Optimizing the lignin based synthesis of flexible polyurethane foams employing reactive liquefying agents

The present work is focused on the optimization of a green process based on the employment of by‐products obtained from wood treatments as raw materials for producing flexible polyurethane foams. More specifically, lignin was employed in flexible polyurethane foams in order to partially replace the usual fossil polyols; therefore glycerol (GLY) and glycerin polyglycidyl ether (EJ 300) were used as the polyol fraction for lignin liquefaction. Polypropylene glycol triol was used as a chain extender in different ratios with liquefaction solvents, and polymeric diphenylmethane diisocyanate as an isocyanate fraction. Liquefaction of lignin was performed by microwave irradiation, thus reducing the processing time and energy required compared to present industrial production processes. All the foams were produced in controlled expansion through the adoption of a ‘one‐shot’ approach, using water as a blowing agent and with an isocyanate index (NCO/OH) of less than 100 to improve the flexibility of the foam. This approach allowed for the substitution of up to 12% of common petro derived polyol with commercial soda lignin. Finally, the foams were characterized, presenting properties that could be modulated as a function of lignin content, GLY/EJ 300 ratio and isocyanate index. The qualities of the foams were compatible with existing materials used for furniture and for the interiors of car seats and couches. © 2015 Society of Chemical Industry     

CTNS mutations in an American-based population of cystinosis patients

Nephropathic cystinosis is an autosomal recessive lysosomal storage disease characterized by renal failure at 10 years of age and other systemic complications. The gene for cystinosis, CTNS, has 12 exons. Its 2.6-kb mRNA codes for a 367-amino-acid putative cystine transporter with seven transmembrane domains. Previously reported mutations include a 65-kb "European" deletion involving marker D17S829 and 11 small mutations. Mutation analysis of 108 American-based nephropathic cystinosis patients revealed that 48 patients (44%) were homozygous for the 65-kb deletion, 2 had a smaller major deletion, 11 were homozygous and 3 were heterozygous for 753G-->A (W138X), and 24 had 21 other mutations. In 20 patients (19%), no mutations were found. Of 82 alleles bearing the 65-kb deletion, 38 derived from Germany, 28 from the British Isles, and 4 from Iceland. Eighteen new mutations were identified, including the first reported missense mutations, two in-frame deletions, and mutations in patients of African American, Mexican, and Indian ancestry. CTNS mutations are spread throughout the leader sequence, transmembrane, and nontransmembrane regions. According to a cystinosis clinical severity score, homozygotes for the 65-kb deletion and for W138X have average disease, whereas mutations involving the first amino acids prior to transmembrane domains are associated with mild disease. By northern blot analysis, CTNS was not expressed in patients homozygous for the 65-kb deletion but was expressed in all 15 other patients tested. These data demonstrate the origins of CTNS mutations in America and provide a basis for possible molecular diagnosis in this population.     

Cooperation in Games and Epistemic Readings of Independence-Friendly Sentences

In the literature on logics of imperfect information it is often stated, incorrectly, that the Game-Theoretical Semantics of Independence-Friendly (IF) quantifiers captures the idea that the players of semantical games are forced to make some moves without knowledge of the moves of other players. We survey here the alternative semantics for IF logic that have been suggested in order to enforce this “epistemic reading” of sentences. We introduce some new proposals, and a more general logical language which distinguishes between “independence from actions” and “independence from strategies”. New semantics for IF logic can be obtained by choosing embeddings of the set of IF sentences into this larger language. We compare all the semantics proposed and their purported game-theoretical justifications, and disprove a few claims that have been made in the literature.     

Nanostructure and Micromechanical Properties of Silica/Silicon Oxycarbide Porous Composites

The microhardness–nanostructure correlation of a series of silica/silicon oxycarbide porous composites has been investigated, as a function of pyrolysis temperature, T _p. The pyrolyzed products have been studied by means of scanning electron microscopy, mercury porosimetry, chemical analysis, solid-state ²⁹Si-NMR, X-ray diffraction, Raman spectroscopy, and microindentation hardness. Two distinct regimes are found for the microhardness behavior with T _p. In the low-temperature regime (1000°C ≤ T _p < 1300°C), the material response to indentation seems to be dominated by the large amount of pores present in the samples. In this T _p range, low microhardness values, H , are found (<110 MPa). Above T _p= 1300°C, a conspicuous H increase is observed. In this high-temperature regime ( T _p= 1300–1500°C), microhardness values are shown to notably increase with increasing pyrolysis temperature. The H behavior at T _p= 1300–1500°C is discussed in terms of (i) the volume fraction of pores and the average pore size, (ii) the bond density of the oxycarbide network, and (iii) the occurrence of a nanocrystalline SiC phase.     

