Dual-target sensors: the effect of the encapsulation route on pH measurements and ammonia monitoring

Six different sensors were prepared using hydrolytic and non-hydrolytic sol–gel routes and three different pH indicators as receptor elements. These materials were employed as dual-target sensors for ammonia gas sensing and pH measurements in real samples. Ultraviolet–visible diffuse reflectance spectroscopy and a colorimetric analysis were used to evaluate the pH transitions and the color change that resulted from the ammonia that was employed as a probe for gas sensing. The colorimetric analysis was performed using the CIELAB color space model with the D65 standard illuminant. The resulting $ \Updelta {\text{E}}_{\text{ab}}^{*} $ values correlated with the response time for the observation of the first visible color change detected by the human eye (N = 50), and the average time values ranged from 48 to 117 s. In addition, the response times were evaluated as a function of sample characteristics, namely, the gender, age and eye color. Only groups of these characteristics exhibited relevance to the response time and could be associated with a specific range of time. The sensors were also employed for pH measurements of an aqueous solution, and a double-color scale could be established both with the sensors synthesized by the acid route and with the pH indicators alizarin red and brilliant yellow. From this color scale, it was possible to identify a shift in the turning point of the pH indicator from the free molecule to the encapsulated molecule. The double-color scale was applied to evaluate real samples from a galvanic industry using the synthesized encapsulated sensors.     

Fabrication of titania and titania–silica aerogels using rapid supercritical extraction

Titania (TiO₂) and titania–silica (TiSi) aerogels are suitable for photocatalytic oxidation of volatile organic compounds for pollution mitigation; however, methods for fabricating these aerogels can be complex. In this work we describe the use of a rapid supercritical extraction (RSCE) technique to prepare TiO₂ and TiSi aerogels in as little as 8 h. The RSCE technique uses a metal mold and a four-step hydraulic hot press procedure to bring the solvents in the sol–gel pores to a supercritical state and control the supercritical fluid release process. Resulting TiO₂ aerogels were powdery with BET surface areas of 130–180 m²/g, pore volumes ~0.5 cm³/g and skeletal densities of 3.6 g/mL. Monolithic TiSi aerogels were made using two different methods. An impregnation process, in which titania precursor was added to a silica sol–gel, took 4–8 days to complete with a 7-h RSCE and resulted in translucent aerogels with high surface area (560–650 m²/g) and pore volume (2.0–2.6 cm³/g), bulk densities ranging from 0.1 to 0.4 g/mL and skeletal densities of 2.3 g/mL. A co-precursor method for preparing TiSi aerogels took 8 h to complete. The precursor chemical mixture was poured directly into the mold and processed in a 7-h RSCE process. The resulting aerogels were opaque, with high surface areas (510–580 m²/g), low bulk density (0.03 g/mL), skeletal densities of 2 g/mL and pore volumes of 2.6–3.5 cm³/g. Preliminary solar simulator studies show that TiO₂ and TiSi aerogels are capable of photocatalytic degradation of methylene blue in aqueous solution.     

Evaluation of the binding ability of tetraaza[2]arene[2]triazine receptors anchoring l-alanine units for aromatic carboxylate anions

The binding affinities of three new tetraaza[2]arene[2]triazine based macrocycles anchoring one (AC1A) and two (AC2A and Me₄AC2A) l-alanine amino acid units for five aromatic carboxylate anions (bz^?, ph^2?, iph^2?, tph^2? and btc^3?) were investigated in DMSO-d₆. ¹H NMR titrations revealed that the AC1A and AC2A receptors exhibit comparable anion affinities, suggesting that the two l-alanine binding units in AC2A are not simultaneously involved in the anion recognition as indicated by molecular dynamics simulations carried out for selected AC1A and AC2A associations using the AMBER force field (GAFF). New force field parameters were developed in order to mimic the structural singularity derived from the N–H macrocyclic bridges.     

Discriminant analysis in the presence of interferences: Combined application of target factor analysis and a Bayesian soft-classifier

A method is described for performing discriminant analysis in the presence of interfering background signal. The method is based on performing target factor analysis on a data set comprised of contributions from analyte(s) and interfering components. A library of data from representative analyte classes is tested for possible contributing factors by performing oblique rotations of the principal factors to obtain the best match, in a least-squares sense, between test and predicted vectors. The degree of match between the test and predicted vectors is measured by the Pearson correlation coefficient, r, and the distribution of r for each class is determined. A Bayesian soft classifier is used to calculate the posterior probability based on the distributions of r for each class, which assist the analyst in assessing the presence of one or more analytes. The method is demonstrated by analyses performed on spectra obtained by laser induced breakdown spectroscopy (LIBS). Single and multiple bullet jacketing transfers to steel and porcelain substrates were analyzed to identify the jacketing materials. Additionally, the metal surrounding bullet holes was analyzed to identify the class of bullet jacketing that passed through a stainless steel plate. Of 36 single sample transfers, the copper jacketed (CJ) and non-jacketed (NJ) class on porcelain had an average posterior probability of the metal deposited on the substrate of 1.0. Metal jacketed (MJ) bullet transfers to steel and porcelain were not detected as successfully. Multiple transfers of CJ/NJ and CJ/MJ on the two substrates resulted in posterior probabilities that reflected the presence of both jacketing materials. The MJ/NJ transfers gave posterior probabilities that reflected the presence of the NJ material, but the MJ component was mistaken for CJ on steel, while non-zero probabilities were obtained for both CJ and MJ on porcelain. Jacketing transfer from a bullet to steel as the projectile passed through the steel also proved difficult to analyze. Over 50% of the samples left insufficient transfer to be identified. Transfer from NJ and CJ jacketing was successfully identified by posterior probabilities greater than 0.8.     

