Chemistry of Pentafluorosulfanyl Derivatives and Related Analogs: From Synthesis to Applications

Pentafluorosulfanyl (SF₅)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF₅ bond formation as well as the use of SF₅-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF₅ group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015.     

Visible-Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione-Catechol Redox Couple

Controlling redox activity of judiciously appended redox units on a photo-sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer - electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo-responsive Ru-diimine module conjugated with redox-active catechol groups in [Ru(II)(phenanthroline-5,6-diolate)₃]⁴⁻ photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge-discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm⁻². This proof-of-concept molecular system marks an important milestone towards a new generation of molecular photo-rechargeable materials.     

Multivariate Reversed Hazard Rates and Inactivity Times of Systems

Methodology and Computing in Applied Probability - The family of the multivariate conditional hazard rate functions often reveals to be a convenient tool to describe the joint probability...     

On solutions to a FitzHugh–Rinzel type model

Ricerche di Matematica - A ternary autonomous dynamical system of FitzHugh–Rinzel type is analyzed. The system, at start, is reduced to a nonlinear integro differential equation. The...     

The COVID-19 pandemic: model-based evaluation of non-pharmaceutical interventions and prognoses

For the electrically actuated microbeam subjected to a combination of DC and AC voltage loadings, we studied the nonlinear dynamical responses and internal resonance analytically. The flexible boundary condition is considered. The modal interaction due to three-to-one internal resonance between the first and second modes is highlighted. The method of multiple scales is employed to get the modulation equation, which describes the amplitude and phases of the involving modes. Then, the equilibrium solutions of the modulation equation are calculated and their stability is examined. The frequency and force response curves reflecting the primary resonance (the first mode) are presented. We find that the first and second modes in the proposed model are coupled, and hence the energy transfer can occur between the involving modes. Moreover, it is found that the response of the system may encounter Hopf bifurcation for some specific parameters. As for simulation, the Galerkin scheme is applied to verify the analytical results in terms of time history, phase-plane portrait, Fourier spectrum, and Poincare section. The simulation results are in good agreement with the analytical ones.     

The maximum size of short character sums

The Ramanujan Journal - In the present note, we prove new lower bounds on large values of character sums $$\varDelta (x,q):=\max _{\chi \ne \chi _0} \big \vert \sum _{n\le x} \chi (n)\big \vert $$...     

There is no (95, 40, 12, 20) strongly regular graph

We show that there is no (95, 40, 12, 20) strongly regular graph and, consequently, there is no (96, 45, 24, 18) strongly regular graph, no nontrivial regular two‐graph on 96 vertices, and no partial geometry pg(4, 9, 2). The main idea of the result is based on the star complement technique and requires a moderate amount of computation.     

Biomimetic Approach for Highly Selective Artificial Water Channels Based on Tubular Pillar[5]arene Dimers

Artificial water channels mimicking natural aquaporins (AQPs) can be used for selective and fast transport of water. Here, we quantify the transport performances of peralkyl-carboxylate-pillar[5]arenes dimers in bilayer membranes. They can transport ≈10⁷ water molecules/channel/second, within one order of magnitude of the transport rates of AQPs, rejecting Na⁺ and K⁺ cations. The dimers have a tubular structure, superposing pillar[5]arene pores of 5 Å diameter with twisted carboxy-phenyl pores of 2.8 Å diameter. This biomimetic platform, with variable pore dimensions within the same structure, offers size restriction reminiscent of natural proteins. It allows water molecules to selectively transit and prevents bigger hydrated cations from passing through the 2.8 Å pore. Molecular simulations prove that dimeric or multimeric honeycomb aggregates are stable in the membrane and form water pathways through the bilayer. Over time, a significant shift of the upper vs. lower layer occurs initiating new unexpected water permeation events through toroidal pores.