The Role of Ligand Topology in the Decomplexation of Luminescent Lanthanide Complexes by Dipicolinic Acid

In this study, we present the aqueous solution behavior of two luminescent lanthanide antenna complexes (Eu³⁺? 1 , Dy³⁺? 9 ) with different ligand topologies in the presence of dipicolinic acid (DPA, pyridine‐2,6‐dicarboxylic acid). Macrocyclic (1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid, DO3A, 9 ) and acyclic (1,4,7‐triazaheptane‐1,1,7,7‐tetraacetic acid, DTTA, 1 ) ligands have been selected to form a ratiometric pair in which Dy³⁺? 9 acts as a reference and Eu³⁺? 1 acts as a probe for the recognition of DPA. The pair of luminescent complexes in water reveals the capability to work as a DPA luminescent sensor. The change of emission intensity of Eu³⁺ indicates the occurrence of a new sensitization path for the lanthanide cation through excitation of DPA. NMR evidence implies the presence of free 1 and mass spectrometry shows the formation of emitting [EuDPA₂]^? as a result of a ligand exchange reaction.     

Continuous Bulk Process for the Production of High‐Impact Polystyrene: Recent Developments in Modeling and Control

This work presents (in a wider perspective), some of our recent developments in the mathematical modeling and control of bulk polymerization for the production of HIPS. The recent model by Casís assumes the polymerization to be heterogeneous, and it calculates (in two phases) the global molecular structure of the three polymeric components of HIPS (free polystyrene, unreacted polybutadiene, and graft copolymer). At present, a model is being developed capable of estimating the average particle morphology (salami or core‐shell). Assuming a continuous bulk HIPS process as homogeneous, Luciani estimated the evolution of the MFI of the final product during changes of grade, with the aim of minimizing the intermediate off‐spec product. Finally, an unpublished simulation is presented that describes the transitions between the steady state of a HIPS‐grade and that of a general‐purpose polystyrene.

     

Oppenauer oxidation of secondary alcohols with 1,1,1-trifluoroacetone as hydride acceptor

1,1,1-Trifluoroacetone (2a) reacts as a hydride-acceptor in the Oppenauer oxidation of secondary alcohols (1) in the presence of diethylethoxyaluminum. The oxidant allows for selective oxidation of secondary alcohols in the presence of primary alcohols.     

Experimental search for solar axions

A new technique has been used to search for solar axions using a single crystal germanium detector. It exploits the coherent conversion of axions into photons when their angle of incidence satisfies a Bragg condition with a crystalline plane. The analysis of approximately 1.94 kg.yr of data from the 1 kg DEMOS detector in Sierra Grande, Argentina, yields a new laboratory bound on axion-photon coupling of g_αγγ < 2.7 × 10⁻⁹GeV⁻¹, independent of axion mass up to 1 keV.     

Simultaneous quantification of 17 trace elements in blood by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) equipped with a high-efficiency sample introduction system

A quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) equipped with a dynamic reaction cell (DRC) and coupled with a desolvating nebulization system (APEX-IR) was employed to determine 17 elements (Al, As, Ba, Cd, Co, Cr, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, V, and Zr) in blood samples. Ammonia (for Al, Cr, Mn, and V) and O₂ (for As and Se) were used as reacting gases. Selection of the best flow rate of the gases and optimization of the quadrupole dynamic bandpass tuning parameter (RPq) were carried out, using digested blood diluted 1 + 9 with deionized water and spiked with 1 μg L⁻¹ of Al, Cr, Mn, V and 5 μg L⁻¹ of As and Se. Detection limits were determined in digested blood using the 3σ criterion. The desolvating system allowed a sufficient sensitivity to be achieved to determine elements at levels of ng L⁻¹ without detriment of signal stability. The accuracy of the method was tested with the whole blood certified reference material (CRM), certified for Al, As, Cd, Co, Cr, Mn, Mo, Ni, Pb, Sb, Se, and V, and with indicative values for Ba, Li, Sn, Sr, and Zr. The addition calibration approach was chosen for analysis. In order to confirm the DRC data, samples were also analyzed by means of sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), operating in medium (m/Δm = 4000) and high (m/Δm = 10,000) resolution mode and achieving a good agreement between the two techniques.     

