Estimation of the limit of detection using information theory measures

Definitions of the limit of detection (LOD) based on the probability of false positive and/or false negative errors have been proposed over the past years. Although such definitions are straightforward and valid for any kind of analytical system, proposed methodologies to estimate the LOD are usually simplified to signals with Gaussian noise. Additionally, there is a general misconception that two systems with the same LOD provide the same amount of information on the source regardless of the prior probability of presenting a blank/analyte sample. Based upon an analogy between an analytical system and a binary communication channel, in this paper we show that the amount of information that can be extracted from an analytical system depends on the probability of presenting the two different possible states. We propose a new definition of LOD utilizing information theory tools that deals with noise of any kind and allows the introduction of prior knowledge easily. Unlike most traditional LOD estimation approaches, the proposed definition is based on the amount of information that the chemical instrumentation system provides on the chemical information source. Our findings indicate that the benchmark of analytical systems based on the ability to provide information about the presence/absence of the analyte (our proposed approach) is a more general and proper framework, while converging to the usual values when dealing with Gaussian noise.     

Adaption helps for some nonconvex classes

We consider the problem of numerical integration of functions from a given class F. It has been shown that if F is convex and balanced than adaptive quadrature algorithms are not better than nonadaptive ones. We present examples of nonconvex classes of functions F for which adaption is substantially better than nonadaption. We discuss implications of these examples for practical numerical integration.     

On the vibrational behaviour of cyanide adsorbed at Pt(1 1 1) and Pt(1 0 0) surfaces in alkaline solutions

This communication deals with the vibrational behaviour of cyanide adlayers formed on Pt(1 1 1) and Pt(1 0 0) surfaces in the electrochemical environment. In situ FTIR spectroscopy can be employed to follow the potential dependence of the C-N stretching frequency in acidic electrolytes with quite a low uncertainty. Owing to the stability of the cyanide adlayer in alkaline solutions, experiments performed in NaOH medium are usually perturbed by the significant overlapping of the reference and the sample FTIR spectra. Deconvolution of the spectra was carried out assuming a Lorentz oscillator. The procedure allowed to confirm that two potential regions with different band centre frequency tuning coexist for Pt(1 1 1)-CN in perchloric acid medium. Conversely, in the alkaline electrolyte a single tuning rate for the band position was found for both surfaces studied. The lack of reorientation of the C-N molecular axis together with the occurrence of a certain screening effect of negatively charged hydroxyl anions on the electric field at the interface could be at the origin of the different behaviour displayed in both electrolytic media.     

Flame atomic absorption analysis of gold in jewelry samples

Summary A new procedure is proposed for the determination of gold by flame atomic absorption in jewelry samples. The method is based on the acid digestion of 10 mg of sample in a microwave oven and on the on-line dilution, using a three-way valve. The dynamic range of the technique is extended to 100 mg/l gold solutions and using a weighted bracketing method for the treatment of the results, accuracy errors lower than 2% can be found in the analysis of real samples as compared with those obtained by fire assay. The method is very fast and implies only little damage to the jewelry samples.     

Test of right-handed currents in baryon semileptonic decays

The effect of a right-handed boson on baryon semileptonic decay is considered. The analysis of polarized and unpolarized decays is carried out and it is shown that the best place to look for a right-handed current (RHC) signature is in polarized baryon decay. However, our results are useful for high statistics experiments. In order to see the contribution of the right-handed currents in the case of unpolarized hyperon decay, the Cabibbo theory should be assumed.     

Dynamics of sequential decision making

We suggest a new paradigm for intelligent decision-making suitable for dynamical sequential activity of animals or artificial autonomous devices that depends on the characteristics of the internal and external world. To do it we introduce a new class of dynamical models that are described by ordinary differential equations with a finite number of possibilities at the decision points, and also include rules solving this uncertainty. Our approach is based on the competition between possible cognitive states using their stable transient dynamics. The model controls the order of choosing successive steps of a sequential activity according to the environment and decision-making criteria. Two strategies (high-risk and risk-aversion conditions) that move the system out of an erratic environment are analyzed.     

Linear and non-linear optical properties of 2,5-disubstituted pyrroles supported by a catalyst-free SiO2 sonogel network

The preparation and optical characterization of pyrrole based sol-gel hybrid materials generated by ultrasonic irradiation (Sonogel composites) are presented in this work. Pyrrole compounds were recently synthesized in our group by a modification of the Schulte-Reisch reaction; these molecular systems were dissolved at different concentrations in tetrahydrofuran (THF) and optimally embedded into a catalyst-free SiO₂ sonogel network. For this purpose, we exploited the novel catalyst-free (CF) sonolysis route to produce highly pure sol-gel glasses, generated via sonochemical reactions. This approach has been recently developed in our research group and has been successfully implemented to develop several hybrid composites for optical applications. By this method, homogeneous and stable solid-state hybrid samples suitable for optical characterization can be produced. The high porosity exhibited by the sonogel matrix allowed us to prepare several pyrrole doped composites with variable dopant concentration. The linear and nonlinear optical (NLO) properties of these amorphous hybrid structures were determined by absorption- and photoluminescent (PL)-spectroscopies, and by the optical third harmonic generation (THG) techniques, respectively. The implemented catalyst-free sonolysis route produced SiO₂-host networks of high chemical and optical purity, suitable for optical and photonic applications.     

Electrochemical behavior of an aminotrithioether ligand: copper(II)-mediated oxidative C-C bond formation

A neutral aminotrithioether interacts with CuI, generating a coordination polymer in the solid state. Electrochemical studies indicate that the ligand is prone to oxidation by CuII, which results in a novel C-C bond formation reaction.     

Polymers from aryl cyclic sulfonium zwitterions—photosensitive materials cast from and developed in water

Upon photolysis or heating, aryl cyclic sulfonium (ACS) zwitterions polymerize by ring‐opening and loss of charge to yield nonionic polymers. These water‐soluble monomers potentially are useful for photolithography because they can be cast from and developed in water. The ACS zwitterion from bisphenol A, 1,1′‐[isopropylidenebis(6‐hydroxy‐3,1‐phenylene)] bis (tetrahydrothiophenium hydroxide) bis(inner salt) (1) is a negative‐tone, photosensitive material that after photolysis yields a crosslinked film. Unexposed regions are removed by water. The cured film has a low dielectric constant, high volume resistivity, a high degree of planarization, low residual stress, thermogravimetric stability, acceptable fracture toughness, and high hardness. These are desirable properties for a dielectric material used in microelectronic applications. However, a shortcoming of the material is its low T_g, at about 140 °C. A second ACS zwitterion, 1,1′‐[fluorenylidenebis(6‐hydroxy‐3,1‐phenylene)] bis(tetrahydrothiophenium hydroxide) bis(inner salt) (2) was prepared that yields a crosslinked polymer with a higher T_g of about 190 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1283–1290, 2000     

Synthesis and optical nondestructive evaluation of GaN nanorods on silicon surfaces with gold catalyst

Nanometric gallium-nitride rods were grown on a silicon (1 1 1) substrate through a chemical vapor deposition process with gold particles as the catalyst. Randomly distributed gallium-nitride rods of 20–200 nm in diameter and of various densities and lengths were formed under different deposition conditions. Characterization analyses, such as scanning electron microscopy and optical reflection spectroscopy, have been carried out on samples containing gallium-nitride rods different in size, shape, length and density. While the scanning electron microscopy shows directly the images of the sample surfaces, the optical spectroscopy provides a nondestructive evaluation of the sample surfaces, especially helpful for checking the uniformity of the samples.