Co/SiO2 catalysts prepared from Co2(CO)8 for CO hydrogenation into alcohols and hydrocarbons: characterization by magnetic methods and temperature-programmed hydrogenation

The hydrogenation of carbon monoxide over Co/SiO₂ catalysts obtained by reduction of precursors prepared by the reaction of dicobaltoctacarbonyl with silica gives rise to a mixture of alcohols and hydrocarbons. The chain growth probability for hydrocarbon synthesis is similar to that observed over conventional catalysts prepared by the ammonia method (=0.74) with a comparable metal dispersion (metal particle size 4 nm). Alcohol formation yields a smaller chain growth probability (=0.42). Magnetic measurements have shown that in the latter catalyst, small cobalt clusters (1 nm) are likely to be present together with the cobalt particles (4 nm), this observation reconciles apparently conflicting results from the literature. It has been speculated that alcohol formation might be related to the presence of these clusters according to a concerted mechanism. Furthermore, the observation of large amounts of acetates by temperature-programmed hydrogenation, not detected in hydrocarbon selective catalysts, suggests that they may play a role in ethanol synthesis.     

How Mixing and Light Heterogeneity Impact the Overall Growth Rate in Photobioreactors

The microalgae growth rate in photobioreactors responds with inertia to light stimuli. Here, light variations experienced by the algae are accessed through a coupling of an irradiance field calculation and a Lagrangian particle tracking. The response of algae to fluctuating light is then described by a relaxation model involving a single time constant, the value of which is identified from published data. The overall growth rate is calculated as the sum of individual growth rates of all particles. Instantaneous adaptation and full integration asymptotic behaviors are recovered whilst a finite time constant reveals that the overall growth rate is dependent both on mixing and light distribution. This methodology thus quantitatively relates the design parameters to the photobioreactor performance.     

Identification of the Elastic–Plastic Behavior of Adhesively Bonded Structures Under Multi-Axial Loadings: Comparison of a Modified Arcan Test and a Tension/Compression–Torsion Test

Structural bonding is nowadays widespread in the industry. However, characterisation methods and 3D modelling of the adhesives need to be improved. The characterisation requires an experimental procedure to obtain a large experimental database under various loading cases, which represents a significant amount of data. The 3D modelling requires advanced models with several parameters to identify and generally uses inverse identification procedures, which can be time expensive. For a good accuracy, the constitutive models need to take into account the dependency on the hydrostatic stress and be written under the non-associated formalism. In this study, the experimental database is obtained via a modified Arcan test that can cover a wide range of loadings between tension, shear, mixed tension–shear, and mixed compression–shear. A second experimental campaign is realized with a tension/compression–torsion (TCT) test that can cover a greater range of loadings: from tension to compression and mixed tension/compression–shear, with an infinite possibility of mixed loadings. The modified Arcan database is used to identify a 3D elastic–plastic Mahnken–Schlimmer type model, according to an inverse identification procedure developed in a previous study. This model identification is validated on the experimental database coming from the TCT test: a numerical/experimental comparison is realized. This allows the validation of the model and emphasizes the benefits of the TCT test. Indeed, it proves that this test is well suited to characterize adhesive joints and presents several capacities that will be really useful for further studies, like an infinite range of non-proportional loadings available.     

Experimental investigation of a new type of interfacial instability in a reactive coextrusion process

This paper deals with the study of new interfacial instabilities, called “grainy” defects, in coextrusion process of reactive multilayer polymers. The main objective was to better understand this phenomenon since no help can be found in the literature. The fundamental approach from a micro‐scale to a macro‐scale involves the study of relationships between polymer structure, processing, and interfacial properties. The influence of these parameters on the generation of “grainy” defects during coextrusion has been assessed in correlation with physicochemical properties. Through this work, rheological properties and the interfacial morphology between tie and barrier layers have been investigated by shear stress relaxation experiments and transmission electronic microscopy, respectively. Depending on the reactive polymers, the interfacial coupling was found to significantly alter the stress relaxation behavior by extending the relaxation time and generating an interfacial roughness. Hence, relations between the copolymer architecture, the relaxation process, and the interfacial morphology were established in correlation with the generation of grainy defects in coextrusion process. POLYM. ENG. SCI., 55:2542–2552, 2015. © 2015 Society of Plastics Engineers     

Engraftment of Prevascularized,Tissue Engineered Constructs in a Novel Rabbit Segmental Bone Defect Model

The gold standard treatment of large segmental bone defects is autologous bone transfer, which suffers from low availability and additional morbidity. Tissue engineered bone able to engraft orthotopically and a suitable animal model for pre-clinical testing are direly needed. This study aimed to evaluate engraftment of tissue-engineered bone with different prevascularization strategies in a novel segmental defect model in the rabbit humerus. Decellularized bone matrix (Tutobone) seeded with bone marrow mesenchymal stromal cells was used directly orthotopically or combined with a vessel and inserted immediately (1-step) or only after six weeks of subcutaneous “incubation” (2-step). After 12 weeks, histological and radiological assessment was performed. Variable callus formation was observed. No bone formation or remodeling of the graft through TRAP positive osteoclasts could be detected. Instead, a variable amount of necrotic tissue formed. Although necrotic area correlated significantly with amount of vessels and the 2-step strategy had significantly more vessels than the 1-step strategy, no significant reduction of necrotic area was found. In conclusion, the animal model developed here represents a highly challenging situation, for which a suitable engineered bone graft with better prevascularization, better resorbability and higher osteogenicity has yet to be developed.     

