Electronic sensors for alkali and alkaline earth cations based on Fullerene-C60 and silicon doped on C60 nanocages: a computational study.

In this research, we have reported the electrical sensitivity of pristine C60 and silicon doped on C60 (SiC59) nanocages as sensors that can be used for detecting the presence of alkali (Li+, Na+, K+) and alkaline earth (Be2+, Mg2+, Ca2+) cations. The computations are carried out at the B3LYP level of theory with a 6-31G(d) basis set. The atoms in molecules (AIM) and natural bond orbital (NBO) analyses are performed to evaluate the intermolecular interactions between cations and nanocages. The physical properties of the selected complexes are also analyzed by the frontier molecular orbital, energy gap, electronegativity, chemical hardness, softness, and other quantities such as work function, number of transferred electron, and dipole moment. The results show that the adsorption process is exothermic and with increasing the charge of cations, the adsorption energies enhance. Our findings also reveal a decrease in the energy gap along with an increase in the electrical conductivity of the respective complexes. Finally, the density of state calculations is presented to confirm the obtained results.

Selective adsorption and dissociation of NO, NO2, and N2O molecules on Si-doped haeckelite boron nitride nanotube: an investigation for sensitive molecular sensors and catalysts.

The current study describes the investigation of the adsorption NO, N2O, and NO2 on haeckelite boron nitride nanotube doped with Si (Si-doped haeck-BNNT) by means of density functional theory calculation (DFT). The obtained results confirmed the energetic stability of the optimized geometries and revealed that the adsorption of the gas molecules with the nanotube sidewall is a spontaneous process. The calculated work function of Si-doped haeck-BNNT in the presence of gas molecules is greater than that of a bare Si-doped haeck-BNNT sheet. The energy gap of the Si-doped haeck-BNNT is sensitive to the adsorption of the gas molecules, which implies possible future applications in gas sensors. For most of the adsorption configurations studied, the adsorption energies for the SiB-doped haeck-BNNT are higher than those for SiN-doped haeck-BNNTones. The N2O gas molecule is totally dissociated into N2 and O species through the adsorption process, while the other gas molecules retain their molecular forms. Thus, the SiN-doped haeck-BNNT is a likely catalyst for dissociation of the N2O gas molecule. Our findings divulge promising potential of the doped haeck-BNNT as a highly sensitive molecular sensor for NO and NO2 detection and a catalyst for N2O dissociation.

Thermodynamic stability, structural and electronic properties for the C20-nAln heterofullerenes (n = 1-5): a DFT study.

DFT calculations are utilized to compare and contrast the substituted aluminum-heterofullerenes, C20-nAln (with n = 1-5) from thermodynamically view point, at density functional theory (DFT). Vibrational frequency analysis confirms that apart from C15Al5, all studied species are true minima. Considering the optimized geometries shows that all heterofullerenes are isolated-pentagon cage and none collapse to open deformed as segregated structure. The highest binding energy (5.56 eV/atom) and absolute heat of atomization (3323.68 kcal mol-1) reveals open-shell C19Al1 as the most stable thermodynamic heterofullerene. The most NICS (0) (isotropic and anisotropic parameters, -49.58 and - 46.47 ppm, respectively) introduces closed-shell C18Al2-2 as the most aromatic structure. Also, closed-shell C16Al4-1 heterofullerene emerges with the most polarizability (307.71 a.u.) and hence activity to interact with the surrounding polar species. The lowest and the highest charge transfer on the surfaces of C20 and C16Al4-2 without weak Al-Al bond, as the worst and the best candidate, respectively, provokes further investigation on impossible and possible application for hydrogen storage, respectively. We wish that the present survey will stimulate new experiments.

Progress and recent trends in the direct selenocyanation of (hetero)aromatic C-H bonds.

This review covers recent advances in the direct selenocyanation of (hetero)aromatic C-H bonds with an emphasis on the reaction mechanisms. This novel approach is an effective means of preparing a variety of aromatic and heteroaromatic selenocyanates, which are extremely versatile synthetic precursors of selenium-containing compounds, such as selenols, seleninic acids, selenides, diselenides, and trifluoromethyl selenides.

Recent trends in the direct oxyphosphorylation of C-C multiple bonds.

Due to the wide importance of ß-phosphorylated ketones as key building-blocks in the fabrication of various pharmaceutically active organophosphorus compounds, finding new and truly efficient methods for their preparation from simple, low-cost and ubiquitous feedstock materials within a single click is an interesting subject in organic synthesis. Recently, oxyfunctionalization of carbon-carbon multiple bonds has arisen as a straightforward and versatile tool for the synthesis of complex organic molecules from the simple and easily accessible alkenes/alkynes via a single operation. In this context, oxyphosphorylation of alkenes/alkynes with P(O)-H compounds has attracted considerable attention as a unique procedure for the construction of ß-phosphorylated ketones. In this review, we outline the recent advances and developments in this fast-growing research field with particular emphasis on the mechanistic aspects of reaction.

