Probing molecular environments with a fictitious isotopic dipole

A HD-like (HD: mono-deuterated hydrogen molecule) isotopic dipole moment is proposed as a sensible probe for molecular environments, in particular for electrostatic fields and polarizable (reactive) sites of molecules. Fictitious nuclear masses are chosen in order to yield a rigid dipole with a small appropriate magnitude. Upon subtracting the Born-Oppenheimer energy, the interaction is reduced to field-dipole-like and dipole-polarizability-like terms, the last one being particularly informative since connected to potentially reactive sites. Possible asymmetries of this term appear as signatures of charged sites in the molecule. The field strength and orientation are easily obtained by identifying the minimum field-dipole energy configuration and flipping the dipole from it. Tests with hydrogen, water, benzene, and chlorobenzene molecules confirm the good performance of the method. In an application to test the present models for hydrogen activation by a frustrated Lewis pair, the full potential of the method is assessed.     

Intramolecular Hydroamination of Selenoalkynes to 2-Selenylindoles in the Absence of Catalyst

In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.     

Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

From superhydrophobic‐ to superhydrophilic‐patterned poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) architectures as a novel platform for biotechnological applications

The manufacture of three‐dimensional patterned electroactive poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) microstructures with tailored architecture, morphology, and wettability is presented. The patterned microstructures are fabricated using a simple, effective, low cost, and reproducible technique based on microfluidic technology. These novel structures can represent innovative platforms for advanced strategies in a wide range of biotechnological applications, including tissue engineering, drug delivery, microfluidic, and sensors and actuators devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1802–1810     

The powder X-band electron paramagnetic resonance spectroscopy of septet pyridyl-2,4,6-trinitrene

The first X-band EPR spectrum containing only non-overlapping signals of septet pyridyl-2,4,6-trinitrene and triplet pyridylnitrenes is reported. This spectrum was recorded after photolysis of 2,4,6-triazidopyridine in solid argon at 5 K. The zero-field splitting (ZFS) parameters of this trinitrene as well as of intermediate triplet mononitrenes and quintet dinitrenes formed at early stages of the photolysis were determined using the combination of modern computer line-shape spectral simulations and density functional theory (DFT) calculations. It was found that septet pyridyl-2,4,6-trinitrene has the record negative parameter D_S = −0.1031 cm⁻¹ among all known to date septet pyridyl-2,4,6-trinitrenes and may be of interest as a model multi-qubit spin system for investigations of quantum computation processing.     

On the Herbrand functional interpretation

We show that the types of the witnesses in the Herbrand functional interpretation can be simplified, avoiding the use of “sets of functionals” in the interpretation of implication and universal quantification. This is done by presenting an alternative formulation of the Herbrand functional interpretation, which we show to be equivalent to the original presentation. As a result of this investigation we also strengthen the monotonicity property of the original presentation, and prove a monotonicity property for our alternative definition.     

Babassu mesocarp (Orbignya phalerata Mart) nanoparticle-based biosensors for indirect sulfite detection in industrial juices

Journal of Solid State Electrochemistry - The present work proposes a new electrochemical sulfite biosensor based on babassu mesocarp nanoparticles (BMNPs) immobilized on the surface of a pyrolytic...