Conducting Elastomer Blends Based on Nitrile Rubber and Pani.DBSA

Electrically conductive elastomer blends based on polyaniline-dodecylbenzene sulfonic acid (Pani.DBSA) and nitrile rubber (NBR) were prepared by polymerization of aniline in the presence of NBR, using a direct, one-step in situ emulsion polymerization method. At the same PAni content, the conductivity of the in situ emulsion-polymerized blends is higher than that of blends produced by mechanical mixing of both components. In addition, a morphology with the presence of PAni in the form of microtubules was achieved by the in situ process. Stronger interaction between the components were also confirmed by Rheological processing analysis (RPA). The vulcanization process decreases the conductivity of the blends prepared by both methods. The in situ polymerized blends also display higher tensile strength and also higher crosslink density     

BP-M345, a New Diarylpentanoid with Promising Antimitotic Activity

Previously, we reported the in vitro growth inhibitory effect of diarylpentanoid BP-M345 on human cancer cells. Nevertheless, at that time, the cellular mechanism through which BP-M345 exerts its growth inhibitory effect remained to be explored. In the present work, we report its mechanism of action on cancer cells. The compound exhibits a potent tumor growth inhibitory activity with high selectivity index. Mechanistically, it induces perturbation of the spindles through microtubule instability. As a consequence, treated cells exhibit irreversible defects in chromosome congression during mitosis, which induce a prolonged spindle assembly checkpoint-dependent mitotic arrest, followed by massive apoptosis, as revealed by live cell imaging. Collectively, the results indicate that the diarylpentanoid BP-M345 exerts its antiproliferative activity by inhibiting mitosis through microtubule perturbation and causing cancer cell death, thereby highlighting its potential as antitumor agent.     

Stochastic model for energy commercialisation of small hydro plants in the Brazilian energy market

Computational Management Science - This paper presents a stochastic model for energy commercialisation strategies of small hydro plants (SHPs) in the Brazilian electricity market. The model aims to...     

Bis[1,1'-N,N'-(2-picolyl)aminomethyl]ferrocene as a redox sensor for transition metal ions

The compound bis[1,1'-N,N'-(2-picolyl)aminomethyl]ferrocene, L(1), was synthesized. The protonation constants of this ligand and the stability constants of its complexes with Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were determined in aqueous solution by potentiometric methods at 25 degrees C and at ionic strength 0.10 mol dm(-3) in KNO(3). The compound L(1) forms only 1:1 (M:L) complexes with Pb(2+) and Cd(2+) while with Ni(2+) and Cu(2+) species of 2 [ratio] 1 ratio were also found. The complexing behaviour of L(1) is regulated by the constraint imposed by the ferrocene in its backbone, leading to lower values of stability constants for complexes of the divalent first row transition metals when compared with related ligands. However, the differences in stability are smaller for the larger metal ions. The structure of the copper complex with L(1) was determined by single-crystal X-ray diffraction and shows that a species of 2:2 ratio is formed. The two copper centres display distorted octahedral geometries and are linked through the two L(1) bridges at a long distance of 8.781(10) Angstrom. The electrochemical behaviour of L(1) was studied in the presence of Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Pb(2+), showing that upon complexation the ferrocene-ferrocenium half-wave potential shifts anodically in relation to that of the free ligand. The maximum electrochemical shift ([capital Delta]E(1/2)) of 268 mV was found in the presence of Pb(2+), followed by Cu(2+)(218 mV), Ni(2+)(152 mV), Zn(2+)(111 mV) and Cd(2+)(110 mV). Moreover, L(1) is able to electrochemically and selectively sense Cu(2+) in the presence of a large excess of the other transition metal cations studied.     

