Structural basis for selective inhibition of trypanosomatid glyceraldehyde-3-phosphate dehydrogenase: molecular docking and 3D QSAR studies

The glycolytic enzyme glyceraldehyde-3-phosphate dehydrogenase (GAPDH) is as an attractive target for the development of novel antitrypanosomatid agents. In the present work, comparative molecular field analysis and comparative molecular similarity index analysis were conducted on a large series of selective inhibitors of trypanosomatid GAPDH. Four statistically significant models were obtained ( r2 > 0.90 and q2 > 0.70), indicating their predictive ability for untested compounds. The models were then used to predict the potency of an external test set, and the predicted values were in good agreement with the experimental results. Molecular modeling studies provided further insight into the structural basis for selective inhibition of trypanosomatid GAPDH.     

Theoretical understanding of the increment of beta upon protonation of pyridine peripheral octupolar molecules: toward nonlinear optical sensors

In this article, we present a computational study of the nonlinear optical properties of pyridine-based octupolar molecules in their neutral and fully triprotonated states. The effect of the core substitution and the degree of conjugation with the periphery has been also established and confirms the possibility of fine-tuning the nonlinear optical response. Computations involving the time-dependent density-functional theory approach serve to further explore the existence of excited states with nonzero dipole moment. From these results, the origin of the high second-order nonlinear optical activity upon protonation is addressed.     

Time-invariant portfolio strategies in structured products with guaranteed minimum equity exposure

We introduce a new exotic option to be used within structured products to address a key disadvantage of standard time-invariant portfolio protection: the well-known cash-lock risk. Our approach suggests enriching the framework by including a threshold in the allocation mechanism so that a guaranteed minimum equity exposure (GMEE) is ensured at any point in time. To be able to offer such a solution still with hard capital protection, we apply an option-based structure with a dynamic allocation logic as underlying. We provide an in-depth analysis of the prices of such new exotic options, assuming a Heston–Vasicek-type financial market model, and compare our results with other options used within structured products. Our approach represents an interesting alternative for investors aiming at downsizing protection via time-invariant portfolio protection strategies, meanwhile being also afraid to experience a cash-lock event triggered by market turmoils.     

Synthesis,Aromaticity and Photophysical Behaviour of Ferrocene‐ and Ruthenocene‐Appended Semisynthetic Chlorin Derivatives

Two novel synthetic strategies to covalently link a metallocene electron‐donor unit to a chlorin ring are presented. In one approach, pyropheophorbide a is readily converted into its 13¹‐ferrocenyl dehydro derivative by nucleophilic addition of the ferrocenyl anion to the 13¹‐carbonyl group. In another approach, the corresponding 13¹‐pentamethylruthenocenyl derivative is synthesised from 13¹‐fulvenylchlorin by a facile ligand exchange/deprotonation reaction with the [RuCp*(cod)Cl] (Cp*=pentamethylcyclopentadienyl; cod=1,5‐cyclooctadiene) complex. The resulting metallocene–chlorins exhibit reduced aromaticity, which was unequivocally supported by ring‐current calculations based on the gauge‐including magnetically induced current (GIMIC) method and by calculated nucleus‐independent chemical shift (NICS) values. The negative ring current in the isocyclic E ring suggests the antiaromatic character of this moiety and also clarifies the spontaneous reactivity of the complexes with oxygen. The oxidation products were isolated and their electrochemical and photophysical properties were studied. The ruthenocene derivatives turned out to be stable under light irradiation and showed photoinduced charge transfer with charge‐separation lifetimes of 152–1029 ps.     

EPR spectroscopy revealing the mechanism of methane flameless combustion catalyzed by La0.9M0.1CoO3 (M = Eu, Ce)

The electron paramagnetic resonance spectra of La_0.9M_0.1CoO₃ (M = Eu, Ce) can explain the lower oxygen availability observed with the Eu-, with respect to the Ce-doped catalyst for methane flameless combustion. With the former sample, paramagnetic O⁻ ions adsorb more easily on the internal-pore surfaces, forming ferromagnetic spin bags.     

