New cis-clerodane diterpenoids from Croton schiedeanus

The acid fraction of extracts from the aerial part of Croton schiedeanus afforded six cis-clerodane type diterpenoids. Two of them (1 and 4) are new natural compounds. Structural elucidation was achieved on the basis of their spectral data.     

Amine containing cationic methacrylate copolymers as efficient gene delivery vehicles to retinal epithelial cells

Non‐viral gene delivery vectors have emerged as potential alternatives in the field of gene therapy by replacing the biological viral vectors. DNA–cationic polymer complexes are one of the most promising systems to target many inborn or acquired diseases without the utilization of conventional drugs. Despite the excellent binding efficiency of cationic polymers, the gene transfection seems limited to date. In this work, a series of ammonium‐based block‐copolymers with different alkyl side chains (ethyl, butyl, and hexyl) and functionality (alcohol, amine, and alkyl) have been prepared to evaluate their capacity to deliver genetic material. First, different ionic liquid monomers with different pendent functional groups were prepared and characterized. Then, polyplexes elaborated with different polymers at several polymer DNA ratios (w/w) were characterized in terms of size, zeta potential, and DNA binding, release, and protection capacity. Finally, the transfection efficiency and cell viability was evaluated in ARPE19 cells. We found that only the systems containing the amine pendent group were able to transfect ARPE19 cell and, that this amine containing polymer was less cytotoxic even at high polymer/DNA ratios (30:1). In conclusion, our studies suggested that the proper selection of the pendent group substantially impacts overall transfection efficiency of cationic polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 280–287     

Radiative decay channel assessment to understand the sensing mechanism of a fluorescent turn-on Al3+ chemosensor

The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al³⁺ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S₁ excited state were assessed in order to elucidate the selective sensing mechanism of L to Al³⁺ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al³⁺, the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn²⁺ and Cd²⁺, the luminescence quenching is caused by PET, while for Ni²⁺, ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence.     

DFT studies on coordination models for adsorption essays of Cu(II) and Ni(II) solutions in modified silica gel with iminodiacetic groups

Research in functionalized inorganic supports faces special challenges regarding the inmobilization of organic chains and efficient computational methods for the quantum chemical modeling of coordination compounds. The silylant 3-cloropropyltriethoxysilyl (R1) was anchored over silica gel in anhydrous conditions, in order to react with diethyl Iminodiacetate (DIDA) to obtain modified silica gel (R2), which was hydrolized in basic conditions previously synthesized and characterized by S _BET, TGA and FTIR spectroscopy to obtain iminodiacetic acid groups IDA to prepare an modified inorganic support (R3) that is able to get hands on metals from the first transition series such as copper and nickel. The obtained experimental values showed that the functionalized grade of R3 corresponds to 0.1598 mmol of the nitrogen indicated that the adsorbed Cu(II) or Ni(II) have the stoichiometry for both cation of 1:1. Based on this relation, the three different structures were proposed to carry out the computational studies using density functional theory (DFT) in its LDA and PW91 with the TZP slater type basis set. The primary coordination sphere of copper(II) or nickel (II) ion in R3 are optimized, structural parameters are calculated, vibrational bands are assigned and energy gaps of frontier orbital (HOMO–LUMO) have been calculated. The calculated results reproduced the experimental data with good agreement. An energy decomposition analysis (EDA) of the different models proposed here was performed and suggest a 1:1 coordination form.     

Pitch-interval discrimination and musical expertise: Is the semitone a perceptual boundary?

The ability to discriminate pitch changes (or intervals) is foundational for speech and music. In an auditory psychophysical experiment, musicians and non-musicians were tested with fixed- and roving-pitch discrimination tasks to investigate the effects of musical expertise on interval discrimination. The tasks were administered parametrically to assess performance across varying pitch distances between intervals. Both groups showed improvements in fixed-pitch interval discrimination as a function of increasing interval difference. Only musicians showed better roving-pitch interval discrimination as interval differences increased, suggesting that this task was too demanding for non-musicians. Musicians had better interval discrimination than non-musicians across most interval differences in both tasks. Interestingly, musicians exhibited improved interval discrimination starting at interval differences of 100 cents (a semitone in Western music), whereas non-musicians showed enhanced discrimination at interval differences exceeding 125 cents. Although exposure to Western music and speech may help establish a basic interval-discrimination threshold between 100 and 200 cents (intervals that occur often in Western languages and music), musical training presumably enhances auditory processing and reduces this threshold to a semitone. As musical expertise does not decrease this threshold beyond 100 cents, the semitone may represent a musical training-induced intervallic limit to acoustic processing.     

Magnetic response and its relation to the keto-enol tautomerism of 3,3′-(1,4-phenylene)bis(pentane-2,4-dione): Experimental and theoretical insights

A direct correlation between aromaticity and the thermodynamic stability in the tautomeric equilibrium of 3,3′-(1,4-phenylene)bis(pentane-2,4-dione) is studied using experimental methods and theoretical approaches. According to the results, the most abundant tautomer corresponds to the bis-β-keto-enol tautomer when conditions such as temperature, solvent polarity, and pH are deliberately changed. Theoretical results of aromaticity analysis showed good concordance with the experimental results, using rigorous computations such as induced magnetic field (B^ind) and free of in-plane component NICS (FIPC-NICS).     

DFT/MRCI assessment of the excited-state interplay in a coumarin-schiff Mg2+ fluorescent sensor

Fluorescent sensors with selectivity and sensitivity to metal ions are an active field in supramolecular chemistry for biochemical, analytical, and environmental problems. Mg²⁺ is one of the most abundant divalent ions in the cell, and it plays a critical role in many biological processes. Coumarin-based sensors are widely used as desirable fluorophore and binding moieties showing a remarkable sensitivity and fluorometric enhancement for Mg²⁺. In this work, density functional theory/multireference configuration interaction (DFT/MRCI) calculations were performed in order to understand the sensing behavior of the organic fluorescent sensor 7-hydroxy-4-methyl-8-((2-(pyridin-2-yl)hydrazono)methyl)-2H-chromen-2-one (PyHC) in ethanol to solvated Mg²⁺ ions. The computed optical properties reproduce well-reported experimental data. Our results suggest that after photoexcitation of the free PyHC, a photo-induced electron transfer (PET) mechanism may compete with the fluorescence decay to the ground state. In contrast, this PET channel is no longer available in the complex with Mg²⁺ making the emissive decay more efficient. © 2019 Wiley Periodicals, Inc.     

Non‐Newtonian blood flow dynamics in a right internal carotid artery with a saccular aneurysm

Flow dynamics plays an important role in the pathogenesis and treatment of cerebral aneurysms. The temporal and spatial variations of wall shear stress in the aneurysm are hypothesized to be correlated with its growth and rupture. In addition, the assessment of the velocity field in the aneurysm dome and neck is important for the correct placement of endovascular coils. This work describes the flow dynamics in a patient‐specific model of carotid artery with a saccular aneurysm under Newtonian and non‐Newtonian fluid assumptions. The model was obtained from three‐dimensional rotational angiography image data and blood flow dynamics was studied under physiologically representative waveform of inflow. The three‐dimensional continuity and momentum equations for incompressible and unsteady laminar flow were solved with a commercial software using non‐structured fine grid with 283 115 tetrahedral elements. The intra‐aneurysmal flow shows complex vortex structure that change during one pulsatile cycle. The effect of the non‐Newtonian properties of blood on the wall shear stress was important only in the arterial regions with high velocity gradients, on the aneurysmal wall the predictions with the Newtonian and non‐Newtonian blood models were similar. Copyright © 2005 John Wiley & Sons, Ltd.