Assessing the Antimicrobial Activity of Polyisoprene Based Surfaces

There has been an intense research effort in the last decades in the field of biofouling prevention as it concerns many aspects of everyday life and causes problems to devices, the environment, and human health. Many different antifouling and antimicrobial materials have been developed to struggle against bacteria and other micro- and macro-organism attachment to different surfaces. However the “miracle solution” has still to be found. The research presented here concerns the synthesis of bio-based polymeric materials and the biological tests that showed their antifouling and, at the same time, antibacterial activity. The raw material used for the coating synthesis was natural rubber. The polyisoprene chains were fragmented to obtain oligomers, which had reactive chemical groups at their chain ends, therefore they could be modified to insert polymerizable and biocidal groups. Films were obtained by radical photopolymerization of the natural rubber derived oligomers and their structure was altered, in order to understand the mechanism of attachment inhibition and to increase the efficiency of the anti-biofouling action. The adhesion of three species of pathogenic bacteria and six strains of marine bacteria was studied. The coatings were able to inhibit bacterial attachment by contact, as it was verified that no detectable leaching of toxic molecules occurred.     

Tribological behavior of composites fabricated by reactive SPS sintering in Ti-Si-C system

In this study, wear and friction behavior of two based-composites from the Ti-Si-C system, (40 wt% TiC; 28 wt% Ti₅Si₃; 17 wt% Ti₃SiC₂) and (18 wt% TiC; 26 wt% Ti₅Si₃; 41 wt% Ti₃SiC₂) reinforced by 15 wt% of large size SiC (100-150 µm) particles were investigated. The four-phase composites exhibited approximatively the same friction coefficient (µ ~ 0.9) under high loads (10 N and 7 N). The composite with high Ti₃SiC₂ showed higher wear rate values by one order of magnitude. However, under 1 N, the composite with high TiC content showed a higher running-in period and a lower steady state µ value (0.37 after 1000 m sliding distance). Scanning electron microscopy, Energy Dispersive X-Ray and Raman spectroscopy analysis of the worn surfaces of the two composites revealed that oxidation was the dominant wear mechanism. The oxidation process and the removal kinetics of the oxides during sliding controlled the tribological behavior of the composites. The influence of processing variables on microstructures development and wear mechanisms of the composites is discussed.     

Characterization of biodegradable core–clad borosilicate glass fibers with round and rectangular cross-section

Here, we report on core–clad bioactive borosilicate fibers, that we have prepared both with round and rectangular cross-section profile. The exposed approach, which relies on the stacking and drawing of glass slabs, demonstrates our ability to develop bioactive-based glass fibers with tailored cross-section profiles. Tens-of-meters-long fibers were successfully drawn, although suffering from elevated losses in the case of the rectangular ones. The response of the fibers in simulated body fluid was studied for both geometries. We found that a round cladding can act as protective layer, tempering effects of the corrosion. We also noticed that rectangular fibers are more prone to degradation, the enhanced corrosion beginning from their sharp corners as they accumulated residual tensile stress during drawing. To the best of our knowledge, this is the first report on the effect of residual tensile stresses from surface tension deformations applied to the corrosion of rectangular fibers. As geometry plays a critical role on the biodegradation behavior of the fiberglass, we believe the enclosed results could lead to the design of fiber devices with tailored cross-section profile in order to tune their rate of degradation on solely based geometrical effects.     

Synthesis of N-acryloxysuccinimide copolymers by RAFT polymerization, as reactive building blocks with full control of composition and molecular weights

The reversible addition-fragmentation chain transfer (RAFT) polymerization process was used to synthesize well-defined N-acryloxysuccinimide (NAS) based copolymers, very useful reactive building blocks for various applications. Kinetic studies of RAFT copolymerization of NAS with a bi-substituted acrylamide derivative, N-acryloylmorpholine (NAM), were performed in the presence of tert-butyl dithiobenzoate (tBDB). An excellent control was reached with very high conversions (>95%), molecular weights (MW) up to 80?000 g mol⁻¹ and very narrow molecular weight distributions (MWD) (polydispersity indices, PDI<1.1), as determined by aqueous size exclusion chromatography with on-line light scattering detector (SEC/LS). In addition, the comparison of RAFT and conventional NAM/NAS free radical copolymerization indicated that the apparent reactivity ratios in RAFT are similar to the reactivity ratios determined from conventional copolymerization. An identical azeotropic composition (60/40 NAM/NAS molar ratio) was obtained providing perfectly random poly(NAM-co-NAS) copolymers with full control of composition and MW. These copolymer chains with regularly-distributed reactive functions can be integrated into more complex architectures. As an example, poly[(NAM-co-NAS)-b-NAM] block copolymers with length-varying poly(NAM) block were synthesized with a very efficient control over MW, MWD and composition.     

Accepting its random coil nature allows a partial NMR assignment of the neuronal Tau protein

A combined strategy to obtain a partial NMR assignment of the neuronal Tau protein is presented. Confronted with the extreme spectral degeneracy that the spectrum of this 441 amino acid long unstructured protein presents, we have introduced a graphical procedure based on residue type-specific product planes. Combining this strategy with the search for pairwise motifs, and combining the spectra of different Tau isoforms and even of peptides derived from the native sequence, we arrive at a partial assignment that is sufficient to map the interactions of Tau with its molecular partners. The obtained assignments equally confirm the absence of regular secondary structure in the isolated protein.