Unpredictable Dynamic Behaviour of Ruthenium Chelate Pyrrole Derivatives.

Reaction of [Ru(H)(CO)(PPh)] with an equimolar amount of pyrrole-2-carboxylic acid () leads to the homoleptic chelate derivative k(O,O)-[RuH(CO)(HL)(PPh)] . Prolonged acetonitrile refluxing promotes an unusual k(O,O)- → k(N,O)- dynamic chelate conversion, forming a neutral, stable, air- and moisture- insensitive, solvento-species k(N,O)-[Ru(MeCN)(CO)(L)(PPh)] . Analogously, reaction of with the pyrrole-2-carboxyaldehyde () affords k(N,O)-[RuH(CO)(HL)(PPh)] , , as a couple of functional isomers.

Suberoylanilide Hydroxamic Acid Analogs with Heteroaryl Amide Group and Different Chain Length: Synthesis and Effect on Histone Deacetylase.

This review covers the last 25 years of the literature on analogs of suberoylanilide hydroxamic acid (SAHA, known also as vorinostat) acting as an HDAC inhibitor. In particular, the topic has been focused on the synthesis and biological activity of compounds where the phenyl group (the surface recognition moiety, CAP) of SAHA has been replaced by an azaheterocycle through a direct bond with amide nitrogen atom, and the methylene chain in the linker region is of variable length. Most of the compounds displayed good to excellent inhibitory activity against HDACs and in many cases showed antiproliferative activity against human cancer cell lines.

Synthesis and Antiproliferative Insights of Lipophilic Ru(II)-Hydroxy Stearic Acid Hybrid Species.

Metallodrugs represent a combination of multifunctionalities that are present concomitantly and can act differently on diverse biotargets. Their efficacy is often related to the lipophilic features exhibited both by long carbo-chains and the phosphine ligands. Three Ru(II) complexes containing hydroxy stearic acids (HSAs) were successfully synthesized in order to evaluate possible synergistic effects between the known antitumor activity of HSA bio-ligands and the metal center.

Ru-Controlled Thymine Tautomerization Frozen by a k(O)-, k(N,O)-Metallacycle: An Experimental and Theoretical Approach.

The reaction of -(Ru(H)(CO)(PPh)) () with one equivalent of thymine acetic acid (THAcH) unexpectedly produces the macrocyclic dimer k(O), k(N,O)-(Ru(CO)(PPh)THAc) () and, concomitantly, the doubly coordinated species k(O), k(O,O)-(Ru(CO)(PPh)THAc) (). The reaction promptly forms a complicated mixture of Ru-coordinated mononuclear species. With the aim of shedding some light in this context, two plausible reaction paths were proposed by attributing the isolated or spectroscopically intercepted intermediates on the basis of DFT-calculated energetic considerations.

Scintillation light detection in the 6-m drift-length ProtoDUNE Dual Phase liquid argon TPC.

DUNE is a dual-site experiment for long-baseline neutrino oscillation studies, neutrino astrophysics and nucleon decay searches. ProtoDUNE Dual Phase (DP) is a 6   6   6 m liquid argon time-projection-chamber (LArTPC) that recorded cosmic-muon data at the CERN Neutrino Platform in 2019-2020 as a prototype of the DUNE Far Detector. Charged particles propagating through the LArTPC produce ionization and scintillation light.

Social Network and Environment as Determinants of Disability and Quality of Life in Aging: Results From an Italian Study.

Background: The increase in life expectancy is leading to a worldwide increase in chronic diseases and disability, with significant concern about their management and long-term care. Investigating the aging process using a bio-psychosocial perspective is essential to understanding how to reduce disability and improve the quality of life of aging people. This study aims to explore the role of social networks and built environment as predictors of disability and quality of life in the Italian population aged over 50 years.

Effects of Regioisomerism on the Antiproliferative Activity of Hydroxystearic Acids on Human Cancer Cell Lines.

A series of regioisomers of the hydroxystearic acid () was prepared, and the effect of the position of the hydroxyl group along the chain on a panel of human cancer cell lines was investigated. Among the various regioisomers, those carrying the hydroxyl at positions 5, 7, and 9 had growth inhibitor activity against various human tumor cell lines, including CaCo-2, HT29, HeLa, MCF7, PC3, and NLF cells. and showed a very weak effect.

Prospects for beyond the Standard Model physics searches at the Deep Underground Neutrino Experiment: DUNE Collaboration.

The Deep Underground Neutrino Experiment (DUNE) will be a powerful tool for a variety of physics topics. The high-intensity proton beams provide a large neutrino flux, sampled by a near detector system consisting of a combination of capable precision detectors, and by the massive far detector system located deep underground. This configuration sets up DUNE as a machine for discovery, as it enables opportunities not only to perform precision neutrino measurements that may uncover deviations from the present three-flavor mixing paradigm, but also to discover new particles and unveil new interactions and symmetries beyond those predicted in the Standard Model (SM).

