Synthesis of Fibrin-Type I Collagen Biomaterials via an Acidic Gel

Fibrin-Type I collagen composite gels have been widely studied as biomaterials, in which both networks are usually formed simultaneously at a neutral pH. Here, we describe a new protocol in which mixed concentrated solutions of collagen and fibrinogen were first incubated at acidic pH to induce fibrinogen gel formation, followed by a pH change to neutral inducing collagen fiber formation. Thrombin was then added to form fibrin-collagen networks. Using this protocol, mixed gels containing 20 mg.mL⁻¹ fibrin and up to 10 mg.mL⁻¹ collagen could be prepared. Macroscopic observations evidenced that increasing the content of collagen increases the turbidity of the gels and decreases their shrinkage during the fibrinogen-to-fibrin conversion. The presence of collagen had a minor influence on the rheological properties of the gels. Electron microscopy allowed for observation of collagen fibers within the fibrin network. 2D cultures of C2C12 myoblasts on mixed gels revealed that the presence of collagen favors proliferation and local alignment of the cells. However, it interferes with cell differentiation and myotube formation, suggesting that further control of in-gel collagen self-assembly is required to elaborate fully functional biomaterials.     

Bone matrix like assemblies of collagen: from liquid crystals to gels and biomimetic materials

Skeletal tissues associate in close interaction, a dense organic matrix and a mineral network. In bone, the major structural protein is type I collagen, associated with inorganic crystals of hydroxyapatite. The three-dimensional arrangement of collagen fibrils in compact bone forms regularly ordered networks and a parallel was evidenced between these structures and molecular assemblies described in liquid crystals. Similar structures are now obtained in vitro. Indeed, when purified type I collagen is highly concentrated in an acid soluble state, the protein spontaneously assembles into ordered liquid crystalline phases. After a sol/gel transition triggered by pH increase, biomimetic materials are formed which resemble the exact compact bone matrix architecture over distances reaching centimetres and more. The properties of these highly ordered materials will be reviewed recalling their supramolecular arrangement and the corresponding patterns when visualised in polarised light microscopy (birefringence) and transmission electron microscopy (TEM). The association of inorganic phases (amorphous silica) to form chiral hybrid materials will also be described so as the behaviour of cells (fibroblast adhesion and migration) when seeded on these dense biomimetic matrices.     

Surface morphology and reaction at Cu/Si interface—Effect of native silicon suboxide

Copper thin films are deposited by thermal evaporation on unetched and etched monocrystalline silicon. The study by alpha particles backscattering (RBS) raises a strong diffusion of copper in silicon substrates with and without native suboxide layer. On the other hand, the X-rays diffraction shows the formation and the growth of Cu₃Si and Cu₄Si silicides. Whereas the scanning microscopy underlines large crystallites growth surrounded by black zones of silicon coming from the uncovered substrate, independently to the surface state of the substrate, after annealing at high temperature. The presence of native silicon suboxide at Cu/Si interface, influences in a drastic way the minimal temperature to which the interfacial reaction occurs. The oxygen impurities detected by microanalysis, after heat treatment under vacuum, are closely related to the growth of silicides crystallites.     

Aes study of the segregation behaviour of silicon in high-silicon steel during oxidation

The segregation behaviour of silicon during oxidation of a high-silicon steel has been investigated by AES. The results show that silicon seems to have two states of oxidation: one leading to the formation of SiO_x and iron oxides when the oxidation and the following heat treatments in vacuum are performed below 500°C and the other occurring at temperatures higher than 500°C, leading to the formation of SiO₂ and segregation of this species toward the surface without oxidation of iron.     

Use of hydrostatic pressure in determining the nature of DX centers in GaAiAs-Si

Abstract

We report on activated capture and emission experiments obtained under hydrostatic pressure. The observed structures in the thermostimulated capture curves are interpreted as a competition between capture and emission from the different configurations of the DX center, which are related to the local environment of the Si atom. The analysis of the capture kinetic experiments supports the hypothesis of the negative charge state of the DX center.     