A Grouping Differential Evolution Algorithm Boosted by Attraction and Repulsion Strategies for Masi Entropy-Based Multi-Level Image Segmentation

Masi entropy is a popular criterion employed for identifying appropriate threshold values in image thresholding. However, with an increasing number of thresholds, the efficiency of Masi entropy-based multi-level thresholding algorithms becomes problematic. To overcome this, we propose a novel differential evolution (DE) algorithm as an effective population-based metaheuristic for Masi entropy-based multi-level image thresholding. Our ME-GDEAR algorithm benefits from a grouping strategy to enhance the efficacy of the algorithm for which a clustering algorithm is used to partition the current population. Then, an updating strategy is introduced to include the obtained clusters in the current population. We further improve the algorithm using attraction (towards the best individual) and repulsion (from random individuals) strategies. Extensive experiments on a set of benchmark images convincingly show ME-GDEAR to give excellent image thresholding performance, outperforming other metaheuristics in 37 out of 48 cases based on cost function evaluation, 26 of 48 cases based on feature similarity index, and 20 of 32 cases based on Dice similarity. The obtained results demonstrate that population-based metaheuristics can be successfully applied to entropy-based image thresholding and that strengthening both exploitation and exploration strategies, as performed in ME-GDEAR, is crucial for designing such an algorithm.     

Bulk High‐Impact Polystyrene Process, 1

In relation to the bulk high‐impact polystyrene process, this work investigates the partition between phases of styrene and an initiator: tert‐butyl peroctoate. A Flory‐Huggins model was applied for predicting the phase separation point and the partitions of styrene and tert‐butyl peroctoate. For blends of styrene, polystyrene, and a styrene‐butadiene diblock copolymer, the model provides reasonable predictions of a ternary equilibrium diagram. For blends of styrene, polystyrene, polybutadiene, and tert‐butyl peroctoate, the partition of tert‐butyl peroctoate was measured at 25 °C. At emulated conversions of 13% or lower, equilibrium was reached after 1 h of mixing time. For the higher molar masses and conversion of 16%, equilibrium was not reached after 24 h of mixing time. To fit the equilibrium measurements, the solubility parameter of tert‐butyl peroctoate was adjusted.

     

A Novel Route to Graft-Copolymers with Tailored Structures for the Compatibilization of Polymeric Blend

A new method to synthesize graft-copolymers based on isotactic polypropylene (iPP) with tailored structure has been developed. The synthesis is a two-step process: synthesis of P-co-(p-MS-E) copolymers, by using ansa-metallocene catalysts, and metallation of p-Me groups followed by living anionic polymerisation for the graft growth. This method turn out to be versatile because, by changing experimental conditions, in the first step backbones with a tuned number of the graft growth sites and polypropylene lengths can be obtained, whereas in the second step, graft chains of different types and lengths can be synthesized. The particular ability of these copolymers to compatibilize polymeric blends was evaluated analyzing the morphology of the products copolymers/blends by using a scanning electron microscopy (SEM).     

Ethanol production from lignocellulosic byproducts of olive oil extraction

The recent implementation of a new two-step centrifugation process for extracting olive oil in Spain has substantially reduced water consumption, thereby eliminating oil mill wastewater. However, a new high sugar content residue is still generated. In this work the two fractions present in the residue (olive pulp and fragm ented stones) were assayed as substrate for ethanol production by the simultaneous saccharification and fermentation (SSF) process. Pretreatment of fragmented olive stones by sulfuric acid-catalyzed steam explosion was the most effective treatment for increasing enzymatic digestibility; however, a pretreatment step was not necessary to bioconvert the olive pulp into ethanol. Theolive pulp and fragmented olive stones were tested by the SSF process using a fed-batch procedure. By adding the pulp three times at 24-h intervals, 76% of the theoretical SSF yield was obtained. Experiments with fed-batch pretreated olive stones provided SSF yields significantly lower than those obtained at standard SSF procedure. The preferred SSF conditions to obtain ethanol from olives stones (61% of theoretical yield) were 10% substrate and addition of cellulases at 15 filter paper units/g of substrate.