Rheokinetic model to characterize the maturation process of gelatin solutions under shear flow

The characterization of maturing gelatin solutions in shear flow is required for an appropriate formulation of food products. Under static conditions, the maturation process of gelatin solutions may be described through a basic structural parameter evolving to the percolation value (gel point). Within the rheological framework, two asymptotic viscosities are well identified for the maturing process of gelatin solutions at the limit zero shear rate. One involves the initial solution viscosity that may be associated with the null structural parameter (the microstructure is not formed yet). The other is the percolation zero shear rate viscosity (assuming an infinite value when approaching the gel time) and corresponds to the maximum value of the structural parameter. Under flow, thixotropic theories combined with the knowledge of suspension rheology allow one to convert directly experimental data obtained as shear stress versus time for a given shear rate into the time evolution of the structural parameter. Consequently rheometric experimental data available places the search for a rheokinetic model of the structural parameter. Here, different expressions for this model are investigated, mainly those involving both the rates of structure breakdown and buildup, where the average cluster size is affected by the shear rate. The rate equation thus obtained may be then applied to arbitrary shear rate histories. Numerical results of the rheokinetic model proposed in this work fit well experimental rheometric data obtained in shear flow for the maturing of different gelatin solutions. Experimental data acquired in this work are presented and discussed in relation to those reported previously in the literature.     

Fatty acid composition of egg yolk phospholipid fractions following feed supplementation of Lohmann Brown hens with humic-fat preparations

The effect of feed supplementation with humic-fat preparations on the fatty acid composition of egg yolk phospholipid fractions was studied. The Lohmann Brown was the experimental hen strain and two feeding mixtures were applied – the standard feed and the mixture supplemented with humic-fat preparations. The fatty acid profile of yolk lipids was significantly affected (P = .05) by the supplementation of feed and total increase of n-3 polyunsaturated fatty acids (PUFA) was established. A different distribution of n-3 PUFA in egg yolk lipid fractions was observed: α-linolenic acid (18:3) was found in the triacylglycerol fraction, whereas docosahexaenoic acid (22:6) was detected in the phospholipid fractions. Supplementation of the hen’s diet with humic-fat preparations resulted in the production of n-3 enriched eggs with decreased n-6/n-3 ratio in all phospholipid fractions in comparison to the eggs from the control group.     

Modeling and simulation of an industrial‐scale parex process

The Parex unit for industrial‐scale purification of p‐xylene was studied through detailed simulation and the accuracy of the developed model tested against real industrial data. Starting from a comprehensive analysis of the construction and operation of the industrial unit, a simulation model was developed that incorporates the existing three major types of dead volumes: bed lines, which connect the beds to the rotary valve, circulation lines, which connect adjacent adsorbent chambers, and bed‐head dead volumes, which are located upstream of each bed due to the existence of internals. By gathering operation data and surveys in the pumparound line and in the extract stream, three case studies were defined and compared with simulation results. The model is capable of predicting the performance of the industrial unit. Further simulations were made and compared with plant data to assess the effect of adsorbent capacity loss on the long‐term performance of the unit. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1345–1363, 2015     

Towards Supramolecular Catalysis with Small Self-assembled Peptides

Self-assembly of small peptides offers unique opportunities for the bottom-up construction of supramolecular catalysts that aim to emulate the efficiency and selectivity of natural enzymes. Small, information-rich, simple molecules based on amino acids can self-organise autonomously into complex systems with emergent catalytic properties. The power of noncovalent interactions can be used to construct supramolecular peptidic tertiary structures. Moreover, specific functional groups present in amino acid side-chains may present either a catalytic activity by themselves or be able to bind cofactors such as metal ions. In this scenario, although relevant progress has been achieved in recent years, promising applications in biomaterials science are foreseen. In this review, we discuss the state-of-the-art of this approach at the interface between supramolecular chemistry and peptide science.     