Comparison of conventional and spherical reactor for the industrial auto-thermal reforming of methane to maximize synthesis gas and minimize CO2

Auto-thermal reforming (ATR), a combination of exothermic partial oxidation and endothermic steam reforming of methane, is an important process to produce syngas for petrochemical industries. In a commercial ATR unit, tubular fixed bed reactors are typically used. Pressure drop across the tube, high manufacturing costs, and low production capacity are some disadvantages of these reactors. The main propose of this study is to offer an optimized radial flow, spherical packed bed reactor as a promising alternative for overcoming the drawbacks of conventional tubular reactors. In the current research, a one dimensional pseudo-homogeneous model based on mass, energy, and momentum balances is applied to simulate the performance of packed-bed reactors for the production of syngas in both tubular and spherical reactors. In the optimization section, the proposed work explores optimal values of various decision variables that simultaneously maximize outlet molar flow rate of H₂, CO and minimize molar flow rate of CO₂ from novel spherical reactor. The multi-objective model is transformed to a single objective optimization problem by weighted sum method and the single optimum point is found by using genetic algorithm. The optimization results show that the pressure drop in the spherical reactor is negligible in comparison to that of the conventional tubular reactor. Therefore, it is inferred that the spherical reactor can operate with much higher feed flow rate, more catalyst loading, and smaller catalyst particles.     

Titration force microscopy on supported lipid bilayers

The use of chemically modified atomic force microscopy (AFM) probes allows us to measure the surface charges of supported planar lipid bilayers with high sensitivity through the force spectroscopy operation mode. By controlling the chemistry of the tip, we can perform a classical analytical chemistry titration where the titration agent is a weak acid (attached to the AFM tip) with the particularity of being performed in surface rather than in solution and, especially, at the nanometric scale. Thus, the AFM tip acts as a real "nanosensor". The approaching curves of the force plots reveal that electrostatic interactions between the tip and the supported membrane play a key role. Besides, the plot of the adhesion force (measured from the retracting curve of the force plots) versus pH displays a nonsigmoidal shape with a peak in the adhesion force attributed to high-energy hydrogen bonds. One of these peaks corresponds to the pKa of the surface under study and the other to the pKa of the titrating probe attached to the tip.     

Modelling the Floating Ladder Track Response to a Moving Load by an Infinite Bernoulli-Euler Beam on Periodic Flexible Supports

An infinite Bernoulli-Euler beam (representing the "combined rail" consisting of the rail and longitudinal sleeper) mounted on periodic flexible point supports (representing the railpads) has already proven to be a suitable mathematical model for the floating ladder track (FLT), to define its natural vibrations and its forced response due to a moving load. Adopting deliberately conservative parameters for the existing FLT design, we present further results for the response to a steadily (uniformly) moving load when the periodic supports are assumed to be elastic, and then introduce the mass and viscous damping of the periodic supports. Typical support damping significantly moderates the resulting steady deflexion at any load speed, and in particular substantially reduces the magnitude of the resonant response at the critical speed. The linear mathematical analysis is then extended to include the inertia of the load that otherwise moves uniformly along the beam, generating overstability at supercritical speeds — i.e. at load speeds notably above the critical speed predicted for the resonant response when the load inertia is neglected. Neither the resonance nor the overstability should prevent the safe implementation of the FLT design in modern high speed rail systems.     

Use of homogenisation pressure to improve quality and functionality of probiotic fermented milks containing Lactobacillus rhamnosus BFE 5264

The effects of 60‐MPa milk homogenisation treatment were investigated on the viability of the probiotic strain Lactobacillus rhamnosus BFE5264, when used as yoghurt co‐starter, as well as on the aroma profile, texture and microstructure of the resulting set‐type fermented milks. The results demonstrated that the combined use of homogenisation pressure and co‐inoculation of the probiotic strain with the traditional yoghurt starters allowed the reduction in the product coagulation time, the increase of the probiotic strain viability and the improvement of the product volatile molecule profiles. The rheological indices and the microstructure results indicated the positive effects of the milk homogenisation treatment on the product viscosity index and exopolysaccharide production.