Spider silk as a blueprint for greener materials : a review

Spider silk exhibits remarkable properties, especially its well-known tensile performances. They rely on a complex nanostructured hierarchical organisation that studies progressively elucidate. Spider silk encompasses a vast range of fibres that exhibit diverse and captivating physical and biological characteristics. The full understanding of the relation between structure and properties may lead in the future to the design of a variety of high-performance, tailored materials and devices. Reknown for being produced in mild and benign conditions, this outstanding biological material constitutes one of the more representative example of biomimetism. In addition, silk’s structure is produced with limited means, i.e. low energy and relatively simple renewable constituents (silk proteins). Then, if successfully controlled and adequately transposed in biomaterials, some properties of natural silk could lead to innovative green materials that may contribute to reduce the ecological footprint of societies. In fact, striking recent advanced applications made with B. mori silk suggest that spider silk-based materials may lead to advanced resistant and functional materials, then becoming among the most promising subject of study in material science. However, several challenges have to be overcome, especially our ability to produce native-like silk, to control biomaterials’ structure and properties and to minimise their ecological footprint. This paper reviews the characteristics of spider silk that make it so attractive and that may (or may not) contribute to reduce ecological footprint of materials and the challenges in producing innovative spider silk-based materials. First, from a biomimetic perspective, the structure and models that explain the tensile resistance of natural silk are presented, followed by the state of knowledge regarding natural silk spinning process and synthetic production methods. Biocompatibility (biosafety and biofunctionality) as well as biodegradability issues are then addressed. Finally, examples of applications are reviewed. Features that may lead to the design of green materials are emphasised throughout

Using infrared and raman microspectroscopies to compare ex vivo involved psoriatic skin with normal human skin

Psoriasis is a chronic dermatosis that affects around 3% of the world’s population. The etiology of this autoimmune pathology is not completely understood. The barrier function of psoriatic skin is known to be strongly altered, but the structural modifications at the origin of this dysfunction are not clear. To develop strategies to reduce symptoms of psoriasis or adequate substitutes for modeling, a deep understanding of the organization of psoriatic skin at a molecular level is required. Infrared and Raman microspectroscopies have been used to obtain direct molecular-level information on psoriatic and healthy human skin biopsies. From the intensities and positions of specific vibrational bands, the lipid and protein distribution and the lipid order have been mapped in the different layers of the skin. Results showed a similar distribution of lipids and collagen for normal and psoriatic human skin. However, psoriatic skin is characterized by heterogeneity in lipid/protein composition at the micrometer scale, a reduction in the definition of skin layer boundaries and a decrease in lipid chain order in the stratum corneum as compared to normal skin. A global decrease of the structural organization is exhibited in psoriatic skin that is compatible with an alteration of its barrier properties

Transdermal diffusion, spatial distribution and physical state of a potential anticancer drug in mouse skin as studied by diffusion and spectroscopic techniques

Background:Understanding the efficiency of a transdermal medical drug requires the characterization of its diffusion process, including its diffusion rate, pathways and physical state. Objective:The aim of this work is to develop a strategy to achieve this goal. Methods:FTIR spectroscopic imaging in conjunction with a Franz cell and HPLC measurements were used to examine the transdermal penetration of deuterated tert-butyl phenylchloroethylurea (tBCEU), a molecule with a potential anticancer action. tBCEU has been solubilized in an expedient solvent mixture and its diffusion in hairless mouse skin has been studied. Results:The results indicate that tBCEU diffuses across the skin for more than 10 hours with a rate comparable to selegiline, an officially-approved transdermal drug. IR image analyses reveal that after 10 hours, tBCEU penetrates skin and that its spatial distribution does not correlate with neither the distribution of lipids nor proteins. tBCEU accumulates in cluster domains but overall low concentrations are found in skin. FTIR spectroscopic imaging additionally reveals that tBCEU is in a crystalline form. Conclusions:The results suggest that tBCEU is conveyed through the skin without preferential pathway. FTIR spectroscopic imaging and transdermal diffusion measurements appear as complementary techniques to investigate drug diffusion in skin

