Conformational and NBO analysis on cis and trans isomers of methyl-1-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydro-9H-β-carboline-3-carboxylate

The cis and trans-methyl-1-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydro-9H-β-carboline-3-carboxylates were prepared and ¹H and ¹³C NMR spectra were recorded for both isomers. Conformational and NBO analysis were carried out for the cis and trans isomers. Conformer structures were pre-optimized using the hybrid method B3LYP along with the 6-311+G(d) basis set. Frequency calculations were employed to confirm the structures as minimum points. Potential energy surfaces (PES) were built at the same level of theory. Geometries obtained from DFT calculations were used to perform NBO analysis by the NBO 3.1 module in GAUSSIAN 03. The results obtained through theoretical calculations revealed that the shielding observed at C1 for the trans isomer can be attributed to carbomethoxy γ-effect, together with the hyperconjugative effect, while only hyperconjugative effects were found to explain the shielding of C3. The higher chemical shift value of C3 of the cis isomer was attributed to the carbonyl substituent, which plays an important role by capturing part of the electronic density in C3.     

Ugi multicomponent reaction with hydroxylamines: an efficient route to hydroxamic acid derivatives

Ugi condensations with O-protected hydroxylamines have been successfully performed in THF using ZnCl₂ as activating agent. This synthetic strategy opens up the route to a very convergent assemblage of `internal' hydroxamic acid derivatives (N-acyl-N-hydroxypeptides).     

RESEARCH NOTE

Abstract— The endogenous levels of indole-3-acetic acid (IAA), abscisic acid (ABA) and gibberellins (GA) were examined by gas chromatography-mass spectrometry in Prunus cerasus plantlets grown under different light conditions in relation to previous work on the photocontrol of stem elongation. The endogenous levels of free and conjugated IAA in the apical sections of red-grown shoots were about two-fold higher than those in the blue-treated plants, and these corresponded with maximum shoot elongation. By contrast, greater concentrations of ABA and GA were found in blue-grown plants compared to red with intermediate shoot growth. When blue was combined with red or far red, lower levels of IAA, ABA and GA correlated with less growth. These results suggest that the regulation of stem elongation by phytochrome and a blue-absorbing pigment may, at least in part, occur through a modulation of hormone levels.     

Organization and energy properties of metastable states for the random-field Ising model

Random-field Ising model (RFIM) systems are characterized by a large number of metastable states corresponding to local minima of the system energy with respect to single spin flip. We classified the minima in a hierarchical way based on the possibility of a given state to escape from a basin of mutually reachable states. We investigate the energy properties of the metastable states in relation to the basin they belong to: states of particularly high energy, obtained by fast-quenching randomly initial spin configurations, tend to have access to a complex structure of correlated basins, opposite to what is found for low-energy states. The purpose of this paper is to investigate the connection between the properties of the basin oriented graph and the energy of the corresponding states.     

Induction of apoptosis by photoexcited tetracyclic compounds derivatives of benzo[b]thiophenes and pyridines

The antiproliferative activity, upon UVA irradiation, of two tetracyclic derivatives of benzo[b]thiophenes and pyridines, a benzo[b]thienopyridopyrimidone (1) and a thienocarboline (2), has been investigated in a panel of human tumor cell lines. The two compounds present a remarkable cytotoxicity after UVA irradiation (365 nm), reaching an IC50 of 0.1 microM in the leukaemia cell lines and 0.3-0.5 microM in the solid tumour cell lines. Their effect on the cell cycle was measured by flow cytometry in Jurkat cells. The compounds induce cell cycle perturbations and trigger a massive apoptosis as revealed by the externalisation of Annexin V-targeted residues at the outer plasmatic membrane. Furthermore the drugs induce, upon UVA irradiation significant variations of the mitochondrial potential (Deltapsi(mt)) measured by flow cytometry using the fluorochrome JC-1. In addition we characterized the mitochondrial production of reactive oxygen species (ROS) using the probe dihydroethidine (HE) and the oxidations of the mitochondrial phospholipid cardiolipin using the interacting probe nonyl acridine orange (NAO). Both compounds stimulate the production of ROS, and remarkably induce oxidation of cardiolipin. We have investigated the DNA-binding properties of these two compounds by means of UV-Vis spectroscopy and fluorescence. The two compounds exhibit a low affinity toward the macromolecule. The mode of binding was also investigated by means of flow linear dichroism (LD) which has revealed that the two compounds do not efficiently intercalate into DNA. Finally, the DNA-photocleavaging properties of the test compounds were studied on pBR322 plasmid DNA as a model. Only compound 1 is able to induce a significant production of single strand breaks only after digestion with the base excision repair enzyme Endo III. Altogether these data suggest that DNA is not a preferential target of these molecules and other subcellular structures may be responsible for their high phototoxic activity.     

