Silver-mediated palladium-catalyzed direct C-H arylation of 3-bromoisothiazole-4-carbonitrile

Silver(I) fluoride-mediated Pd-catalyzed C-H direct arylation/heteroarylation of 3-bromoisothiazole-4-carbonitrile (1a) gives twenty-four 5-aryl/heteroaryl-3-bromoisothiazole-4-carbonitriles. The reaction was partially optimized with respect to catalyst, ligand, and base. During this study 3,3'-dibromo-5,5'-biisothiazole-4,4'-dicarbonitrile (3a) was isolated as a byproduct and subsequently prepared via the silver-mediated Pd-catalyzed oxidative dimerization of 3-bromoisothiazole-4-carbonitrile in 67% yield. The analogous phenylation and oxidative dimerization of 3-chloroisothiazole-4-carbonitrile (1b) gave 3-chloro-5-phenylisothiazole-4-carbonitrile (4) and 3,3'-dichloro-5,5'-biisothiazole-4,4'-dicarbonitrile (3b) in 96% and 69% yields, respectively.     

Palladium catalyzed C-C coupling reactions of 3,5-dichloro-4H-1,2,6-thiadiazin-4-one

Palladium catalyzed Suzuki-Miyaura, Stille, and Sonogashira coupling reactions are reported for the electron-deficient heterocyclic scaffold 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (1). Furthermore, 3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin-4-one (7m) is further elaborated to afford the tetrathienyl 3,5-bis[(2,2'-bithien)-5-yl]-4H-1,2,6-thiadiazin-4-one (9). All compounds are fully characterized.     

Probability densities in configuration space and the Hamilton-Jacobi equation

The characteristic solutions of the Hamilton-Jacobi equation give the energies of conservative physical systems as functions of position and time. It is shown that these expressions are useful in the formation of probability densities in configuration space for canonical ensembles. Applications are given and discussed.     

Statistical interpretation of the Planck constant and the uncertainty relation

A statistically founded derivation of the quanta of energy is presented, which yields the Planck formula for the mean energy of the blackbody radiation without making use of the quantum postulate. The derivation presupposes an ensemble of particles and leads to a statistical interpretation of the Planck constant, which is defined and discussed. By means of the proposed interpretation ofh and as an application of it, the quantum uncertainty relation is derived classically and results as a statistical inequality. On the whole this paper is compatible with the statistical ensemble interpretation of quantum mechanics.     

Eco-friendly location of small hydropower

We address the problem of locating small hydropower dams in an environmentally friendly manner. We propose the use of a multi-objective optimization model to maximize total hydropower production, while limiting negative impacts on river connectivity. Critically, we consider the so called “backwater effects” that dams have on power generation at nearby upstream sites via changes in water surface profiles. We further account for the likelihood that migratory fish and other aquatic species can successfully pass hydropower dams and other artificial/natural barriers and how this is influenced by backwater effects. Although naturally represented in nonlinear form, we manage through a series of linearization steps to formulate a mixed integer linear programing model. We illustrate the utility of our proposed framework using a case study from England and Wales. Interestingly, we show that for England and Wales, a region heavily impacted by a large number of existing river barriers, that installation of small hydropower dams fitted with even moderately effective fish passes can, in fact, create a win-win situation that results in increased hydropower and improved river connectivity.     

Physicochemical investigation of some archaeometallurgical findings from locality Kmpije (Bor,Serbia)

Preliminary results of physicochemical investigation of some archaeometallurgical findings from Kmpije locality in vicinity of Bor (Serbia) are presented in this paper. Ancient samples of prehistoric origin were investigated using different instrumental analytic methods—chemical, differential thermal, X-ray diffraction, and energy dispersive X-ray fluorescence analysis. Obtained results indicate to the presence of ancient metallurgical activities, so locality Kmpije may be considered as an archaeometallurgical site, which should be investigated more in future for more precise details.     

Hydrogen Bonding between Metal‐Ion Complexes and Noncoordinated Water: Electrostatic Potentials and Interaction Energies

The hydrogen bonding of noncoordinated water molecules to each other and to water molecules that are coordinated to metal‐ion complexes has been investigated by means of a search of the Cambridge Structural Database (CSD) and through quantum chemical calculations. Tetrahedral and octahedral complexes that were both charged and neutral were studied. A general conclusion is that hydrogen bonds between noncoordinated water and coordinated water are much stronger than those between noncoordinated waters, whereas hydrogen bonds of water molecule in tetrahedral complexes are stronger than in octahedral complexes. We examined the possibility of correlating the computed interaction energies with the most positive electrostatic potentials on the interacting hydrogen atoms prior to interaction and obtained very good correlation. This study illustrates the fact that electrostatic potentials computed for ground‐state molecules, prior to interaction, can provide considerable insight into the interactions.     

Alkynyl ruthenium colorimetric sensors: optimizing the selectivity toward fluoride anion

We report on the synthesis of alkynyl ruthenium colorimetric sensors whose receptors are constituted by thiazolidinedione, rhodanine, or barbituric heads as recognition centers for anions. As modifications in the charge density at these recognition centers affect the whole molecule, through the alkynyl ligand acting as a communicating wire, the effects of hydrogen-bonding interactions with the anions were observed with the naked eye and monitored by UV-vis absorption spectrometry. The selectivity of the sensors was improved through electronic modifications of the alkynyl ruthenium subunit: the higher the electron density at the receptor head, the higher the selectivity is. TD-DFT calculations rationalize the long-range electronic communication as a main characteristic of the alkynyl ruthenium species and as a key to improve the selectivity of alkynyl ruthenium-based sensors toward anions.     

The Antiproliferative and Apoptosis-Inducing Effects of the Red Macroalgae Gelidium latifolium Extract against Melanoma Cells

The red macroalga Gelidium latifolium is widely distributed in the coastal areas of Indonesia. However, current knowledge on its potential biological activities is still limited. In this study, we investigated the potential bioactive compounds in Gelidium latifolium ethanol extract (GLE), and its cytotoxic effects against the murine B16-F10 melanoma cell line. GLE shows high total phenolic content (107.06 ± 17.42 mg GAE/g) and total flavonoid content (151.77 ± 3.45 mg QE/g), which potentially contribute to its potential antioxidant activity (DPPH = 650.42 ± 2.01 µg/mL; ABTS = 557.01 ± 1.94 µg/mL). ESI-HR-TOF-MS analysis revealed large absorption in the [M-H]^- of 327.2339 m/z, corresponding to the monoisotopic molecular mass of brassicolene. The presence of this compound potentially contributes to GLE’s cytotoxic activity (IC₅₀ = 84.29 ± 1.93 µg/mL). Furthermore, GLE significantly increased the number of apoptotic cells (66.83 ± 3.06%) compared to controls (18.83 ± 3.76%). Apoptosis was also confirmed by changes in the expression levels of apoptosis-related genes (i.e., p53, Bax, Bak, and Bcl2). Downregulated expression of Bcl2 indicates an intrinsic apoptotic pathway. Current results suggest that components of Gelidium latifolium should be further investigated as possible sources of novel antitumor drugs.     

Noncommutative baby Skyrmions

We subject the baby Skyrme model to a Moyal deformation, for unitary or Grassmannian target spaces and without a potential term. In the Abelian case, the radial BPS configurations of the ordinary noncommutative sigma model also solve the baby Skyrme equation of motion. This gives a class of exact analytic noncommutative baby Skyrmions, which have a singular commutative limit but are stable against scaling due to the noncommutativity. We compute their energies, investigate their stability and determine the asymptotic two-Skyrmion interaction.