Effect of pH on the electrochemical properties of polyaniline nanoparticle suspension in strongly acidic solution: an experimental and theoretical study

Journal of Solid State Electrochemistry - A stable suspension of nanopolyaniline (nPANI) particles can be used in various applications instead of a polyaniline film. The electrochemical behavior of...     

NMR spectral analysis of strongly second-order 6-, 8-, 9- and 10- spin-systems (1H─19F, 19F─19F,and 13C─19F) in perfluorotoluyl- and tetrafluoro-pyridyl-aromatics using the lineshape method ANATOLIA

A simple to use nuclear magnetic resonance analysis method has been tested on complex ¹H, ¹⁹F, and ¹³C multiplets. This open-source line-shape analysis method analysis of total lineshape (ANATOLIA)¹ provides some significant advantages over traditional assign-iterate methods of NMR spectral analysis by avoiding false minima and progressing optimisation to the global minimum. The target molecules are 1-perfluorotol-4-yl-2-perfluorotol-4-yl-oxymethyl-1H-benzimidazole (molecule-I) and 1-tetrafluoropyrid-4-yl-2-tetrafluoropyrid-4-yl-thio-1H-benzimidazole (molecule-II) which were produced as part of a family of fluorinated drug scaffolds prepared for anticancer and antiparasitic screening. Spectra display significant second-order effects with ¹H Δδ = 3.68 and 4.67 Hz for the aromatic hydrogen “triplets”, with ¹⁹F ⁴J_AA', ⁴J_BB', ⁴J_XX', and ⁴J_YY' coupling constants range from +4.8 to −14.0 Hz and for ¹³C-isotopomers ¹⁹F Δδ of up to 111.56 Hz. A spin-system of six coupling nuclei (H_aH_bH_cH_d F_YF_Y') was analysed in 12 s, a spin-system of nine coupling fluorine nuclei (AA'BB'CCC-YY') was analysed within 2 min, and 10 coupling nuclei (XX'YY'ZZZ-BB'-H_d) was optimised in 6 min using a laptop computer. ANATOLIA was also robust enough to be able to yield accurate spectral values from inaccurate input values. In both compounds, a fluorine–fluorine coupling constant was identified between the two fluoro-aromatic rings (F_BB' and F_YY') of +4.05 and +4.67 Hz and attributed to a through-space interaction. Ab initio structure optimisations and coupling constant calculations provided useful input data for spectral analysis. A modern ¹⁹F nuclear magnetic resonance spectrum of perfluorotoluene (octafluorotoluene) and analysis from 1975 was used as a test data set to assess ANATOLIA.     

Constructing a new optical sensor for monitoring ammonia in water samples using bis(acetylacetoneethylendiamine)-tributylphosphin cobalt(III) tetraphenylborate complex-coated triacetylcellulose.

A new ammonia optical sensor was designed using bis(acetylacetoneethylendiamine)tributylphosphin cobalt(III) tetraphenylborate complex, coated on transparent triacetylcellulose film as membrane. The change in the absorbance of the optode at the maximum wavelength of 408 nm was related to ammonia concentration in aqueous samples. A buffer solution with a pH of 9 (sodium borate-HCl) was used. The optode was fully regenerated in pH 2. The linear dynamic range for determination of ammonia was 3.3 x 10(-4) to 6.9 x 10(-3) mol l(-1) with a detection limit of 5.0 x 10(-5) mol l(-1) and a response time range of 4 - 6 min. This membrane was successfully applied for determination of ammonia in drinking water.     

A rate-dependent algebraic stress model for turbulence

Based on the stress transport model, a rate-dependent algebraic expression for the Reynolds stress tensor is developed. It is shown that the new model includes the normal stress effects and exhibits viscoelastic behavior. Furthermore, it is compatible with recently developed improved models of turbulence. The model is also consistent with the limiting behavior of turbulence in the inertial sublayer and is capable of predicting secondary flows in noncircular ducts. The TEACH code is modified according to the requirements of the rate-dependent model and is used to predict turbulent flow fields in a channel and behind a backward-facing step. The predicted results are compared with the available experimental data and those obtained from the standard k-ε and algebraic stress models. It is shown that the predictions of the new model are in better agreements with the experimental data.     

The use of Nafion-H® as an efficient catalyst for the direct conversion of primary and secondary trimethylsilyl ethers to their corresponding ethers under mild and heterogeneous conditions

Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence Nafion-H® with good to excellent yields under mild and heterogeneous conditions.     

Selective Acetylation of Alcohols and Amines with Ethyl Acetate in the Presence of H<Subscript>6</Subscript>[PMo<Subscript>9</Subscript>V<Subscript>3</Subscript>O<Subscript>40</Subscript>] as the Catalyst

Summary. Acetylation of various alcohols and benzyl amine was tested in the presence of H₆[PMo₉V₃O₄₀], a mixed addenda heteropolyacid, in ethyl acetate under reflux condition. Phenols and anilines are not affected under the reaction conditions. Selective transestrification of alcohols can be achieved in the presence of phenol and aniline derivatives using this method.     

Interfacial segregation in Ag-Au,Au-Pd,and Cu-Ni alloys: I. (100) surfaces

Atomistic simulations of segregation to (100) free surface in Ag–Au, Au–Pd, and Cu–Ni alloy systems have been performed for a wide range of temperatures and compositions within the solid solution region of these alloy phase diagrams. In addition to the surface segregation profiles, surface free energies, enthalpies, and entropies were determined. These simulations were performed within the framework of the free energy simulation method, in which an approximate free energy functional is minimized with respect to atomic coordinates and atomic site occupation. The effects of the relaxation with respect to either the atomic positions or the atomic concentrations are discussed. For all alloy bulk compositions (0.05 C 0.95) and temperatures (400 T(K) 1,100) examined, Ag, Au, and Cu segregates to the surface in the Ag–Au, Au–Pd, and Cu–Ni alloy systems, respectively. The present results are compared with several theories for segregation. The resultant segregation profiles in Au–Pd and Ag–Au alloys are shown to be in good agreement with an empirical segregation theory, while in Cu–Ni alloys the disagreement in Ni-rich alloys is substantial. The width of the segregation profile is limited to approximately three to four atomic planes. The surface thermodynamic properties depend sensitively on the magnitude of the surface segregation, and some of them are shown to vary linearly with the magnitude of the surface segregation.     

Structure–retardation factor relationship of natural amino acids in two different mobile phases of RP-TLC

Abstract

Separation of amino acids (AAs) and their simple and inexpensive determination/identification is an interesting topic in biological and protein science, different food industries, and drug factories. Also, the presentation of the chromatographic behavior of compounds in a predictive model can be effective to estimate the structural/chemical properties of analyte and mobile phases. In this work for the first time, retardation factor (R_F) of 42 AAs in reversed-phase thin layer chromatography (RP-TLC) was modeled. Acetonitrile-sodium azide solution and 1,2 dioxane-sodium azide solution were two mobile phases which have been studied in this work. Results showed that the values of R_F are correlated with the structural properties of AAs and these properties had some similarities and differences in two noted mobile phases. For the TLC data in two mobile phases, five parametric linear models were suggested (R²_train = 0.93 and 0.97; R²_test = 0.93 and 0.99). The models were also evaluated with different statistical approaches. It was shown that increasing the sum of geometrical distances between N and O in AAs causes decreasing their R_F in RP-TLC using both mobile phases. Other structural effects of AAs on their separation in the desired RP-TLC system were also discussed.