On a new semi‐empirical electrotopological index for QSRR models

A new semi‐empirical electrotopological index, I_SET, for quantitative structure–retention relationships (QSRR) models was developed based on the refinement of the previously published semi‐empirical topological index, I_ET. We demonstrate that the values of C_i fragments that were firstly attributed from the experimental chromatographic retention and theoretical deductions have an excellent relationship with the net atomic charge of the carbon atoms. Thus, the values attributed to the vertices in the hydrogen‐suppressed graph of carbon atoms (C_i) are calculated from the correlation of the net atomic charge in each carbon atom, which is obtained from quantum chemical semi‐empirical calculations, and the C_i fragments for primary, secondary, tertiary and quaternary carbon atoms (1.0, 0.9, 0.8 and 0.7, respectively) obtained from the experimental values. This shows that I_ET encoded this quantum physical reality and that it is possible to calculate a new I_SET (the semi‐empirical electrotopological index) through the net atomic charge values obtained from a Mulliken population analysis using the semi‐empirical AM1 method and their correlation with the values attributed to the different types of carbon atoms. This demonstrates that the I_SET encodes information on the charge distribution of the solute on which dispersive and electrostatic interactions between the solute (alkanes and alkenes) and the stationary phase strongly depend. Thus, this new method can be considered as an initial step towards forthcoming QSRR/QSAR studies. Copyright © 2008 John Wiley & Sons, Ltd.     

Metal complex derivatives of bis(pyrazol-1-yl)methane ligands: synthesis,characterization and anti-Trypanosoma cruzi activity

Transition Metal Chemistry - In this work, the synthesis and characterization of seven complexes (1–7) was performed with Zn(II), Cu(II), Co(II) and Ni(II) transition metals and ligands...     

Photoelectrochemical platform for sensing propyl gallate in edible oil samples based on CdTe quantum dots and poly(D-glucosamine)

Journal of Solid State Electrochemistry - This paper reports the development of a photoelectrochemical platform based on indium tin oxide (ITO) electrode modified with carboxyl-functionalized...     

Courtship and agonistic sounds by the cichlid fish Pseudotropheus zebra

Courtship and agonistic interactions in an African cichlid species present a richer diversity of acoustic stimuli than previously reported. Male cichlids, including those from the genus Pseudotropheus (P.), produce low frequency short pulsed sounds during courtship. Sounds emitted by P. zebra males in the early stages of courtship (during quiver) were found to be significantly longer and with a higher number of pulses than sounds produced in later stages. During agonistic intrasexual quiver displays, males produced significantly longer sounds with more pulses than females. Also, male sounds had a shorter duration and pulse period in courtship than in male-male interactions. Taken together, these results show that the acoustic repertoire of this species is larger than what was previously known and emphasize the importance of further research exploiting the role of acoustic stimuli in intra- and interspecific communication in African cichlids.     

Nonlinear modeling and analysis of rotors supported by magnetorheological squeeze film journal bearings

Meccanica - The driver coupled to a driven system through mechanical couplings is very common in rotating machinery. These couplings can present angular and parallel misalignments with more or less...     

On the influence of fatty acid chain unsaturation on supramolecular gelation of aminocarbohydrate-based supra-amphiphiles

Supramolecular gels are soft materials formed mainly by low molecular weight units held together by intermolecular interactions. Stabilizing these kinds of materials is quite a challenge due to the influence of multiple factors interfering with the integrity of the supramolecular structure. In our previous studies, we have shown that the aminocarbohydrate meglumine (MEG) interacts with organic acids by ion-pairing leading to the formation of MEG–carboxylate adducts. These adducts undergo supramolecular polymerization by heat treatment, but the macromolecular assembly was stable for a short period due to hydrogen bond (H-bond) breakup. Herein, we attempt to study the influence of hydrophobic building blocks on the formation of these compounds aiming to stabilize H-bonds to produce polymerizable supra-amphiphiles in water. Oleic acid and stearic acid are two analogous fatty acids differing only in the presence of unsaturation that were used in our studies. Results demonstrated that the presence of unsaturation hinders gelation in water by interfering with the self-assembly behavior of supra-amphiphiles. Thus, unsaturated supra-amphiphiles behave like traditional surfactants and gelify water at high concentrations (above 30% w/w). On the other hand, supramolecular gels with a polymer-like behavior could be produced with a saturated supra-amphiphile in water (above 4% w/w). The material was characterized by a lamellar arrangement that facilitates the alignment of H-bonds necessary to stabilize the self-assembled structure. These results have pivotal importance on the design of polymerizable supra-amphiphiles and demonstrate that the double bond of hydrophobic building blocks is an important design factor to be considered by scientists studying similar materials.     

A change of variables formula for mappings in

A change of variables formula for mappings in is obtained, where the usual jacobian is replaced by the determinant of the approximate differential.

     

Ultrasonic-assisted enzymatic digestion (USAED) for total elemental determination and elemental speciation: a tutorial

Due to its potential as sample treatment for Analytical Chemistry, the Ultrasonic-Assisted Enzymatic Digestion (USAED) for total elemental determination and elemental speciation is described under the most recent achievements published in literature, focusing on the variables that critically affect the performance of this relatively new sample treatment, such as the type of enzymes or the type of ultrasonic system used for the acceleration of the solid-liquid extraction process. Moreover, analytical chemists are aware of common errors produced in data interpretation concerning USAED. In addition, a guide for the rapid application of this methodology is also provided along with detailed explanations. Finally, future trends regarding USAED are also given and commented.     

Semi-empirical topological index: development of QSPR/QSRR and optimization for alkylbenzenes

The semi-empirical topological index, I(ET), was developed and optimized to describe the chromatographic retention of alkylbenzenes on the squalane stationary phase. The simple linear regression between the chromatographic retention and the proposed index, for 122 alkylbenzenes studied, is of good quality (determination coefficient, r(2)=0.9996, standard deviation, S.D.=5.5, and leave-one-out cross-validation correlation coefficient, r(CV)(2)=0.9996). The predictive ability of I(ET) was also verified for stationary phases with two different polarities (SE-30 and Carbowax 20 M), and good results were obtained, especially for the stationary phase with low polarity, showing that the specific molecular interactions occur on highly polar phases. The I(ET) was applied to construct quantitative structure-property relationship (QSPR) models for representative properties such as boiling point, Bp(degrees C), octanol/water partition coefficient, log P, van der Waals volume (V(W)) and molar refractivity (R(M)). Satisfactory quality QSPR models were obtained with Bp, V(W) and R(M) showing that the molecular size and dispersive forces are dominating factors with respect to the chromatographic retention.     

Host-guest Assembly Based on γ-Cyclodextrin-functionalized Multiwalled Carbon Nanotubes for Rutin Electrochemical Sensing

Here, we report multiwalled carbon nanotubes (MWCNTs) functionalized with γ-cyclodextrins (γCD) as a novel electrochemical strategy for Rutin determination, showing superior performance than β-cyclodextrins (βCD) modified MWCNTs, suggesting an adequate environment for host-guest interactions. Under optimized conditions, the sensor showed a linear range of 39–975 nmol L⁻¹ and a limit of detection of 7 nmol L⁻¹. When tested with quercetin, catechin, and caffeine, the platform presented high selectivity with an interference response <10 %. The method was employed to quantify Rutin in spiked pharmaceutical and herbal extracts, providing recovery of 93–98.4 %. Also, HPLC-PDA confirmed the method‘s accuracy.