Wetting by liquid sodium and fracture path analysis of sodium induced embrittlement of 304L stainless steel

The wettability of the 304L steel is an important parameter in Liquid Metal Embrittlement studies. Empirically, it is found to be greatly enhanced by pre-exposure to oxygenated liquid sodium. The corrosion interface formed during exposure to sodium has been analyzed at the nanoscale by transmission electron microscopy using the focused ion beam sampling. A thin layer of sodium chromite (Na xCrO2 with x ≤ 1) is detected at the interface validating wetting on an oxide mechanism for the enhanced wetting after pre-exposure. Fracture micromechanisms and the crack path of liquid sodium-embrittled austenitic steel 304L at 573 K have been investigated down to the nanoscale. High-resolution orientation mapping analyses immediately below the fracture surface show that abundant martensitic transformations (γ → α) and twinning occur during deformation of austenite. The preferential crack path is intergranular along the newly formed γ/γ interfaces. It is concluded that these transformations play a major role in the fracture process

Patients’ high acceptability of a future therapeutic HIV vaccine in France: a French paradox?

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Investigation of crack propagation resistance of 304L, 316L and 316L(N) austenitic steels in liquid sodium

In order to assess the susceptibility of candidate structural materials to Liquid Metal Embrittlement (LME), the fracture behavior of three grades of austenitic steels was investigated in oxygenated (200 wppm) liquid sodium in the temperature range [473–673 K] on notched axisymmetric tensile specimens. The tests were carried out in an inert glove box at very low concentrations of dioxygen and humidity (<1 ppm) to prevent further contamination after pre-exposure in oxygenated liquid sodium. A decrease in crack propagation resistance of the three austenitic steels (304 L, 316 L(N), 316 L) is observed in oxygenated liquid sodium (200 wppm) from 573, 623 and 673 K respectively after pre-wetting in oxygenated sodium. This reduction is correlated with a ductile to brittle change of the fracture surface. This effect observed with the three austenitic steels is attributed to the onset of LME after significant plastic deformation

Liquid metal embrittlement of a dual-phase Al0.7CoCrFeNi high-entropy alloy exposed to oxygen-saturated lead-bismuth eutectic

This paper reports a new liquid metal embrittlement (LME) system in which a dual-phase Al0.7CoCrFeNi (equimolar fraction) high-entropy alloy (HEA) is embrittled by lead-bismuth eutectic (LBE) at 350 and 500°C. At 350°C, (Ni, Al)-rich BCC phase is embrittled, leading to intragrain cracking within this phase, while the predominant cracking mode changes to BCC/FCC phase boundary decohesion at 500°C. At both temperatures, cracks are rarely seen in the (Co, Cr, Fe)-rich FCC phase, indicating that this phase is immune to LME. Furthermore, the results suggest a transition from an adsorption-dominated LME mechanism at 350°C to a phase boundary wetting-dominated LME mechanism at 500°C

ENDOTHELIUM-INDEPENDENT AND ENDOTHELIUM-DEPENDENT VASORELAXATION BY A DICHLOROMETHANE FRACTION FROM ANOGEISSUS LEIOCARPUS (DC) GUILL. ET PERR. (COMBRETACEAE): POSSIBLE INVOLVEMENT OF CYCLIC NUCLEOTIDE PHOSPHODIESTERASE INHIBITION.