A comprehensive PIV measurement campaign on a fully equipped helicopter model

The flow field around a helicopter is characterised by its inherent complexity including effects of fluid?Cstructure interference, shock?Cboundary layer interaction, and dynamic stall. Since the advancement of computational fluid dynamics and computing capabilities has led to an increasing demand for experimental validation data, a comprehensive wind tunnel test campaign of a fully equipped and motorised generic medium transport helicopter was conducted in the framework of the GOAHEAD project. Different model configurations (with or without main/tail rotor blades) and several flight conditions were investigated. In this paper, the results of the three-component velocity field measurements around the model are surveyed. The effect of the interaction between the main rotor wake and the fuselage for cruise/tail shake flight conditions was analysed based on the flow characteristics downstream from the rotor hub and the rear fuselage hatch. The results indicated a sensible increment of the intensity of the vortex shedding from the lower part of the fuselage and a strong interaction between the blade vortex filaments and the wakes shed by the rotor hub and by the engine exhaust areas. The pitch-up phenomenon was addressed, detecting the blade tip vortices impacting on the horizontal tail plane. For high-speed forward flight, the shock wave formation on the advancing blade was detected, measuring the location on the blade chord and the intensity. Furthermore, dynamic stall on the retreating main rotor blade in high-speed forward flight was observed at r/R?=?0.5 and 0.6. The analysis of the substructures forming the dynamic stall vortex revealed an unexpected spatial concentration suggesting a rotational stabilisation of large-scale structures on the blade.     

Chemical composition and antibacterial activity of the essential oil of Espeletia nana

The essential oil of the leaves of Espeletia nana Cuatrec., obtained by hydrodistillation, was analyzed by GC-MS, which allowed the identification of 24 components, which made up 99.9% of the oil. The most abundant compounds were a-pinene (38.1%), beta-pinene (17.2%), myrcene (15.0%), spathulenol (4.2%), bicyclogermacrene (4.0%), a-zingiberene (4.0%), and gamma-himachalene (3.7%). Antibacterial activity was tested against Gram-positive and Gram-negative bacteria using the agar disk diffusion method. Activity was observed only against Gram-positive bacteria. MIC values were determined for Staphylococcus aureus ATCC 25923 (200 microg/mL) and Enterococcusfaecalis ATCC 29212 (600 microg/mL).     

On Random Flights with Non-uniformly Distributed Directions

This paper deals with a new class of random flights in ℝ ^d , d≥2, characterized by non-uniform probability distributions on the multidimensional sphere. These random motions differ from similar models appeared in literature where the directions are taken according to the uniform law. The family of angular probability distributions introduced in this paper depends on a parameter ν≥0, which gives the anisotropy of the motion. Furthermore, we assume that the number of changes of direction performed by the random flight is fixed. The time lengths between two consecutive changes of orientation have joint probability distribution given by a Dirichlet density function.     

Synthesis and stereochemical studies of 2‐substituted thiazolidine‐4‐carboxamide derivatives

A series of new 2‐substituted thiazolidine‐4‐carboxamide derivatives which have potentially useful immunological properties, have been synthesized in a stereoselective manner by coupling 2‐subsituted thiazolidine‐4‐carboxylic acids with amines or amino esters. The structure of these compounds was established by combination of NMR methods and by X‐ray analysis.     

On the Nitroxide Quasi‐Equilibrium in the Alkoxyamine‐Mediated Radical Polymerization of Styrene

Summary: The range of validity of two popular versions of the nitroxide quasi‐equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, k_c[P][N] = k_d[P N], where P, N and P N are living, nitroxide radicals and dormant species respectively, with kinetic constants k_c and k_d, is found valid only for small values of the equilibrium constant K (10⁻¹¹–10⁻¹² mol · L⁻¹) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, k_c[P][N] = k_d[P N]₀ was found to be remarkably good up to values of K around 10⁻⁸ mol · L⁻¹. This upper bound is numerically found to be 2–3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico‐chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested.

Validity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.