Chloride‐Selective Electrodes Based on “Two‐Wall” Aryl‐Extended Calix[4]Pyrroles: Combining Hydrogen Bonds and Anion–π Interactions to Achieve Optimum Performance

The performance of chloride‐selective electrodes based on “two‐wall” aryl‐extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso‐positions. When the meso‐phenyl groups are decorated with strong electron‐withdrawing substituents, attractive anion–π interactions may exist between the receptor’s aromatic walls and the sandwiched anion. These anion–π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p‐nitro withdrawing group on each of the meso‐phenyl rings, afforded sensors that display anti‐Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion‐specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids.     

On the low-temperature anomalies of specific heat in disordered carbon nanotubes

The low-temperature behavior of the specific heat in disordered nanotubes strongly depends on structure changes and is not explained by the phonon contribution. Expression for electronic specific heat is carried out taking into account the multiple elastic electron scattering on impurities and structural inhomogeneities of short-range order type. The calculated electronic specific heat depends on diameter of nanotube, concentration of impurities, parameters of short-range order (structural heterogeneity) and describes the peculiarities of low-temperature behavior of specific heat observed in disordered CNT.     

Study of blood collection and sample preparation for analysis of vitamin D and its metabolites by liquid chromatography–tandem mass spectrometry

The analysis of vitamin D status, with special emphasis on 25-hydroxyvitamin D and 1,25-dihydroxyvitamin D, is gaining interest in clinical studies due to the classical and non-classical effects attributed to this prohormone. In this research, the influence of the two steps preceding determination (viz. sample collection and preparation) on the quantitative analysis of vitamin D and its more important metabolites has been studied. Two preparation approaches, deproteination and solid-phase extraction (SPE), have been evaluated in terms of sensitivity to delimit their application, thus establishing that detection of 1,25-dihydroxyvitamin D cannot be addressed by protein precipitation. Concerning sample collection, serum and plasma reported high accuracy (above 83.3%) for vitamin D and metabolites, while precision, expressed as relative standard deviation, was below 12.9% for all analytes in both samples. Statistical analysis revealed that serum and plasma provided similar physiological levels for vitamin D₃, 24,25-dihydroxyvitamin D₃ and 25-hydroxyvitamin D₃, while significantly different levels were obtained for 1,25-dihydroxyvitamin D₃, always higher in plasma than in serum. Sample collection and treatment have proved to be significant in the analysis of vitamin D and its relevant metabolites.     

Methylthiouracil‐modified Carbon Paste Electrode as a New Voltammetric Sensor Based on a 1,4‐Michael Addition Reaction for Detection of Dopamine

A sensitive dopamine sensor was constructed based on the modified carbon paste electrode with methylthiouracil as a nucleophile in the 1,4‐Michael addition reaction. An ECE mechanism was suggested for dopamine oxidation at the modified electrode. Design of experiments was used in the optimization of variables. Under the optimum conditions, calibration graph was linear in the range of 0.20–15.0 µM with a detection limit of 73 nM. The relative standard deviations (n=5) for 0.50 µM of dopamine was 3.83 %. The selectivity of the sensor was also studied. The developed sensor was applied for analysis of pharmaceutical and biological samples.     

Simple and Precise Quantification of Iron Catalyst Content in Carbon Nanotubes Using UV/Visible Spectroscopy

Iron catalysts have been used widely for the mass production of carbon nanotubes (CNTs) with high yield. In this study, UV/visible spectroscopy was used to determine the Fe catalyst content in CNTs using a colorimetric technique. Fe ions in solution form red–orange complexes with 1,10-phenanthroline, producing an absorption peak at λ=510 nm, the intensity of which is proportional to the solution Fe concentration. A series of standard Fe solutions were formulated to establish the relationship between optical absorbance and Fe concentration. Many Fe catalysts were microscopically observed to be encased by graphitic layers, thus preventing their extraction. Fe catalyst dissolution from CNTs was investigated with various single and mixed acids, and Fe concentration was found to be highest with CNTs being held at reflux in HClO₄/HNO₃ and H₂SO₄/HNO₃ mixtures. This novel colorimetric method to measure Fe concentrations by UV/Vis spectroscopy was validated by inductively coupled plasma optical emission spectroscopy, indicating its reliability and applicability to asses Fe content in CNTs.     

Infinite family of transmission irregular trees of even order

Distance between two vertices is the number of edges in a shortest path connecting them in a connected graph $G$. The transmission of a vertex $v$ is the sum of distances from $v$ to all the other vertices of $G$. If transmissions of all vertices are mutually distinct, then $G$ is a transmission irregular graph. It is known that almost no graphs are transmission irregular. Infinite families of transmission irregular trees of odd order were presented in Alizadeh and Klav?ar (2018). The following problem was posed in Alizadeh and Klav?ar (2018): do there exist infinite families of transmission irregular trees of even order? In this article, such a family is constructed.     

Molecular dynamics of the intramolecular 1, 3-dipolar ene reaction of a nitrile oxide and an alkene: non-statistical behavior of a reaction involving a diradical intermediate*

ABSTRACT

Potential energy surfaces and molecular dynamics of the intramolecular 1, 3-dipolar cycloaddition and ene reaction of a nitrile oxide with an alkene were performed in the gas phase and in dichloromethane with density functional theory. One hundred trajectories were propagated in the gas phase and in dichloromethane, respectively. Twenty percent of the trajectories in the gas phase involve bicyclic intermediate and the mean time gap is 472fs. A dynamically stepwise reaction is observed. In dichloromethane, more reactive trajectories were obtained and the time gap is larger than that in the gas phase.