Passive acoustic detection and localization of whales: effects of shipping noise in Saguenay-St. Lawrence Marine Park

The performance of large-aperture hydrophone arrays to detect and localize blue and fin whales' 15-85 Hz signature vocalizations under ocean noise conditions was assessed through simulations from a normal mode propagation model combined to noise statistics from 15 960 h of recordings in Saguenay-St. Lawrence Marine Park. The probability density functions of 2482 summer noise level estimates in the call bands were used to attach a probability of detection/masking to the simulated call levels as a function of whale depth and range for typical environmental conditions. Results indicate that call detection was modulated by the calling depth relative to the sound channel axis and by modal constructive and destructive interferences with range. Masking of loud infrasounds could reach 40% at 30 km for a receiver at the optimal depth. The 30 dB weaker blue whale D-call were subject to severe masking. Mapping the percentages of detection and localization allowed assessing the performance of a six-hydrophone array under mean- and low-noise conditions. This approach is helpful for optimizing hydrophone configuration in implementing passive acoustic monitoring arrays and building their detection function for whale density assessment, as an alternative to or in combination with the traditional undersampling visual methods.     

Liquid crystallinity in collagen systems in vitro and in vivo

Collagens are unique triple helical proteins present in large quantities in a fibrillar form in tissues like tendon, bone, skin, cornea, where type I collagen predominates. The passage from triple helical molecules to fibrils obeys to controlled assembly properties, both in vitro by pH raise and in vivo through enzymatic control. The passage from individual fibrils to ordered fibrillar arrays could rely on self-assembly processes as suggested by the liquid crystalline properties of collagen. The present review considers this question recalling the liquid crystalline ordering properties of collagen or procollagen at high concentrations and the question of molecular packing within fibrils. The presence of alignments, undulations and twist at a suprafibrillar level will be described both from basic data in living tissues and recent experiments in self assembled materials. The possible link between laboratory experiences and biological processes will be discussed.     

Influencing the regioselectivity of lipase-catalyzed hydrolysis with [bmim]PF6

An easy preparation of mono-deprotected thioglucopyranosides via a selective Candica cylindracea lipase-catalyzed hydrolysis of a commercially available peracetylated precursor is described. Especially, ethyl 2,3,4-tri-O-acetyl-1-thio-β-d-glucopyranoside and ethyl 2,3,6-tri-O-acetyl-1-thio-β-d-glucopyranoside were obtained in 100% and 54% isolated yields, respectively. The influence of the ratio of [bmim]PF₆/buffer toward the regioselectivity of the deacetylation step and the acyl migration is discussed.     

Modal depth function estimation using time-frequency analysis

Acoustic propagation in shallow water is characterized by a set of depth-dependent modes, the modal depth functions, which propagate in range according to their horizontal wavenumbers. For inversion purposes, modal depth function estimation in shallow water is an issue when the environment is not known. Classical methods that provide blind mode estimation rely on the singular value decomposition of the received field at different frequencies over a vertical array of transducers. These methods require that the vertical array spans the full water column. This is obviously a strong limitation for the application of such methods in an operational context. To overcome these shortcomings, this study proposes to replace the spatial diversity constraint by a frequency diversity condition, and thus considers the case of a field emanating from an impulsive source. Indeed, because of the discrete nature of the wavenumber spectrum and due to their dispersive behavior, the modes are separated in the time-frequency domain. This phenomenon enables the design of a modal filtering scheme for signals received on a single receiver. In the case of a vertical receiver array, the modal contributions can be isolated for each receiver even when using a partial water column spanning array. This method thus eliminates the receiving constraints of classical methods of modal depth function estimation, although it imposes the use of an impulsive source. The developed algorithm is benchmarked on numerical simulations and validated on laboratory experimental data recorded in an ultrasonic waveguide. Practical applications are also discussed.