Oxygen Radical Scavenger Activity, EPR, NMR, Molecular Mechanics and Extended-Hückel Molecular Orbital Investigation of the Bis(Piroxicam)Copper(II) Complex

The oxygen radical scavenger activity (ORSA) of [CuII(Pir)2] (HPir = Piroxicam = 4-hydroxy -2- methyl -N-2- pyridyl -2H- 1,2-benzothiazine -3- carboxamide 1,1-dioxide) was determined by chemiluminescence of samples obtained by mixing human neutrophils (from healthy subjects) and [CuII(Pir)2(DMF)2] (DMF = N,N -dimethylformammide) in DMSO/GLY/PBS (2:1:2, v/v) solution (DMSO = dimethylsulfoxide, GLY = 1,2,3-propantriol, PBS = Dulbecco’s buffer salt solution). The ratio of the residual radicals, for the HPir (1.02·10−4M) and [CuII(Pir)2(DMF)2] (1.08·10−5M)/HPir (8.01·10−−5M) systems was higher than 12 (not stimulated) [excess of piroxicam was added (Cu/Pir molar ratio ≈1:10) in order to have most of the metal complexed as bischelate]. In contrast, the ratio of residual radicals for the CuCl2 (1.00·10−5M) and [CuII(Pir)2(DMF)2] (1.08·10−5M)/Hpir (8.01·10−5M)system was 5. The [CuII(Pir)2] compound is therefore a stronger radical scavenger than either HPir or CuCl2. A molecular mechanics (MM) analysis of the gas phase structures of neutral HPir, its zwitterionic (HPir+-) and anionic (Pir-) forms, and some CuII-piroxicam complexes based on X-ray structures allowed calculation of force constants. The most stable structure for HPir has a ZZZ conformation similar to that found in the CuII (and CdII complexes) in the solid state as well as in the gas phase. The structure is stabilized by a strong H bond which involves the N(amide)-H and O(enolic) groups. The MM simulation for the [CuII(Pir)2(DMF)2] complex showed that two high repulsive intramolecular contacts exist between a pyridyl hydrogen atom of one Pir- molecule with the O donor of the other ligand. These interactions activate a transition toward a pseudo-tetrahedral geometry, in the case the apical ligands are removed. On refluxing a suspension of [CuII(Pir)2(DMF)2] in acetone a brown microcystalline solid with the Cu(Pir)2·0.5DMF stoichiometry was in fact prepared. 13C spin-lattice relaxation rates of neutral, zwitterionic and anionic piroxicam, in DMSO solution are explained by the thermal equilibrium between the three most stable structures of the three forms, thus confirming the high quality of the force field. The EPR spectrum of [CuII(Pir)2(DMF)2] (DMSO/GLY, 2:1, v/v, 298 and 110 K) agrees with a N2O2+O2 pseudo-octahedral coordination geometry. The EPR spectrum of [CuII(Pir)2·0.5DMF agrees with a pseudo-tetrahedral coordination geometry. The parameters extracted from the room temperature spectra of the solution phases are in agreement with the data reported for powder and frozen solutions. The extended-Hückel calculations on minimum energy structures of [CuII(Pir)2(DMF)2] and [CuII(Pir)2] (square planar) revealed that the HOMOs have a relevant character of dx2−y2. On the other hand the HOMO of a computer generated structure for [CuII(Pir)2] (pseudo-tetrahedral) has a relevant character of dxy atomic orbital. A dxy orbital is better suited to allow a dπ-pπ interaction to the O2- anion. Therefore this work shows that the anti-inflammatory activity of piroxicam could be due in part to the formation of [CuII(Pir)2] chelates, which can exert a SOD-like activity

Examination of isospin effects in multi-dimensional Langevin fission dynamics

One-dimensional and three-dimensional dynamical fission calculations based on Langevin equations are performed for the compound nuclei Pb-194, Pb-200, Pb-206, Hg-182, and Hg-204 to investigate the influence of the compound nucleus isospin on the prescission particle multiplicities and oil the fission fragment mass-energy distribution It is found that the prescission neutron, proton, and alpha particle multiplicities have approximately the same sensitivity to the dissipation strength for a given nucleus This is at variance with Conclusions of recent papers The sensitivity of the calculated prescission particle Multiplicities to the dissipation strength becomes higher with decreasing isospin of fissioning compound nucleus, and the increase of prescission particle multiplicities could reach 200%, when the reduction coefficient of one-body viscosity k(s) increases from 0 1 to 1, for the most neutron deficient nuclei considered The variances of fission fragment mass and kinetic energy distributions are less sensitive to the change of dissipation strength than the prescission light particle multiplicities A comparison to experimental data concerning Pb-200 nucleus is also presented

ATLANTIC EPIPHYTES: a data set of vascular and non-vascular epiphyte plants and lichens from the Atlantic Forest