Stereoelectronic interactions: A booster for 4JHF transmission

Long-range proton-fluorine coupling constants (ⁿJ_HF) are helpful for the structure elucidation of fluorinated molecules. However, their magnitude and sign can change with the relative position of coupled nuclei and the presence of substituents. Here, trans-4-tert-butyl-2-fluorocyclohexanone was used as a model compound for the study of the transmission of ⁴J_HF. In this compound, the ⁴J_H6axF was measured to be +5.1 Hz, which is five times larger than the remaining ⁴J_HF in the same molecule (⁴J_H4F = +1.0 Hz and ⁴J_H6eqF = +1.0 Hz). Through a combination of experimental data, natural bond orbital (NBO) and natural J-coupling (NJC) analyses, we observed that stereoelectronic interactions involving the π system of the carbonyl group are involved in the transmission pathway for the ⁴J_H6axF. Interactions containing the π system as an electron acceptor (e.g., σ_{C6 H6ax} → π^*_C═O and σ_{C F} → π^*_C═O) increase the value of the ⁴J_H6axF, while the interaction of the π system as an electron donor (e.g., π_C═O → σ^*_{C F}) decreases it. Additionally, the carbonyl group was shown not to be part of the transmission pathway of the diequatorial ⁴J_H6eqF coupling in cis-4-tert-butyl-2-fluorocyclohexanone, revealing that there is a crucial symmetry requirement that must be fulfilled for the π system to influence the value of the ⁴J_HF in these systems.     

Control over the Redox Cooperative Mechanism of Radical Carbene Transfer Reactions for the Efficient Active-Metal-Template Synthesis of [2]Rotaxanes

A 5,15-bis(1,1′-biphenyl)porphyrin-based molecular clip covalently connected to a ditopic aliphatic ester loop moiety yields a semi-rigid macrocycle with a well-defined cavity. The resulting macrocycle fits the structural requirements for the preparation of porphyrinates capable of promoting formation of C−C bonds. To demonstrate the usefulness of porphyrin-based macrocycles, an active-metal-template synthesis of rotaxanes through a redox non-innocent carbene transfer reaction is described. Coordination of Co^II ions into the porphyrin subunit followed by addition of appropriate monodentate nitrogen-based additives to function as axial ligands enables the radical carbene transfer reactions to styrene derivatives to occur exclusively through the cavity of the macrocycle to afford cyclopropane-linked rotaxanes in excellent 95 % yield. Investigation of the product distribution afforded from the rotaxane assembly reaction reveals how the redox cooperative action between the carbene species and the Co^II ions can be manipulated to gain control over the radical-type mechanism to favor the productive rotaxane forming process.     

Complex dynamics of multi-regional economic interactions

Nonlinear Dynamics - Dynamical systems are being employed over the last decades to investigate complex behaviors in traditional fields as engineering and physics, but also in biology, medicine,...     

Photochemical Properties of trans‐[Ru(NH3)4(bpa)(L)]2+ (L = py,isn, 4‐acpy or 4‐pic)

Photochemical reactions of ruthenium (II) complexes of type trans‐[Ru(NH₃)₄LL']²⁺, where L is a nitrogenous heterocyclic ligand, pyridine (py), isonicotinamide (isn), 4‐acetylpyridine (4‐acpy) or 4‐picoline (4‐pic), and L´ is a 1,2‐bis(4‐pyridyl)ethane (bpa) ligand, were studied with the purpose of evaluating the ligand exchange when, in solution, the complexes are irradiated at the wavelengths of 365, 436, 480 and 519 nm. The study revealed that at lower wavelengths, a labilization process is observed for py and 4‐pic ligands, even at low quantum yields, indicating the dependence of the photolabeling process on the wavelength. The study also reveals that for the filters of greater wavelength, the processes of photolabilization do not occur for any of the studied complexes. The study also shows that there are no photolization processes for the complexes obtained with the isn and 4‐acpy ligands, and it is therefore possible to classify them as nonreactive.     

Electrical,structural and thermal properties of new conductive blends (PANICG) based on polyaniline and cashew gum for organic electronic

Journal of Thermal Analysis and Calorimetry - The application of cashew gum, in particular the one which is abundant in northeastern Brazil, remains limited to the foods and pharmaceutics industry....