Modification of the luminescence properties of an Europium(III) Tris(β-diketonate) Complex by Inclusion in γ-cyclodextrin and 2,3,6-trimethyl-γ-cyclodextrin

A 1:1 inclusion compound between octakis(2,3,6-tri-O-methyl)-γ-cyclodextrin (TRIMEG) and the chelate complex Eu(NTA)₃·2H₂O (NTA=1-(2-naphthoyl)-3,3,3-trifluoroacetonate) was prepared and characterized by powder X-ray diffraction, thermogravimetric analysis and photoluminescence spectroscopy. The results were compared with those obtained for the corresponding native γ-CD adduct. Excitation and emission spectra were measured, and the lifetimes were determined for the Eu³⁺ first excited state (⁵D₀). The results indicate the presence of only one low-symmetry environment for the Eu³⁺ cations in the inclusion compounds. Encapsulation of the Europium complex in the two CDs increases the quantum efficiency of the ligand-to-metal energy transfer pathway, but the efficiency of the Eu³⁺ sensitization was significantly higher with TRIMEG as the host molecule. This may be related with the observation that the two hosts appear to have different influences on the Eu³⁺ coordination environments for the guest molecule.     

Direct versus resonances mediated F+OH collisions on a new 3A" potential energy surface

A theoretical study of the F(2P) + OH(2Pi) --> HF(1Sigma+) + O(3P) reactive collisions is carried out on a new global potential energy surface (PES) of the ground 3A" adiabatic electronic state. The ab initio calculations are based on multireference configuration interaction calculations, using the aug-cc-pVTZ extended basis sets of Dunning et al. A functional representation of the PES shows no nominal barrier to reaction, contrary to previous results by others. Wave packet and quasiclassical trajectory calculations have been performed for this PES to study the F + OH(v = 0,j) reactive collision. The comparison was performed at fixed and constant values of the total angular momentum from 0 to 110 and relative translational energy up to 0.8 eV. The reaction presents a dynamical barrier, essentially due to the zero-point energy for the bending vibration near the saddle point. This determines two different reaction mechanisms. At energies higher than approximately 0.125 eV the reaction is direct, while below that value it is indirect and mediated by heavy-light-heavy resonances. Such resonances, also found in the simulations of the photodetachment spectrum of the triatomic anion, manifest themselves in the quasiclassical simulations, too, where they are associated to periodic orbits.     

A continuous flow system design for simultaneous determination of heavy metals in river water samples

A new design of a continuous flow system applied to the simultaneous determination of the concentration of zinc(II), cadmium(II), lead(II), copper(II), nickel(II), cobalt(II) and chromium(VI) in river water is described. A flow cell made in the laboratory, which has been patented, based on a 'wall-jet' configuration with a three-electrode system is described. Optimum conditions for the determination of the metal ions are reported. The detection limits and relative standard deviation values were 4.01x10(-9) M and 0.078 for Zn(II), 1.76x10(-10) M and 0.056 for Cd(II), 4.69x10(-10) M and 0.134 for Pb(II), 2.29x10(-10) M and 0.138 for Cu(II), 1.61x10(-9) M and 0.093 for Ni(II), 1.91x10(-9) M and 0.113 for Co(II), and 1.35x10(-9) M and 0.081 for Cr(VI). The procedure was applied to a sample of water from the Arlanzón river and the results were compared with inductively coupled mass plasma spectrometry (ICP-MS) as reference method. The final aim of this work is to design a flow system, which can be automated.     

Fluorometric sensors based on chemically modified enzymes Glucose determination in drinks

In this paper an enzymatic fluorometric sensor for glucose determination in drinks is presented. The sensor film was obtained by immobilisation of glucose oxidase chemically modified with a fluorescein derivative (GOx-FS) in a polyacrylamide polymer. During the enzymatic reaction the changes in the fluorescence intensity of the GOx-FS are related to the glucose concentration. Working in FIA mode, the optimum conditions found were: 0.7 ml min(-1) flow rate, 300 mul sample injection and pH 6.5. The sensor responds to glucose concentrations ranging from 400 to 2000 mg l(-1), the reproducibility is around 3% and the life-time is at least 3 months (more than 350 measurements). The sensor was applied to direct glucose determination in drinks with good accuracy; interference caused by the filter effect was avoided by the kinetics of the reaction.     

A peroxidase-tetrathiafulvalene biosensor based on self-assembled monolayer modified Au electrodes for the flow-injection determination of hydrogen peroxide

The construction and performance under flow-injection conditions of an integrated amperometric biosensor for hydrogen peroxide is reported. The design of the bioelectrode is based on a mercaptopropionic acid (MPA) self-assembled monolayer (SAM) modified gold disk electrode on which horseradish peroxidase (HRP, 24.3 U) was immobilized by cross-linking with glutaraldehyde together with the mediator tetrathiafulvalene (TTF, 1 μmol), which was entrapped in the three-dimensional aggregate formed.