Many traditional medicinal herbs from Burkina Faso are used to treat arterial hypertension (HTA). Among them, Anogeissus leiocarpus (A. Leiocarpus) which is well known and widely used in Burkina traditional medicine. Herein we assess the effects of dichloromethane fraction from A. leiocarpus stem bark (ALF), selected as the most active on cyclic nucleotide phosphodiesterases (PDEs) and characterized its specificity towards purified vascular PDE1 to PDE5 isoenzymes and study its effects on a vascular model. ALF potently and preferentially inhibits (IC50=1.6 ± 0.6 µg/mL) the calmodulin-dependent phosphodiesterase PDE1, being mainly present in vascular smooth muscle and preferentially hydrolyses cGMP. In the same range (IC50 =2.8 ±0.2 µg/ml) ALF inhibits PDE2, a cGMP-activated enzyme that is only present in endothelial cells and hydrolyses both cAMP and cGMP. PDE5, which specifically hydrolyses cGMP and which mainly contributes to cGMP hydrolysis is also potently inhibited by ALF (IC50=7.6±3.5 µg/ml). The potencies of ALF on cAMP hydrolyzing isoenzymes was lesser, being more effective on PDE4 (IC50= 17.6±3.5 µg/ml) than on PDE3 (60.9 ± 1.8 µg/ml). Since the major effect of ALF were against cGMP hydrolysis and since cGMP is implicated in endothelium-dependent relaxation, the endothelium-dependent vasorelaxation was studied on isolated porcine coronary arteries rings pre-contracted with U46619. The endothelium-dependent vasorelaxation is significantly inhibited by Nω-nitro-L-arginine (LNA 300 µmol/L, an inhibitor of endothelial NO synthase), but not affected by charybdotoxin (CTX, 100nM) plus apamin (APA, 100nM) (two inhibitors of EDHF-mediated responses). The combination of 4-aminopyridine (4-AP, 1 mmol/L, inhibitor of voltage-dependent potassium channels, Kv) plus baryum (Ba2+, 30 µmol/L, inhibitor of the potassium channels with entering correction, Kir) plus ouabain (3 µmol/L, inhibitor of ATPase Na+/K+ channels) partially inhibits endothelium-independent vasorelaxant effect. This endothelium-independent relaxant effect was also sensitive to combination of 1H-[1,2,4]-oxadiazole-[4,3-α]-quinoxalin-1-one (ODQ, 10 µM, soluble guanylyl cyclase inhibitor) and N-[2-(p-Bromocinnamylamino)ethyl]-5-isoquinoline sulfonamide dihydrochloride (H89, 100 nM, Protein Kinase A inhibitor). Taken together, these results indicate that ALF is a powerful vasodilator modulated by the formation of NO from endothelium, but also act by directly relaxing the vascular smooth muscle cells, by inhibiting cGMP hydrolyzing PDEs (PDE1, PDE2 and PDE5) and to a lesser extend on cAMP degradation (PDE3 and PDE4), cAMP and cGMP being second messengers involved in vascular relaxation

Validity of Crystal Plasticity Models Near Grain Boundaries: Contribution of Elastic Strain Measurements at Micron Scale

Synchrotron Laue microdiffraction and digital image correlation measurements were coupled to track the elastic strain field (or stress field) and the total strain field near a general grain boundary in a bent bicrystal. A 316L stainless steel bicrystal was deformed in situ into the elasto-plastic regime using a four-point bending setup. The test was then simulated using finite elements with a crystal plasticity model comprising internal variables (dislocation densities on discrete slip systems). The predictions of the model are compared with both the total strain field and the elastic strain field obtained experimentally. While activated slip systems and total strains are reasonably well predicted, elastic strains appear overestimated next to the grain boundary. This suggests that conventional crystal plasticity models need improvement to correctly model stresses at grain boundaries

Molecular mechanisms of the cardiovascular protective effects of polyphenols

Epidemiological studies have reported a greater reduction in cardiovascular risk and metabolic disorders associated with diets rich in polyphenols. The antioxidant effects of polyphenols are attributed to the regulation of redox enzymes by reducing reactive oxygen species production from mitochondria, NADPH oxidases and uncoupled endothelial NO synthase in addition to also up-regulating multiple antioxidant enzymes. Although data supporting the effects of polyphenols in reducing oxidative stress are promising, several studies have suggested additional mechanisms in the health benefits of polyphenols. Polyphenols from red wine increase endothelial NO production leading to endothelium-dependent relaxation in conditions such as hypertension, stroke or the metabolic syndrome. Numerous molecules contained in fruits and vegetables can activate sirtuins to increase lifespan and silence metabolic and physiological disturbances associated with endothelial NO dysfunction. Although intracellular pathways involved in the endothelial effects of polyphenols are partially described, the molecular targets of these polyphenols are not completely elucidated. We review the novel aspects of polyphenols on several targets that could trigger the health benefits of polyphenols in conditions such as metabolic and cardiovascular disturbances