Intermolecular interactions in organofluorine aggregates probed by laser R2PI spectroscopy

Resonant Two Photon Ionization (R2PI) spectroscopy has been applied to the study of host–guest interactions in molecular clusters formed by supersonic exspansion. Here, the results of R2PI spectroscopy of the fluorinated organic molecules para and ortho-fluoro-sec-butylbenzene and their complexes with water and argon are reported and discussed. In particular, it is shown that the position of the fluorine atom on the aromatic ring influences the formation of different kind of complexes (σ versus π) with argon and water. Ab initio calculations were performed to get insight into the molecular shape and the structure of these clusters.     

Optimization of Verapamil Drug Analysis by Excitation-Emission Fluorescence in Combination with Second-order Multivariate Calibration

Excitation emission fluorescence matrices (EEMs) of Verapamil drug were obtained by direct and by derivatization fluorescence spectroscopy. The fluorescence excitation and emission wavelengths were displaced to longer wavelengths and the fluorescence intensity was enhanced upon derivation with respect to the native fluorescence of the drug. The complete EEM of the native fluorescence of the drug and of the derivatization product were rapidly acquired by using a charged-coupled device detector (CCD), which is advantageous in terms of speed in the analysis, with respect to the use of a conventional photomultiplier detector. The EEMs were analyzed by several second-order multivariate calibration methods exploiting the second order advantage. The three-dimensional decomposition methods used, based in different assumptions about the trilinearity of the three way data structure under analysis, were parallel factor analysis (PARAFAC), bilinear least squares (BLLS), parallel factor analysis 2 (PARAFAC2) and multivariate curve resolution—alternating least squares (MCR-ALS). The determination was performed by using the standard addition approach. The figures of merit of the PARAFAC and BLLS methods were calculated, obtaining a lower limit of detection with the derivatization procedure, when compared with the direct measurement of the fluorescence of the drug. In Verapamil drug the best estimations were found with the BLLS and the MCR-ALS models. In the quantification of Verapamil in a pharmaceutical formulation the best estimation, when compared with the result obtained by the US Pharmacopeia high performance liquid chromatography approach, was obtained by direct fluorescence spectroscopy with MCR-ALS and by derivatization fluorescence spectroscopy with the PARAFAC2 model.     

A variant temporal-masking-curve method for inferring peripheral auditory compression

Recent studies have suggested that the degree of on-frequency peripheral auditory compression is similar for apical and basal cochlear sites and that compression extends to a wider range of frequencies in apical than in basal sites. These conclusions were drawn from the analysis of the slopes of temporal masking curves (TMCs) on the assumption that forward masking decays at the same rate for all probe and masker frequencies. The aim here was to verify this conclusion using a different assumption. TMCs for normal hearing listeners were measured for probe frequencies (f(P)) of 500 and 4000 Hz and for masker frequencies (f(M)) of 0.4, 0.55, and 1.0 times the probe frequency. TMCs were measured for probes of 9 and 15 dB sensation level. The assumption was that given a 6 dB increase in probe level, linear cochlear responses to the maskers should lead to a 6 dB vertical shift of the corresponding TMCs, while compressive responses should lead to bigger shifts. Results were consistent with the conclusions from earlier studies. It is argued that this supports the assumptions of the standard TMC method for inferring compression, at least in normal-hearing listeners.     

Biolabeling with nanoparticles based on Y2O3: Nd and luminescence detection in the near-infrared

Neodymium based fluorescence presents several advantages in comparison to conventional rare earth or enzyme-substrate based fluorescence emitting sources (e.g.Tb, HRP) . Based on this fact we have herein explored a Nd-based fluoroimmunoassay. We efficiently detected the presence of an oxidized low-density lipoprotein (oxLDL) in human plasma a well-known marker for cardiovascular diseases, which causes around 30% of deaths worldwide. Conventional fluoroimmunoassay uses time-resolved luminescence techniques, with detection in the visible range, to eliminate the fluorescence background from the biological specimens. By using an immunoassay based on functionalized Y₂O₃:Nd³⁺ nanoparticles, where the excitation and emission processes in the Nd³⁺ ion occur in the near-infrared (NIR) region, we have succeeded in eliminating the interferences from the biological fluorescence background, avoiding the use of time-resolved techniques. This yields higher emission intensity from the Nd³⁺-nanolabels and efficient detection of anti-oxidized low-density lipoproteins (anti-oxLDL) by Y₂O₃:Nd³⁺-antibody-antigen conjugation, leading to a novel biolabeling method.     

Randomised circular means of Fourier transforms of measures

We explore decay estimates for circular means of the Fourier transform of a measure on in terms of its -dimensional energy. We find new upper bounds for the decay exponent. We also prove sharp estimates for a certain family of randomised versions of this problem.

     

On distributive modules and rings

In this paper we study ω-distributive modules, where ω is a cardinal number. We extend a characterization of distributive modules to ω-distributive modules. In particular, the case in which ω = n is a finite cardinal is considered. We apply the results to the case n = 2, obtaining new characterizations for distributive modules and rings. Special attention is given to saturated submodules and ideals.     

Systematic parametric investigation on the CVD process of polysiloxane nano- and microstructures

Amorphous polysiloxane nano- and microstructures with different shapes can be synthesized from trifunctional organosilane precursors. In the present study, various polysiloxane nano- and microstructures have been produced via a chemical vapor deposition process using ethyltrichlorosilane as precursor. The structure formation and shape are the result of a delicate interplay between temperature, absolute amount of water, and relative humidity. The impact of these reaction parameters during a chemical vapor deposition process has been examined. Experiments have been performed to find a correlation between the reaction conditions and the final shape. Scanning electron microscopy data show that different structures like polysiloxane microrings, microrods, sprouts, nanofilaments, and mixtures of them can be synthesized depending on the reaction conditions. Furthermore, the in-depth comparison of the nanofilament diameters illustrates the dominating influence of relative humidity on structure formation. There is a general trend that at a higher value of relative humidity, structures with a larger diameter are formed independent from the temperature. Here, we clearly differentiate between relative humidity as major and absolute amount of water and temperature as minor important adjusting screws defining the thickness and shape of the resulting nano- and microstructures. Based on these observations, we proof the mechanism of the initial step of structure formation. It is shown that nano- and micro-sized water droplets formed on the substrate surface are likely to act as starting points for structure formation. All results described here strongly confirm the recently published droplet assisted growth and shaping mechanism.