Perturbations of the Dushman Reaction with Piroxicam: Experimental and Model Calculations

Perturbation of the Bray? Liebhafsky non‐oscillating subsystem (mixture of KIO₃ and H₂SO₄), i.e., Dushman reaction (DR), by piroxicam (PX), was observed in an open reactor, i.e., in the continuously fed well‐stirred tank reactor (CSTR). Monitoring the response of DR to perturbations by different concentrations of PX allows developing a simple procedure for quantitative determination of this analyte in both bulk drug and pharmaceutical preparation (injection). A tentative perturbation mechanism of PX action on the DR matrix, based on a kinetic scheme that was suggested by Agreda et al., is proposed. The PX reactivity in DR has been generally related to the reaction of PX with hypoiodous acid (HIO) present in the matrix.     

Asymmetric synthesis of enantiomerically enriched (S)-α-aminopropionic acids containing heterocyclic side chains

The conjugate addition of S-, N- and O-heterocyclic nucleophiles to the CC bond of dehydroalanine, bonded as a Schiff’s base to the chiral auxiliary (S)-2-[N-(N′-benzylprolyl)amino]benzophenone in the coordination sphere of Ni^II, resulted in the asymmetric synthesis of novel (S)-α-aminopropionic acids containing a heterocyclic side chain, including imidazole, triazole, thiodiazole, thiazole and oxazole moieties (de 20–92%). After purification and cleavage of the metal complexes, the heterocyclic amino acids were isolated with high enantiomeric purity (ee >97%).     

Numerical Optimal Harvesting for a Periodic Age-Structured Population Dynamics with Logistic Term

We investigate an optimal harvesting problem for age-structured population dynamics with logistic term and periodic vital rates. We use first-order necessary optimality conditions in order to derive an algorithm to approximate the optimal harvesting effort. We present corresponding numerical experiments.     

Multiple-color aggregation-induced emission-based Schiff base sensors for ultrafast dual recognition of Hg2+ and pH integrating Boolean logic operations

Seven Schiff base fluorescent sensors (L¹?L⁷) with multiple-color aggregation-induced emission (AIE) properties for detection of Hg²⁺ ions and pH integrating Boolean logic operations were reported. With appropriate ligand-to-metal coordination (L?HgCl₂) and AIE characteristic, L?HgCl₂ can aggregate into nanoparticles, followed by activation of strong emission, therefore, the “turn-on” assay for detection of Hg²⁺ can be established. Sensing mechanism was calculated through single-crystal X-ray diffraction, Job’s Plot, Benesi?Hildebrand equation, dynamic light scattering, scanning electron microscopy, and elemental mapping analysis. Density functional theory calculations revealed that L?HgCl₂ can avoid one-electron transfer and retain bright luminescence compared with that of L. Different (highest unoccupied orbit) HOMO and (Lowest empty orbit) LUMO energy gaps enable the different electron transitions, resulting in the multiple-color fluorescence properties. Especially, L¹?L⁷ exhibit pH-dependent fluorescent characteristics: different electron-donating ability of the substituent groups for L¹?L⁷ show different titration jump of pH. Advanced level molecular logic gates have been constructed integrating the sensing of Hg²⁺ and pH. More importantly, the L-coated test paper applied in Hg²⁺ sensing makes tracing possible, which is convenient for confidential purposes.     

Spirobifluorene Metallaaromatics

Spirobifluorene derivatives find use in many end-user applications. Therefore, further expansion of their scope is the focus of many research studies. However, although the optical properties of spirobifluorenes can be greatly tuned through incorporation of metal complexes, to date, spirobifluorene metallaaromatics remain unknown. Taking advantage of the versatility of our methodology for the synthesis of metallaaromatic systems, this work reports the first metallaaromatic spirobifluorene compound. The presence of an Ir atom was found to redshift the absorption maximum by ca. 1.1 eV compared to bare spirobifluorene. Additionally, X-ray analysis as well as anisotropy of the current-induced density calculations revealed this compound to be of aromatic nature. The high stability in solution, solid state, under air, and at high temperature, as well as distinct optical properties of this new class of compounds are expected to open new frontiers for chiroptical and optoelectronic applications.     

Distinct Helical Molecular Orbitals through Conformational Lock**

Several theoretical studies have proposed strategies to generate helical molecular orbitals (Hel-MOs) in [n]cumulenes and oligoynes. While chiral even-[n] cumulenes feature Hel-MOs, odd-[n] cumulenes may also present them if the terminal groups lie in different planes. However, the proposed systems have been either experimentally unfeasible or resulted in opposite pseudo-degenerated Hel-MOs. We hereby demonstrate the introduction of a remarkable energy difference between helical orbitals of opposite twist by fixing the torsion angle between the terminal groups in butadiyne fragments. To experimentally lock the conformation of the terminal groups, we designed and synthesized cyclic architectures by combining acetylenes with chiral spirobifluorenes. The high stability of these systems with distinct helical orbitals allowed their isolation and full characterization. In our view, these results constitute a step further in the development of real systems presenting helical molecular orbitals.     

Optimal harvesting for periodic age-dependent population dynamics with logistic term

We prove an asymptotic behavior result for an age-dependent population dynamics with logistic term and periodic vital rates. We investigate next an optimal harvesting problem related to a periodic age-structured model with logistic term. Existence of an optimal control and necessary optimality conditions are established. A conceptual algorithm to approximate the optimal pair is derived and some numerical experiments are presented.     

On the spin assignment to the 268 keV state in Au197

It is shown that the recent internal conversion data favour theI=1/2 value if the penetration effects inM1 conversion are fully taken into account. The 191 keV transition is found to be anM1 +E0 mixture with 41 (2)%E0, although the measuredK conversion coefficient is smaller than the theoreticalβ _k(M1) value.     

An Unprecedented Synthesis of 3,3‐Disubstituted Isochroman‐1,4‐diones Using Nitrones as Oxygen Atom Donors

A one‐pot reaction of ninhydrin, N‐methyl‐C‐phenyl nitrone, and secondary amine leading to the unprecedented synthesis of 3,3‐disubstituted isochroman‐1,4‐diones is described here. In this reaction, nitrone acts as an oxygen atom donor producing an imine as a side product. The mild reaction conditions, the flexibility of the secondary amines that can be used, the novelty of the product, and the good yields are the highlights of this reaction.     

Reaction of dimethoxycarbene-DMAD zwitterion with 1,2-diones and anhydrides: a novel synthesis of highly substituted dihydrofurans and spirodihydrofurans

The zwitterion formed by the reaction of dimethoxycarbene and DMAD adds efficiently to one of the carbonyl groups of 1,2-dicarbonyl compounds and anhydrides to generate dihydrofurans and spirodihydrofurans in good yields. In many cases, the carbene inserts into the C-C bond of the dione to yield masked vicinal tricarbonyl systems.