Epiphytes are hyper-diverse and one of the frequently undervalued life forms in plant surveys and biodiversity inventories. Epiphytes of the Atlantic Forest, one of the most endangered ecosystems in the world, have high endemism and radiated recently in the Pliocene. We aimed to (1) compile an extensive Atlantic Forest data set on vascular, non-vascular plants (including hemiepiphytes), and lichen epiphyte species occurrence and abundance; (2) describe the epiphyte distribution in the Atlantic Forest, in order to indicate future sampling efforts. Our work presents the first epiphyte data set with information on abundance and occurrence of epiphyte phorophyte species. All data compiled here come from three main sources provided by the authors: published sources (comprising peer-reviewed articles, books, and theses), unpublished data, and herbarium data. We compiled a data set composed of 2,095 species, from 89,270 holo/hemiepiphyte records, in the Atlantic Forest of Brazil, Argentina, Paraguay, and Uruguay, recorded from 1824 to early 2018. Most of the records were from qualitative data (occurrence only, 88%), well distributed throughout the Atlantic Forest. For quantitative records, the most common sampling method was individual trees (71%), followed by plot sampling (19%), and transect sampling (10%). Angiosperms (81%) were the most frequently registered group, and Bromeliaceae and Orchidaceae were the families with the greatest number of records (27,272 and 21,945, respectively). Ferns and Lycophytes presented fewer records than Angiosperms, and Polypodiaceae were the most recorded family, and more concentrated in the Southern and Southeastern regions. Data on non-vascular plants and lichens were scarce, with a few disjunct records concentrated in the Northeastern region of the Atlantic Forest. For all non-vascular plant records, Lejeuneaceae, a family of liverworts, was the most recorded family. We hope that our effort to organize scattered epiphyte data help advance the knowledge of epiphyte ecology, as well as our understanding of macroecological and biogeographical patterns in the Atlantic Forest. No copyright restrictions are associated with the data set. Please cite this Ecology Data Paper if the data are used in publication and teaching events. © 2019 The Authors. Ecology © 2019 The Ecological Society of Americ

Clustering effects in 48Cr composite nuclei produced via 24Mg+ 24Mg reaction

In the framework of studying clustering effects in N=Z light nuclei, an experiment was carried out to get information on the properties of the 48Cr composite nuclei produced via the 24Mg +24Mg reaction. In particular, the study regards the 48Cr at 60 MeV of excitation energy where a resonance with a narrow width (170 KeV) has been found by measuring the elastic and anelastic channels. To determine the deformation of this state, evaporative Light Charged Particles (LCP) are measured and compared to the Statistical Model (SM) predictions, which are very sensitive to nuclear deformation. The experiment was performed at LNL using the 8LP apparatus to select LCPs and a Parallel Plate Avalanche Counter (PPAC) system to detect the Evaporation Residues (ER). Preliminary results on the measurements of ER - LCP and LCP - LCP angular correlations are presented which indicate the presence of a very large deformation.The analysis will proceed with the extraction of the LCP energy spectra and with the angular correlations for high multiplicity channels to determine the deformation

Clustering effects inCr48composite nuclei produced via theMg24+Mg24reaction

The nuclear properties of Cr-48 composite alpha-like nuclei produced at 60 MeV of excitation energy via the Mg-24 + 24Mg reaction were investigated. This excitation energy corresponds to a resonance with a narrow width (170 keV) observed in the elastic and inelastic channels, which was interpreted as a highly deformed state. To gain insight on the deformation of this state exclusive measurements of light charged particles were carried out with 8 pi LP apparatus at Laboratori Nazionali di Legnaro and compared to statistical model predictions. The measured of alpha-particle energy spectra, alpha-evaporation residues, alpha-alpha, and alpha-alpha-alpha correlations indicate the limitation of the rotating liquid drop model in describing the nuclear shape of the compound nucleus along the decay cascade. To reproduce the full set of experimental data very elongated nuclear shapes had to be considered, with an axis ratio 3 : 1 at the resonance angular momentum. This large deformation is consistent with previous findings for alpha-like nuclei and with the predictions of the cranked cluster model

Fission dynamics: The quest of a temperature dependent nuclear viscosity

This contribution presents a journey within the open questions about the current use of a temperature dependent nuclear viscosity in models of nuclear fission and proposes an alternative experimental approach by using systems of intermediate fissility. This study is particularly relevant because: i) systems of intermediate fissility offer a suitable framework since the intervals between the compound nucleus and scission point temperatures with increasing excitation energy are much smaller than in the case of heavier systems, ii) the measurement of observables in the ER channel translates into a larger set of effective constraints for the models

Fission Dynamics: The Quest of a Temperature Dependent Nuclear Viscosity

This paper presents a journey within some open questions about the current use of a temperature dependent nuclear viscosity in models of nuclear fission and proposes an alternative experimental approach by using systems of intermediate fissility. This study is particularly relevant because: i) systems of intermediate fissility offer a suitable frame-work since the intervals between the compound nucleus and scission point temperatures with increasing excitation energy are much smaller than in the case of heavier systems, ii) the dependence of viscosity on the temperature may change with the fissility of the composite system; iii) the opportunity to measure also observables in the evaporation residues channel translates into a larger set of effective constraints for the models

Fission dynamics with systems of intermediate fissility

A 4 pi light charged particle spectrometer, called 8 pi LP, is in operation at the Laboratori Nazionali di Legnaro, Italy, for studying reaction mechanisms in low-energy heavy-ion reactions. Besides about 300 telescopes to detect light charged particles, the spectrometer is also equipped with an anular PPAC system to detect evaporation residues and a two-arm time-of-flight spectrometer to detect fission fragments. The spectrometer has been used in several fission dynamics studies using as a probe light charged particles in the fission and evaporation residues (ER) channels. This paper proposes a journey within some open questions about the fission dynamics and a review of the main results concerning nuclear dissipation and fission time-scale obtained from several of these studies. In particular, the advantages of using systems of intermediate fissility will be discussed