Laser‐induced surface structures on gold‐coated polymers: Influence of morphology on surface‐enhanced Raman scattering enhancement

The fabrication of highly sensitive and reproducible substrates for Surface‐Enhanced Raman Scattering (SERS) remains a challenging scientific and technological issue. In this work, laser‐induced periodic surface structures are generated on poly(trimethylen terephthalate) films upon laser irradiation with the linearly polarized beams of a Nd:YAG laser (4th harmonic, 266 nm), an ArF excimer laser (193 nm), and a Titanium:sapphire laser (795 nm), resulting in periods close to the laser wavelength when irradiating at normal incidence, and larger periods for different angles of incidence. Additional irradiation with a circularly polarized beam at 266 nm produces superficial circular structures. The nanostructured polymers are coated with a nanoparticle assembled gold layer by pulsed laser deposition at 213 nm. The capabilities of these substrates for SERS are evaluated using benzenethiol as a test molecule and different degrees of Raman signal enhancement are observed depending on the nanostructure type. The highest enhancement factor is obtained by for nanostructured substrates with the highest values of period, depth, and roughness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42770.     

Resilience to increasing temperatures: residential building stock adaptation through codes and standards

The resilience of the current Spanish residential building stock to increased temperatures is modelled. Homogenized daily temperature data recorded at 50 Spanish meteorological stations for the periods 1950–1979 and 1981–2010 were used to investigate anticipated climate warming on the Spanish residential building stock by means of the degree-day method. Impacts on residential buildings were investigated for three different future time periods (2011–2040, 2041–2070 and 2071–2100) for three representative Spanish provincial capitals. Future climate change scenarios comprising two statistical downscaling methods, three general circulation models and two carbon emission scenarios were used to project local climate. Results show that 72% of current residential building stock in Spain is thermally unprotected. In addition, the energy demand for heating the building sector in Spain is expected to decrease by between 30% (Barcelona, B2 scenario) and 36% (Valencia, A2 scenario) by 2100, while the respective energy demand for cooling could increase by between 107% (Valencia, B2 scenario) and 296% (Madrid, A2 scenario) by 2100. To increase resilience to higher winter and summer temperatures, strategies for modifying the built environment are needed, particularly for the role of building codes and standards.

La résilience du parc bâti résidentiel espagnol actuel face à l'augmentation des températures est modélisée. Les données homogénéisées des température journalières enregistrées dans 50 stations météorologiques espagnoles pour les périodes 1950–1979 et 1981–2010 ont été utilisées pour étudier le réchauffement climatique prévu sur le parc bâti résidentiel espagnol en utilisant la méthode des degrés-jours. Les répercussions sur les immeubles résidentiels ont été étudiées pour trois périodes futures différentes (2011–2040, 2041–2070 et 2071–2100) et pour trois capitales provinciales espagnoles représentatives. Il a été utilisé des scénarios de changement climatique futur comprenant deux méthodes de réduction d'échelle statistique, trois modèles de circulation générale et deux scénarios d'émission de carbone pour prévoir le climat local. Les résultats montrent que 72 % du parc bâti résidentiel actuel de l'Espagne est dépourvu de protection thermique. Il est en outre prévu que la demande énergétique liée au chauffage dans le secteur du logement en Espagne diminue de 30 % (Barcelone, scénario B2) à 36 % (Valence, scénario A2) d'ici à 2100, tandis que la demande énergétique respective liée à la climatisation pourrait augmenter de 107 % (Valence, scénario B2) à 296 % (Madrid, scénario A2) d'ici à 2100. Afin d'augmenter la résilience face à des températures hivernales et estivales plus élevées, il est nécessaire de disposer de stratégies de modification du cadre bâti, concernant en particulier le rôle des codes et des normes du bâtiment.

Mots clés: stratégies d'adaptation, performances des bâtiments, réglementation du bâtiment, parc bâti, changement climatique, degrés-jours, surchauffe, confort thermique, vulnérabilité, Espagne     

N‐Benzyl‐4‐((heteroaryl)methyl)benzamides: A New Class of Direct NADH‐Dependent 2‐trans Enoyl–Acyl Carrier Protein Reductase (InhA) Inhibitors with Antitubercular Activity