Bayesian estimation and prediction for the transformed Wiener degradation process

This paper proposes some Bayesian inferential procedures for the transformed Wiener (TW) process, a new degradation process that has been recently suggested in the literature to describe degradation phenomena where degradation increments are not necessarily positive and depend stochastically on the current degradation level. These procedures have been expressly conceived to allow one incorporating into the inferential process the type of prior information, on meaningful physical characteristics of the observed degradation process, that is generally available in practical settings. Several different prior distributions are proposed, each of them reflecting a specific degree of knowledge on the observed phenomenon. Simple strategies for eliciting the prior hyper‐parameters from the available prior information are provided. Estimates of the TW process parameters and some functions thereof are retrieved by adopting a Monte Carlo Markov Chain technique. Procedures that allow predicting the degradation increment, the useful life of a new unit, and the remaining useful life of a used unit are also provided. Finally, an application is developed on the basis of a set of real degradation measurements of some infrared light‐emitting diodes, widely used in communication systems. The obtained results demonstrate the feasibility of the proposed Bayesian approach and the flexibility of the TW process.     

Surfactant self-assembling in gas phase: electrospray ionization- and matrix-assisted laser desorption/ionization-mass spectrometry of singly charged AOT clusters

The self-assembling of sodium bis (2-ethylhexyl) sulfosuccinate (AOT) in gas phase has been investigated by electrospray ionization- and matrix-assisted laser desorption/ionization mass spectrometry. Large surfactant clusters with an aggregation number close to that found in apolar media have been observed either as positive or negative ions. Moreover, the marked predominance of singly charged species as well as preliminary theoretical calculations strongly suggest an aggregate structure characterized by an internal hydrophilic core hosting the extra charge surrounded by an apolar shell constituted by the surfactant alkyl chains. This structure is similar to that of the more familiar reversed micelles formed when an appropriate surfactant is solubilized in apolar solvents. Finally, similar trends are observed independently either on the ionization technique or the polarity of the solvent used. This, together with the large dependence of the aggregation number on the flow rates, strongly indicates that self-assembling of the surfactant molecules occurs during the evaporation step.     

Supported dichlorobis(3-hydroxi-2-methyl-4-pyrone)Ti(IV) catalysts: Evaluation on ethylene polymerization

Dichlorobis(3-hydroxi-2-methyl-4-pyrone)Ti(IV) complex was grafted on different inorganic supports, namely different kinds of SiO₂, MAO-modified silica, MCM-41, Al₂O₃, ZrO₂ and MgO. The resulting supported catalysts were shown to be active in ethylene polymerization using methylaluminoxane (MAO) as cocatalyst, most of them being even more active that the homogeneous complex. The highest catalyst activities were observed for the Ti complex supported on SiO₂ 948 activated at 450 °C, MCM-41 and Al₂O₃.     

The stable set problem and the thinness of a graph

We introduce a poly-time algorithm for the maximum weighted stable set problem, when a certain representation is given for a graph. The algorithm generalizes the algorithm for interval graphs and that for graphs with bounded pathwidth. By a suitable application to the frequency assignment problem, we improved several solutions to relevant benchmark instances.