The amperometric biosensor allows the obtention of reproducible flow injection amperometric responses at an applied potential of 0.00 V in 0.05 mol L⁻¹ phosphate buffer, pH 7.0 (flow rate: 1.40 mL min⁻¹, injection volume: 150 μL), with a range of linearity for hydrogen peroxide within the 2.0 × 10⁻⁷–1.0 × 10⁻⁴ mol L⁻¹ concentration range (slope: (2.33 ± 0.02) × 10⁻² A mol⁻¹ L, r = 0.999). A detection limit of 6.9 × 10⁻⁸ mol L⁻¹ was obtained together with a R.S.D. (n = 50) of 2.7% for a hydrogen peroxide concentration level of 5.0 × 10⁻⁵ mol L⁻¹. The immobilization method showed a good reproducibility with a R.S.D. of 5.3% for five different electrodes. Moreover, the useful lifetime of one single biosensor was estimated in 13 days.

The SAM-based biosensor was applied for the determination of hydrogen peroxide in rainwater and in a hair dye. The results obtained were validated by comparison with those obtained with a spectrophotometric reference method. In addition, the recovery of hydrogen peroxide in sterilised milk was tested.     

On the Fourier Transform of Causal Distributions

We extend the distributional Bochner formula [1, p. 72, Theorem 26] to certain kinds of distributions. Theorem I.1 gives a formula [Eq. (I.1.14)] which makes it possible to obtain easily the Fourier transform of distributions of the form As applications of the formula (I.1.14) we evaluate the Fourier transforms of the distributions G_α(P±i0, m, n) [Eq. (I.4.1)] and H_α(P±i0,n) [Eq. (II.1.1)]. It follows from Theorem II.3 that H_zk(P±i0,n) is, for 2K≠n+2r, r=0,1..., an elementary solution of the n-dimensional ultrahyperbolic operator iterated k times.     

A novel non-invasive electrochemical biosensing device for in situ determination of the alcohol content in blood by monitoring ethanol in sweat

A non-invasive, passive and simple to use skin surface based sensing device for determining the blood's ethanol content (BAC) by monitoring transdermal alcohol concentration (TAC) is designed and developed. The proposed prototype is based on bienzyme amperometric composite biosensors that are sensitive to the variation of ethanol concentration. The prototype correlates, through previous calibration set-up, the amperometric signal generated from ethanol in sweat with its content in blood in a short period of time. The characteristics of this sensor device permit determination of the ethanol concentration in isolated and in continuous form, giving information of the BAC of a subject either in a given moment or its evolution during long periods of time (8 h). Moreover, as the measurements are performed in a biological fluid, the evaluated individual is not able to alter the result of the analysis. The maximum limit of ethanol in blood allowed by legislation is included within the linear range of the device (0.0005–0.6 g L⁻¹). Moreover, the device shows higher sensitivity than the breathalyzers marketed at the moment, allowing the monitoring of the ethanol content in blood to be obtained just 5 min after ingestion of the alcoholic drink. The comparison of the obtained results using the proposed device in the analysis of 40 volunteers with those provided by the gas chromatographic reference method for determination of BAC pointed out that there were no significant differences between both methods.     

Enantioselective synthesis of (+)-gossonorol and related systems using organozinc reagents

The sesquiterpene (+)-gossonorol is prepared in only three synthetic steps in 60% overall yield and 82% ee from commercially available reagents. The key asymmetric step is the catalytic enantioselective addition of dimethylzinc to 5-methyl-1-(2-methylphenyl)hex-4-en-1-one catalyzed by chiral isoborneolsulfonamide ligands in the presence of titanium tetraisopropoxide. The modular approach allows the synthesis not only of the aforementioned natural product but also other products arising from the corresponding processes of ethylation, phenylation, and ethynylation, just by changing the final nucleophilic reagent and using the same isoborneol type ligand.     

Unsupervised learning of pharmacokinetic responses

Pharmacokinetics (PK) is a branch of pharmacology dedicated to the study of the time course of drug concentrations, from absorption to excretion from the body. PK dynamic models are often based on homogeneous, multi-compartment assumptions, which allow to identify the PK parameters and further predict the time evolution of drug concentration for a given subject. One key characteristic of these time series is their high variability among patients, which may hamper their correct stratification. In the present work, we address this variability by estimating the PK parameters and simultaneously clustering the corresponding subjects using the time series. We propose an expectation maximization algorithm that clusters subjects based on their PK drug responses, in an unsupervised way, collapsing clusters that are closer than a given threshold. Experimental results show that the proposed algorithm converges fast and leads to meaningful results in synthetic and real scenarios.