Isoniazid (INH) remains one of the cornerstones of antitubercular chemotherapy for drug‐sensitive strains of M. tuberculosis bacteria. However, the increasing prevalence of multidrug‐resistant (MDR) and extensively drug‐resistant (XDR) strains containing mutations in the KatG enzyme, which is responsible for the activation of INH into its antitubercular form, have rendered this drug of little or no use in many cases of drug‐resistant tuberculosis. Presented herein is a novel family of antitubercular direct NADH‐dependent 2‐trans enoyl–acyl carrier protein reductase (InhA) inhibitors based on an N‐benzyl‐4‐((heteroaryl)methyl)benzamide template; unlike INH, these do not require prior activation by KatG. Given their direct InhA target engagement, these compounds should be able to circumvent KatG‐related resistance in the clinic. The lead molecules were shown to be potent inhibitors of InhA and showed activity against M. tuberculosis bacteria. This new family of inhibitors was found to be chemically tractable, as exemplified by the facile synthesis of analogues and the establishment of structure–activity relationships. Furthermore, a co‐crystal structure of the initial hit with the enzyme is disclosed, providing valuable information toward the design of new InhA inhibitors for the treatment of MDR/XDR tuberculosis.     

Co-Expression and Co-Localization of Cartilage Glycoproteins CHI3L1 and Lubricin in Osteoarthritic Cartilage: Morphological,Immunohistochemical and Gene Expression Profiles

Osteoarthritis is the most common human arthritis characterized by degeneration of articular cartilage. Several studies reported that levels of human cartilage glycoprotein chitinase 3-like-1 (CHI3L1) are known as a potential marker for the activation of chondrocytes and the progression of Osteoarthritis (OA), whereas lubricin appears to be chondroprotective. The aim of this study was to investigate the co-expression and co-localization of CHI3L1 and lubricin in normal and osteoarthritic rat articular cartilage to correlate their modified expression to a specific grade of OA. Samples of normal and osteoarthritic rat articular cartilage were analyzed by the Kellgren–Lawrence OA severity scores, the Kraus’ modified Mankin score and the Histopathology Osteoarthritis Research Society International (OARSI) system for histomorphometric evaluations, and through CHI3L1 and lubricin gene expression, immunohistochemistry and double immuno-staining analysis. The immunoexpression and the mRNA levels of lubricin increased in normal cartilage and decreased in OA cartilage (normal vs. OA, p < 0.01). By contrast, the immunoexpression and the mRNA levels of CHI3L1 increased in OA cartilage and decreased in normal cartilage (normal vs. OA, p < 0.01). Our findings are consistent with reports suggesting that these two glycoproteins are functionally associated with the development of OA and in particular with grade 2/3 of OA, suggesting that in the future they could be helpful to stage the severity and progression of the disease.     

Hydrogenation of vegetable oil using highly dispersed Pt/γ-Al2O3 catalyst: Effects of key operating parameters and deactivation study

In the present work, Pt/γ-Al₂O₃ catalysts with high metal dispersion were prepared and characterized using chloroplatinic acid and platinum acetylacetonate as metal precursors. The activity and selectivity of the catalysts were evaluated in the hydrogenation of sunflower oil. A comprehensive analysis of the effects of key operational parameters on catalytic performance was carried out. The experimental variables were hydrogen pressure (275.8–551.6 kPa), temperature (160–200°C), and catalyst loading (0.005–0.015 kg Pt_exp/m³_oil). Platinum catalysts were active, with a double bond conversion of 28% at 2 h. The metal precursor affected catalyst selectivity. The catalyst prepared with chloroplatinic acid exhibited a lower formation of trans-isomers compared with Pt acetylacetonate. The γ-Al₂O₃ supported platinum catalyst with a metal loading of 0.51 wt.% and a metal dispersion of 98% maintained its initial catalyst activity and selectivity after 10 consecutive uses (1200 min accumulate operation time), without changes in its catalytic properties. The obtained results suggested that Pt catalysts are an attractive alternative to conventional nickel catalysts for the hydrogenation of vegetable oil.     

Selenocarbamates As a Prodrug-Based Approach to Carbonic Anhydrase Inhibition

A study on the activity of selenocarbamates as a novel chemotype acting as carbonic anhydrase (CA, EC 4.2.1.1) inhibitors is reported. Undergoing CA-mediated hydrolysis, selenocarbamates release selenolates behaving as zinc binding groups and effectively inhibiting CAs. A series of selenocarbamates characterised by high molecular diversity and complexity have been studied against different human CA isoforms such as hCA I, II, IX and XII. Selenocarbamates behave as masked selenols with potential biological applications as prodrugs for CAs inhibition-based strategies. X-ray studies provided insights into the binding mode of this novel class of CA inhibitors.