Intriguing enigma of nitrobenzofuroxan's 'Sphinx': Boulton-Katritzky rearrangement or unusual evidence of the -1/-3-oxide rearrangement?

The SAr/SAr reaction between 7-chloro-4,6-dinitrobenzofuroxan (ClDNBF) and 2-morpholinyl-, 2-piperidinyl-, or 2-pyrrolidinylthiazole afforded unexpectedly two isomeric products, bearing the benzofuroxanyl moiety bound to the C-5 carbon atom of the thiazole ring. The relative ratio for the two isomers was dependent on temperature and solvent, suggesting the occurrence of an equilibrium between the two novel species. In order to investigate their structure and to design a plausible mechanistic pathway, a series of synthetic and spectroscopic experiments was planned.

Synthesis of Novel Structural Hybrids between Aza-Heterocycles and Azelaic Acid Moiety with a Specific Activity on Osteosarcoma Cells.

Nine compounds bearing pyridinyl (or piperidinyl, benzimidazolyl, benzotriazolyl) groups bound to an azelayl moiety through an amide bond were synthesized. The structural analogy with some histone deacetylase inhibitors inspired their syntheses, seeking new selective histone deacetylase inhibitors (HDACi). The azelayl moiety recalls part of 9-hydroxystearic acid, a cellular lipid showing antiproliferative activity toward cancer cells with HDAC as a molecular target.

Synthesis of 9-Hydroxystearic Acid Derivatives and Their Antiproliferative Activity on HT 29 Cancer Cells.

9-Hydroxystearic acid (9-HSA) is an endogenous cellular lipid that possesses antiproliferative and selective effects against cancer cells. A series of derivatives were synthesized in order to investigate the effect of the substituent in position 9 and on the methyl ester functionality on the biological activity. The two separate enantiomers of methyl 9-hydroxystearate and of methyl 9-aminostearate showed antiproliferative activity against the HT29 cell line.

Highly conjugated architectures and labile reaction intermediates from coupling between 10π electron-deficient heteroaromatics and -trihydroxy- or triamino-benzene derivatives.

The C-C coupling reaction between neutral aromatic carbon nucleophiles such as 1,3,5-triamino- and 1,3,5-trihydroxy-benzene derivatives and 7-chloro-4,6-dinitrobenzofuroxan (Cl-DNBF) or 7-chloro-4,6-dinitrobenzofurazan (Cl-DNBZ) gave in high yield the corresponding conjugated structures, which are of potential interest in the materials field. When chlorine is absent on the electrophile, as in 4,6-dinitrobenzofurazan (DNBZ), the reaction with 1,3,5-triaminobenzene derivatives produces Wheland-Meisenheimer (WM) zwitterionic intermediates, intercepted and fully characterized NMR at low temperature, whereas stable Meisenheimer complexes (M) were isolated in the reaction of phloroglucinol with 1,3,5-trimethoxybenzene. The latter also gave exclusively M complexes when reacted with 4,6-dinitrobenzofuroxan (DNBF), or 4,6-dinitrotetrazolopyridine (DNTP).

Regioselectivity in Reactions between Bis(2-benzothiazolyl)ketone and Vinyl Grignard Reagents: C- versus O-alkylation-Part III.

The reaction between bis(2-benzothiazolyl)ketone and vinyl Grignard reagents bearing different substituents on the vinyl moiety gave the product derived from attack on the carbonylic carbon- and/or oxygen-atom. The regioselectivity of the attack depends on the kind of substituents bound to the vinylic carbon atoms and on their relative position. The reaction between vinylmagnesium bromide and 2-methyl-1-propenylmagnesium bromide was carried out under different experimental conditions and in the presence of radical scavengers.

Combined Analysis of Neutrino and Antineutrino Oscillations at T2K.

T2K reports its first results in the search for CP violation in neutrino oscillations using appearance and disappearance channels for neutrino- and antineutrino-mode beams. The data include all runs from January 2010 to May 2016 and comprise 7.482×10^{20} protons on target in neutrino mode, which yielded in the far detector 32 e-like and 135  μ-like events, and 7.

C-C Coupling Reactions between Benzofurazan Derivatives and 1,3-Diaminobenzenes.

