Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks

Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.     

Periodic Néel skyrmion transport

In this work, we have used the MuMax3 software to simulate devices consisting of a ferromagnetic thin film placed over a heavy metal thin film. The devices are two interconnected partial-disks where a Néel domain wall is formed in the disks junction. In our simulations we investigate devices with disk radius $r=50$ nm and different distance d between the disks centers (from $d=12$ nm to $d=2R=100$ nm). By applying strong sinusoidal external magnetic fields, we find a mechanism able to create, annihilate and even manipulate a skyrmion in each side of the device. This mechanism is discussed in terms of interactions between skyrmion and domain wall. The Néel domain wall formed in the center of the device interacts with the Néel skyrmion, leading to a process of transporting a skyrmion from one disk to the other periodically. Our results have relevance for potential applications in spintronics such as logical devices.     

Triacetic acid lactone as a bioprivileged molecule in organic synthesis

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PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

Synthesis and antimycobacterial activity of purine conjugates with (S)-lysine and (S)-ornithine

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Cumulant t-Expansion for Strongly Correlated Electrons on a Lattice

Journal of Experimental and Theoretical Physics - A systematic nonperturbative scheme for calculating the ground state energy is adapted for studying systems of strongly correlated electrons on a...     

On the Problem of Spontaneous Isotopic Symmetry Breaking in Nambu–Jona-Lasinio Models

Physics of Particles and Nuclei Letters - The problem of spontaneous isotopic symmetry breaking in Nambu–Jona-Lasinio quark models is considered. It is shown that, in models with light...     

Probability Distributions of the Riemann Wave and an Integral of It

Doklady Physics - In this paper, we study the statistical characteristics of the Riemann wave and the integral of it. Such problems arise in the physics of fronts’ propagation, in particular,...     

Oxidative regulation of the mechanical strength of a C–S bond

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. Methods by which the intrinsic molecular strength of the constituents of a given polymeric material might be switched are therefore potentially useful both for applications in which triggered property changes are desirable, and as tests of molecular theories for bulk behaviors. Here we report that the sequential oxidation of sulfide containing polyesters (PE-S) to the corresponding sulfoxide (PE-SO) and then sulfone (PE-SO2) first weakens (sulfoxide), and then enhances (sulfone), the effective mechanical integrity of the polymer backbone; PE-S ∼ PE-SO2 > PE-SO. The relative mechanical strength as a function of oxidation state is revealed through the use of gem-dichlorocyclopropane nonscissile mechanophores as an internal standard, and the observed order agrees well with the reported bond dissociation energies of C–S bonds in each species and with the results of CoGEF modeling.

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness.