Diastereo-controlled Diels–Alder cycloadditions of erythrose benzylidene-acetal 1,3-butadienes by 4-substituted-1,2,4-triazoline-3,5-dione: Evidence for the stereoelectronic effects on the dienes

Erythrose benzylidene-acetal 1,3-butadienes are studied as partners in Diels–Alder cycloadditions. A high diastereofacial improvement is found in cases where both the alcohol function is protected and a π–π interaction between the diene and dienophile is possible. Several competing factors have been studied independently in order to explain its influence on the selectivity of the cycloadditions.     

The Piracicaba River basin: isotope hydrology of a tropical river basin under anthropogenic stress

The stable isotope content of samples of precipitation and of the river water throughout the Piracicaba basin in Brazil was measured over a two-year period. The isotope values of precipitation follow a consistent pattern of relatively depleted values of both deuterium and oxygen 18 during the rainy summers and enriched ones during the dry winters, with all values aligned slightly above the Global Meteoric Water Line. The isotopic composition of the river water throughout the basin shows a remarkable spatial coherence and much smaller scatter of data than those of the precipitation. The isotope composition of river water is close to that of the precipitation in the rainy season, however, with a consistent lower d-excess value by 1/1000-2/1000. This is attributed to evaporative water loss in the basin, in part an expression of the recycling of water due to the anthropogenic activity in the region. The more divergent values are recorded during high-water stages in the rivers. In many cases, the floods during the beginning of the rainy season are characterized by an enrichment of the heavy isotopes and lower d-excess values when compared to the precipitation, with the opposite situation later in the rainy season. This is interpreted as resulting from the watershed/riverflow interaction pattern, and it thus suggests that the isotope composition can monitor the hydrologic situation in the basin and its changes.     

Quantitative determination of the 3D dipole orientation of single molecules

Recently, different approaches have been implemented to detect single molecules with an optical dipole out of the sample plane. Principles to solve this problem of general interest have been laid but no detailed analysis has been performed to date. This paper is devoted to a quantitative analysis of the dipole orientation of out of plane molecules that we have detected by amplitude and phase masking of the input beam. The accuracy of the orientation is discussed.Received: 22 July 2003, Published online: 2 December 2003PACS: 32.50. + d Fluorescence, phosphorescence (including quenching)     

Phosphate diester hydrolysis and DNA damage promoted by new cis-aqua/hydroxy copper(II) complexes containing tridentate imidazole-rich ligands

The tridentate Schiff base [(2-(imidazol-4-yl)ethyl)(1-methylimidazol-2-yl)methyl)imine (HISMIMI) and its reduced form HISMIMA were synthesized and characterized, as well their mononuclear cis-dihalo copper(II) complexes 1 and 2, respectively. In addition, the dinuclear [CuII(mu-OH)2CuII](2+) complexes (3) and (4) obtained from complexes 1 and 2, respectively, were also isolated and characterized by several physicochemical techniques, including magnetochemistry, electrochemistry, and EPR and UV-vis spectroscopies. The crystal structures of 1 and 2 were determined by X-ray crystallography and revealed two neutral complexes with their tridentate chelate ligands meridionally coordinated. Completing the coordination spheres of the square-pyramidal structures, a chloride ion occupies the apical position and another is bonded in the basal plane. In addition, complexes 1 and 2 were investigated by infrared, electronic, and EPR spectroscopies, cyclic voltammetry, and potentiometric equilibrium studies. The hydrolytic activity on phosphate diester cleavage of 1 and 2 was investigated utilizing 2,4-BDNPP as substrate. These experiments were carried out at 50 degrees C, and the data treatment was based on the Michaelis-Menten approach, giving the following kinetic parameters (complex 1/complex 2): vmax (mol L(-1) s(-1))=16.4x10(-9)/7.02x10(-9); KM (mol L(-1))=17.3x10(-3)/3.03x10(-3); kcat (s(-1))=3.28x10(-4)/1.40x10(-4). Complex 1 effectively promoted the hydrolytic cleavage of double-strand plasmid DNA under anaerobic and aerobic conditions, with a rate constant of 0.28 h(-1) for the decrease of form I, which represents about a 10(7) rate increase compared with the estimated uncatalyzed rate of hydrolysis.     

Application of Fourier transform infrared spectroscopy and orthogonal projections to latent structures/partial least squares regression for estimation of procyanidins average degree of polymerisation

Fourier transform infrared (FTIR) spectroscopy has being emphasised as a widespread technique in the quick assess of food components. In this work, procyanidins were extracted with methanol and acetone/water from the seeds of white and red grape varieties. A fractionation by graded methanol/chloroform precipitations allowed to obtain 26 samples that were characterised using thiolysis as pre-treatment followed by HPLC-UV and MS detection. The average degree of polymerisation (DPn) of the procyanidins in the samples ranged from 2 to 11 flavan-3-ol residues. FTIR spectroscopy within the wavenumbers region of 1800-700 cm⁻¹ allowed to build a partial least squares (PLS1) regression model with 8 latent variables (LVs) for the estimation of the DPn, giving a RMSECV of 11.7%, with a R² of 0.91 and a RMSEP of 2.58. The application of orthogonal projection to latent structures (O-PLS1) clarifies the interpretation of the regression model vectors. Moreover, the O-PLS procedure has removed 88% of non-correlated variations with the DPn, allowing to relate the increase of the absorbance peaks at 1203 and 1099 cm⁻¹ with the increase of the DPn due to the higher proportion of substitutions in the aromatic ring of the polymerised procyanidin molecules.     

Consecutive customer losses in oscillating GIX/M//n systems with state dependent services rates

We address the probability that k or more Consecutive Customer Losses take place during a busy period of a queue, the so-called k-CCL probability, for oscillating GI ^X /M//n systems with state dependent services rates, also denoted as GI ^X /M(m)−M(m)//n systems, in which the service rates oscillate between two forms according to the evolution of the number of customers in the system. We derive an efficient algorithm to compute k-CCL probabilities in these systems starting with an arbitrary number of customers in the system that involves solving a linear system of equations. The results derived are illustrated for specific sets of parameters.     

Consecutive customer losses in regular and oscillating <Emphasis Type="Italic">M</Emphasis><Superscript><Emphasis Type="Italic">X</Emphasis></Superscript>/<Emphasis Type="Italic">G</Emphasis>/1/<Emphasis Type="Italic">n</Emphasis> systems

We derive fast recursions to compute the probability that k or more consecutive customer losses take place during a busy period of a queue, the so called k-CCL probability, for regular and oscillating M ^X /G/1/n systems.     

Structural assessment under uncertain parameters via interval analysis

An efficient health monitoring system for damage detection in civil engineering structures using on-line monitoring data is being developed to identify any possible damage in short time. The present work is based on the treatment of uncertainties, which is one of the basic common difficulties faced when modelling structures. A methodology, based on interval analysis (IA) theory [R.E. Moore, Interval Analysis, Prentice-Hall, Englewood Cliffs, NJ, 1966] applied to a numerical constraint satisfaction problem (CSP) [J.R. Casas, J.C. Matos, J.A. Figueiras, J. Vehí, O. García, P. Herrero, Bridge monitoring and assessment under uncertainty via interval analysis, in: Ninth International Conference On Structural Safety And Reliability—ICOSSAR2005, 2005. pp. 487–494], is implemented in the damage detection [J.R. Casas, J.C. Matos, J.A. Figueiras, J. Vehí, O. García, P. Herrero, Bridge monitoring and assessment under uncertainty via interval analysis, in: Ninth International Conference On Structural Safety And Reliability—ICOSSAR2005, 2005. pp. 487–494] and modelling system of a long-term monitoring project in order to achieve such an objective. An algorithm is being developed for using such methodology with the obtained data.     

An integrated experimental and theoretical investigation of the vibrational modes and molecular structure of a new Cu(II)–phosphocreatine complex

A new complex of Cu(II) of stoichiometry [Cu(PCr)(H₂O)] was prepared from aqueous solution at pH 6. Its synthesis, characterization, thermogravimetric, vibrational spectroscopy, and electron paramagnetic resonance analyses were described and suggest that phosphocreatine (PCr) in solid state is acting as a tridentate ligand (the nitrogen atom of the guanidine group and the oxygen atoms of the phosphate group and the carboxylate group being the donor atoms). The fourth position is occupied by a water molecule. These results were confirmed through computational calculations (DFT/B3LYP:6-311G theoretical procedure). The tetra coordination of Cu(II) arranged in a quadratic planar geometry was found to be more stable in the DFT calculations. The calculated vibrational spectrum agrees well with the FT-IR experimental spectrum.