes tiempos de irradiación con luz UV de longitud de onda de 254 nm. Se ha observado que la radiación UV de 254 nm modifica considerablemente las propiedades mecánicas de este material a tiempos de exposición elevados (a partir de 3 días de irradiación). Además se ha estudiado el comportamiento a fractura de este material cuando es irradiado con luz UV. Se ha observado que a medida que aumenta el tiempo de irradiación las superficies de fractura comienzan a ser cada vez más planas, obteniéndose un aspecto extremadamente especular para muestras irradiadas durante 16 día

Correlation Between Processing Conditions, Microstructure and Mechanical Behavior in Regenerated Silkworm Silk Fibers

Regenerated silkworm fibers spun through a wet-spinning process followed by an immersion postspinning drawing step show a work to fracture comparable with that of natural silkworm silk fibers in a wide range of spinning conditions. The mechanical behavior and microstructure of these high performance fibers have been characterized, and compared with those fibers produced through conventional spinning conditions. The comparison reveals that both sets of fibers share a common semicrystalline microstructure, but significant differences are apparent in the amorphous region. Besides, high performance fibers show a ground state and the possibility of tuning their tensile behavior. These properties are characteristic of spider silk and not of natural silkworm silk, despite both regenerated and natural silkworm silk share a common composition different from that of spider silk

Fractional calculus applied to model arterial viscoelasticity

Arterial viscoelasticity can be described using stress-relaxation experiments. To fit these curves, models with springs and dashpots, based on differential equations, were widely studied. However, uniaxial tests in arteries show particular shapes with an initial steep decay and a slow asymptotic relaxation. Recently, fractional order derivatives were used to conceive a new component called spring-pot that interpolates between pure elastic and viscous behaviors. In this work we modified a standard linear solid model replacing a dashpot with a spring-pot of order α. We tested the fractional model in human arterial segments. Results showed an accurate relaxation response during 1-hour with least squares errors below 1%. Fractional orders α were 0.2-0.4, justifying the extra parameter. Moreover, the adapted parameters allowed us to predict frequency responses that were similar to reported Complex Elastic Moduli in arteries. Our results indicate that fractional models should be considered as real alternatives to model arterial viscoelasticity