Aromatic substitution reactions between 1,3-diaminobenzene and chloronitrobenzofurazan derivatives have never been reported so far. The aim of the current study was to synthesize novel electron-donor and -acceptor architectures of interest in applied fields and to provide new insights on the nucleophilic behavior of 1,3-diaminobenzenes. The reaction of 1,3-dipiperidinyl-, 1,3-dimorpholinyl-, 1,3-dipyrrolidinyl-, or 1,3-dimethylamino-benzene with 7-chloro-4,6-dinitrobenzofuroxan or with a series of chloro-nitrobenzofurazans has been carried out in mild conditions.

The tropical rain belts with an annual cycle and a continent model intercomparison project: TRACMIP.

This paper introduces the Tropical Rain belts with an Annual cycle and a Continent Model Inter-comparison Project (TRACMIP). TRACMIP studies the dynamics of tropical rain belts and their response to past and future radiative forcings through simulations with 13 comprehensive and one simplified atmosphere models coupled to a slab ocean and driven by seasonally varying insolation. Five idealized experiments, two with an aquaplanet setup and three with a setup with an idealized tropical continent, fill the space between prescribed-SST aquaplanet simulations and realistic simulations provided by CMIP5/6.

Measurement of Coherent π^{+} Production in Low Energy Neutrino-Carbon Scattering.

We report the first measurement of the flux-averaged cross section for charged current coherent π^{+} production on carbon for neutrino energies less than 1.5 GeV, and with a restriction on the final state phase space volume in the T2K near detector, ND280. Comparisons are made with predictions from the Rein-Sehgal coherent production model and the model by Alvarez-Ruso et al.

Sensitivity of El Niño intensity and timing to preceding subsurface heat magnitude.

Despite extensive ongoing efforts on improving the long-term prediction of El Niño-Southern Oscillation, the predictability in state-of-the-art operational schemes remains limited by factors such as the spring barrier and the influence of atmospheric winds. Recent research suggests that the 2014/15 El Niño (EN) event was stalled as a result of an unusually strong basin-wide easterly wind burst in June, which led to the discharge of a large fraction of the subsurface ocean heat. Here we use observational records and numerical experiments to explore the sensitivity of EN to the magnitude of the heat buildup occurring in the ocean subsurface 21 months in advance.

Measurement of Muon Antineutrino Oscillations with an Accelerator-Produced Off-Axis Beam.

T2K reports its first measurements of the parameters governing the disappearance of ν[over ¯]_{μ} in an off-axis beam due to flavor change induced by neutrino oscillations. The quasimonochromatic ν[over ¯]_{μ} beam, produced with a peak energy of 0.6 GeV at J-PARC, is observed at the far detector Super-Kamiokande, 295 km away, where the ν[over ¯]_{μ} survival probability is expected to be minimal.

Jet energy measurement and its systematic uncertainty in proton-proton collisions at [Formula: see text] TeV with the ATLAS detector.

The jet energy scale (JES) and its systematic uncertainty are determined for jets measured with the ATLAS detector using proton-proton collision data with a centre-of-mass energy of [Formula: see text] TeV corresponding to an integrated luminosity of [Formula: see text][Formula: see text]. Jets are reconstructed from energy deposits forming topological clusters of calorimeter cells using the anti-[Formula: see text] algorithm with distance parameters [Formula: see text] or [Formula: see text], and are calibrated using MC simulations. A residual JES correction is applied to account for differences between data and MC simulations.

On the borderline between Science and Philosophy: A debate on determinism in France around 1880.

In the second half of the nineteenth century, a new interest in explosive chemical reactions, sudden release of energy in living beings, physical instabilities, and bifurcations in the solutions of differential equations drew the attention of some scholars. New concepts like triggering actions and guiding principles also emerged. Mathematicians, physicists, physiologists, and philosophers were attracted by this kind of phenomena since they raised a question about the actual existence of a strict determinism in science.

Measurement of the inclusive electron neutrino charged current cross section on carbon with the T2K near detector.

The T2K off-axis near detector ND280 is used to make the first differential cross-section measurements of electron neutrino charged current interactions at energies ∼1  GeV as a function of electron momentum, electron scattering angle, and four-momentum transfer of the interaction. The total flux-averaged ν(e) charged current cross section on carbon is measured to be ⟨σ⟩(ϕ)=1.11±0.

Precise measurement of the neutrino mixing parameter θ23 from muon neutrino disappearance in an off-axis beam.

New data from the T2K neutrino oscillation experiment produce the most precise measurement of the neutrino mixing parameter θ23. Using an off-axis neutrino beam with a peak energy of 0.6 GeV and a data set corresponding to 6.

Observation of electron neutrino appearance in a muon neutrino beam.

The T2K experiment has observed electron neutrino appearance in a muon neutrino beam produced 295 km from the Super-Kamiokande detector with a peak energy of 0.6 GeV. A total of 28 electron neutrino events were detected with an energy distribution consistent with an appearance signal, corresponding to a significance of 7.