Pseudodeformations

We study the deformation functor of a reducible pseudocharacter. We show that there is a natural filtration (the complexity filtration) on such a functor, and that this filtration induces a filtration on the tangent space, whose graded pieces can be described in terms of the extension spaces between the irreducible components of the pseudocharacter. We also study the obstruction theory of that deformation problem.     

Sensitive determination of adenosine disodium triphosphate in soil,milk, and pharmaceutical formulation by enoxacin–europium (III) fluorescence complex in solution

A new spectroflurometric method for the determination of adenosine disodium triphosphate (ATP) is developed. Fluorometric interaction between ATP and enoxacin (ENX)–Eu³⁺ complex was studied using UV–vis and fluorescence spectroscopy. Weak luminescence spectra of Eu³⁺ were enhanced after complexation with ENX at 589 nm and 614 nm upon excitation at 395 nm due to energy transfer from the ligand to the lanthanide ion. It was observed that luminescence spectrum of Eu³⁺ was strongly enhanced further at 614 nm after incorporation of ATP into the ENX–Eu³⁺ complex. Under optimal conditions, the enhancement of luminescence at 614 nm was responded linearly with the concentration of ATP. The linearity was maintained in the range of 1.5×10^?10–1.15×10^?8 M (R=0.9973) with the limit of detection (3σ) of 4.71×10^?11 M. The relative standard deviation (RSD) for 9 repeated measurements of 1×10^?9  M ATP was 1.25%. Successful determinations of ATP in soil, milk, and a pharmaceutical formulation with the proposed method were demonstrated.     

The quest for ozone intensities in the 9–11 μm region: A retrospective

We review efforts to experimentally determine absolute line intensities for ozone transitions in the 9–11 μm spectral region over the last several decades. Much of this work has been driven by the requirements for remote sensing of terrestrial atmospheric ozone. While significant progress has been achieved, discrepancies persist among various infrared measurements, and the relation between infrared and ultraviolet standards is not clearly resolved.     

Synthesis and incorporation into cyclic peptides of tolan amino acids and their hydrogenated congeners: construction of an array of A-B-loop mimetics of the Cε3 domain of human IgE

The disruption of the human immunolobulin E-high affinity receptor I (IgE-FcεRI) protein-protein interaction (PPI) is a validated strategy for the development of anti asthma therapeutics. Here, we describe the synthesis of an array of conformationally constrained cyclic peptides based on an epitope of the A-B loop within the Cε3 domain of IgE. The peptides contain various tolan (i.e., 1,2-biarylethyne) amino acids and their fully and partially hydrogenated congeners as conformational constraints. Modest antagonist activity (IC(50) ～660 μM) is displayed by the peptide containing a 2,2'-tolan, which is the one predicted by molecular modeling to best mimic the conformation of the native A-B loop epitope in IgE.     

Mixed-Ligand Complex Formation Equilibria of Vanadium(III) with 2,2′-Bipyridine and the Amino Acids Glycine, Proline, α-Alanine and β-Alanine Studied in 3.0 mol?dm?3 KCl at 25 °C

We studied speciation of the mixed-ligand complex formation equilibria of vanadium(III) with both 2,2??-bipyridine (Bipy) and the amino acids glycine (HGly), proline (HPro), ??-alanine (H??Ala), and ??-alanine (H??Ala) by means of electromotive forces measurements emf(H) using 3.0?mol?dm^?3 KCl as the ionic medium at 25 °C. The experimental data were analyzed by means of the computational least-squares program LETAGROP, taking into account the hydrolysis of the vanadium(III) cation, the respective stability constants of the binary complexes, and the acid/base reactions of the ligands which were kept fixed during the analysis. In all four amino acid systems studied we observed the complexes [V₂O(Bipy)(B)]³⁺, [V₂O(Bipy)₂(B)₂]²⁺, [V(OH)(Bipy)(B)₂] and [V(OH)₂(Bipy)(B)], where B represents the deprotonated form of the amino acids studied in this work. The respective stability constants were determined and the species distribution diagrams as a function of pH are briefly discussed.     

Comparative Study of Ruthenium(II) and Ruthenium(III) Complexes with the Ligand dmbpy (dmbpy = 4, 4′‐Dimethyl‐2, 2′‐bipyridine)

The complex cis‐[Ru^III(dmbpy)₂Cl₂](PF₆) ( 2 ) (dmbpy = 4, 4′‐dimethyl‐2, 2′‐bipyridine) was obtained from the reaction of cis‐[Ru^II(dmbpy)₂Cl₂] ( 1 ) with ammonium cerium(IV) nitrate followed by precipitation with saturated ammonium hexafluoridophosphate. The ¹H NMR spectrum of the Ru^III complex confirms the presence of paramagnetic metal atoms, whereas that of the Ru^II complex displays diamagnetism. The ³¹P NMR spectrum of the Ru^III complex shows one signal for the phosphorus atom of the PF₆^– ion. The perspective view of each [Ru^II/III(dmbpy)₂Cl₂]^0/+ unit manifests that the ruthenium atom is in hexacoordinate arrangement with two dmbpy ligands and two chlorido ligands in cis position. As the oxidation state of the central ruthenium metal atom becomes higher, the average Ru–Cl bond length decreases whereas the Ru–N (dmbpy) bond length increases. The cis‐positioned dichloro angle in Ru^III is 1.3° wider than that in the Ru^II. The dihedral angles between pair of planar six‐membered pyridyl ring in the dmbpy ligand for the Ru^II are 4.7(5)° and 5.7(4)°. The observed inter‐planar angle between two dmbpy ligands in the Ru^II is 89.08(15)°, whereas the value for the Ru^III is 85.46(20)°.