Effect of methoxyl groups on the NMR spectra: configuration and conformation of natural and synthetic indanic and tetralinic structures

Here, we studied the influence of the methoxyl groups attached at C‐7 and C‐2′ of natural and synthetic 1‐arylindanes on the chemical shift of the signal of bibenzylic hydrogen and carbon atoms and J_1,2 coupling constants. This influence was also analysed in natural 1‐aryltetralins and related compounds that possess methoxyl and/or hydroxyl groups bound at C‐8 and C‐2′. The methoxyl groups attached at C‐7 in indanes or at C‐8 in tetralins produce a deshielding signal at H‐1 and shield at C‐1 and a strong decrease in the value of J_1,2 due to the pseudoequatorial location adopted by the aryl group bound at C‐1, avoiding an ‘A^1,3 strain’. Furthermore, compounds with hydroxyl or methoxyl groups in C‐2′, in the absence of substituents of C‐7 or C‐8, present a strong deshielding signal at H‐1, strong shield of the C‐1 signal and a decrease in the value of J_1,2. This is attributed to the stereoelectronic effects of the methoxyl or hydroxyl groups, which we have called ‘Asarone effect’. NOESY experiments were conducted to confirm the configuration and conformation of some of the compounds included in this work. This study shows that both effects, A^1,3 strain and Asarone effect, must be taken into account when the structure of natural indanes and tetralins is analysed by using ¹H‐NMR and ¹³C‐NMR spectra. Copyright © 2016 John Wiley & Sons, Ltd.     

A Zn(II) luminescent complex with a Schiff base ligand: solution,computational and solid state studies

Abstract

A new mononuclear complex of zinc(II), [Zn(HL)₂]?2DMF (H₂L = (E)-N′-((E)-(hydroxyimino)butan-2-ylidene)salicyloylhydrazide, DMF = N,N-dimethylformamide), was prepared and characterized. Single-crystal X-ray crystallography revealed a six-coordinate zinc(II) surrounded by nitrogen of the oxime function and oxygen and distal nitrogens of the acylhydrazone group. This entity also exists in solution as demonstrated by ¹H-NMR and potentiometric titrations. The computational analysis showed that the molecular orbitals involved in the main electronic transitions of the complex species in solution are centered on the ligand with negligible contribution of the metal ion. The photophysical properties of the complex were evaluated in solution and in the solid state. Luminescence studies showed that the solid has a strong emission at 550 nm with a large Stokes shift with respect to absorption. The solid state fluorescence emission is ascribed to ligand-centered and/or ligand-to-ligand charge transfer transitions, following the DFT results in solution. A comparison with a previously reported mononuclear [Zn(HL)₂] allowed the investigation of the influence of DMF molecules in the structural packing and the luminescence properties.     

Novel organometallic chalcones functionalized with a crown ether fragment as optical ion chemosensors

We previously reported the synthesis and characterization of new organometallic chalcones derived from ferrocene, cyrhetrene and cymantrene functionalized with a benzo‐15‐crown‐5 fragment. The ferrocene and cyrhetrene chalcones have been investigated as chemosensors for metal ions with optical response in acetonitrile. Several metal ions were selected considering the diameter of the cavity and the charge‐to‐radius ratio of the cation. The stoichiometry of the complexes was determined using Job's method. It was found that Na⁺ and Ca²⁺ complexes have a 1:1 stoichiometry while a 2:1 (metaloligand‐to‐cation) stoichiometry was determined for Ba²⁺ and Pb²⁺ complexes. The association constants were calculated according to the stoichiometry of the complex and the results showed that they are directly affected by the electron‐withdrawing nature of the organometallic fragment. Moreover, complexes of ferrocenyl chalcone have larger association constants than those of the cyrhetrenyl analogue. This experimental observation is consistent with the electronic properties of the ferrocenyl fragment.     

Monoparameter sensors for the determination of the antioxidants butylated hydroxyanisole and n-propyl gallate in foods and cosmetics by flow injection spectrophotometry.

A flow-through optosensor with solid phase UV spectroscopic detection is proposed for the direct determination of single antioxidants, namely butylated hydroxyanisole (BHA) and n-propyl gallate (n-PG), without previous derivatization. The methods are based on the transient retention behaviour of these compounds in a flow-through cell packed with C-18 silica using ethanol-water mixtures as a carrier, and on the intrinsic absorbance monitored at 290 and 283 nm, respectively. After recording the analytical signal, the antioxidants were easily and quickly desorbed from the solid support by the same carrier. For BHA, calibration graphs were linear over the range 1.0-300.0 mg L-1 using area as the analytical parameter. The relative standard deviation (RSD) was between 0.5 and 1.6%. For n-PG, calibration graphs were linear over the range 1.0-300.0 mg L-1 in area and the RSD was between 1.4 and 1.5%. The methods were applied to the determination of these antioxidants in several food and cosmetics samples, and were validated using the standard additions method and an HPLC reference method.     

Boosted feature selectors: a case study on prediction P-gp inhibitors and substrates

Feature selection is commonly used as a preprocessing step to machine learning for improving learning performance, lowering computational complexity and facilitating model interpretation. This paper proposes the application of boosting feature selection to improve the classification performance of standard feature selection algorithms evaluated for the prediction of P-gp inhibitors and substrates. Two well-known classification algorithms, decision trees and support vector machines, were used to classify the chemical compounds. The experimental results showed better performance for boosting feature selection with respect to the standard feature selection algorithms while maintaining the capability for feature reduction.     

Monte Carlo simulation of salt effect on water structure through 3D mechanistic potentials

Highly concentrated electrolyte solutions were studied through a Monte Carlo-based simulator, developed to consider the water molecules not a homogeneous dielectric as usual, but as dipoles that can move and rotate within a 3D lattice. This approach allowed fast calculations of detailed interactions between the particles, which were described from mechanistic potentials including dipole–dipole, ion–dipole, ion–ion, and hydrogen bonding (HB) interactions. A good agreement was found between experimental data and simulated results. The study also provides new insights about the balance of the different interactions in systems with or without electrolytes, and the effects of the electrolytes addition on the original water structure. The proposed model was also compared with previous explicit models.     

Lifting and Restricting Recollement Data

We study the problem of lifting and restricting TTF triples (equivalently, recollement data) for a certain wide type of triangulated categories. This, together with the parametrizations of TTF triples given in Nicolás and Saorín (Parametrizing recollement data for triangulated categories. To appear in J. Algebra), allows us to show that many well-known recollements of right bounded derived categories of algebras are restrictions of recollements in the unbounded level, and leads to criteria to detect recollements of general right bounded derived categories. In particular, we give in Theorem 1 necessary and sufficient conditions for a right bounded derived category of a differential graded (=dg) category to be a recollement of right bounded derived categories of dg categories. Theorem 2 considers the case of dg categories with cohomology concentrated in non-negative degrees. In Theorem 3 we consider the particular case in which those dg categories are just ordinary algebras.