Methods for direct C(sp2)-H bonds azidation.

Direct functionalization of C-H bonds has attracted great attention in recent years from the perspectives of atom and step economy. In this context, a variety of processes have been developed for the construction of synthetically and biologically important organic azides through the oxidative C-H bonds azidation. In this review, we have summarized recent progress in the direct azidation of C(sp2)-H bonds. The review is divided into three major sections: (i) direct azidation of aromatic C-H bonds; (ii) direct azidation of olefinic C-H bonds; and (iii) direct azidation of aldehydic C-H bonds. Mechanistic aspects of the reactions are considered and discussed in detail.

Recent advances in direct trifluoromethylation of olefinic C-H bonds.

The aim of this review is to provide a comprehensive overview of the direct trifluoromethylation of olefinic C-H bonds with special attention on the mechanistic aspects of the reactions. The review is divided into two major sections. The first focuses exclusively on trifluoromethylation of terminal alkenes, while the second will cover trifluoromethylation of internal alkenes. Literature has been surveyed until the end of April 2019.

Determination of Hg(II) ions in sea food samples after extraction and preconcentration by novel Fe3O 4@SiO 2@polythiophene magnetic nanocomposite.

This work describes a novel Fe3O4@SiO2@polythiophene magnetic nanocomposite and its application in the preconcentration of Hg(II) ions. The parameters affecting the preconcentration procedure were opted by a Box-Behnken design through response surface methodology. Three factors (uptake time, magnetic nanosorbent amount, and pH of sample) were selected as the main factors affecting the sorption step, while four variables (type, volume and concentration of the eluent as well as the elution time) were selected as main factors in the optimization study of the elution step. Following the sorption and elution of Hg(II), it was quantified by cold vapor atomic absorption spectrometry. Under the optimum condition, the limit of detection was 0.02 ng mL(-1) and all the relative standard deviations were less than 9.2 %. The obtained sorption capacity of this new sorbent was 59 mg g(-1). Finally, this nanocomposite was successfully applied to the rapid extraction of trace quantities of Hg(II) ions in sea food samples and satisfactory results were obtained.

Determination of heavy metal ions in vegetable samples using a magnetic metal-organic framework nanocomposite sorbent.

This paper describes the synthesis and application of a novel magnetic metal-organic framework (MOF) [(Fe3O4-benzoyl isothiocyanate)/Cu3(benzene-1,3,5-tricarboxylate)2] to pre-concentrate trace amounts of Cd(II), Pb(II), Zn(II) and Cr(III) ions and their determination by flame atomic absorption spectrometry. A Box-Behnken design was used to find the parameters affecting the pre-concentration procedure through response surface methodology. Three factors including uptake time, amount of the magnetic sorbent and pH of the sample were selected as affecting factors in the sorption step, and four factors including type, volume and concentration of the eluent as well as the elution time were selected in the elution step for the optimisation study. The opted values were 30 mg, 10.1 min, 5.9, EDTA, 4.0 ml, 0.57 mol l(-1) EDTA solution and 13.0 min for the amount of the magnetic sorbent, uptake time, pH of the sample, type, volume, concentration of the eluent, and elution time, respectively. The limits of detection (LODs) were 0.12, 0.7, 0.16, and 0.4 ng ml(-1) for Cd(II), Pb(II), Zn(II) and Cr(III) ions, respectively. The relative standard deviations (RSDs) of the method were less than 7.2% for five separate batch experiments for the determination of 30 µg l(-1) of Cd(II), Pb(II), Zn(II) and Cr(III) ions. The sorption capacity of the [(Fe3O4-benzoyl isothiocyanate)/MOF] was 175 mg g(-1) for Cd(II), 168 mg g(-1) for Pb(II), 210 mg g(-1) for Zn(II) and 196 mg g(-1) for Cr(III). It was found that the magnetic MOF nanocomposite demonstrated a higher capacity compared with Fe3O4-benzoyl isothiocyanate. Finally, the magnetic MOF nanocomposite was successfully applied to the rapid extraction of trace amounts of the heavy metal ions from vegetable samples.

Determination of mercury(II) ions in seafood samples after extraction and preconcentration by a novel functionalized magnetic metal-organic framework nanocomposite.

This work describes a novel functionalized magnetic metal-organic framework nanocomposite [(Fe3O4-2,5-dimercapto-1,3,4-thiadiazole)/metal-organic framework] and its application in the preconcentration of Hg(II) ions. The parameters affecting the preconcentration procedure were optimized by a Box-Behnken design through response surface methodology. Three variables (uptake time, magnetic nanosorbent amount, and pH value) were selected as the main factors affecting the sorption step, while four variables (type, volume, and concentration of the eluent; and elution time) were selected as main factors in the optimization study of the elution step. Following the sorption and elution of analytes, the ions were quantified by cold vapor atomic absorption spectrometry. Under the optimum conditions, the limit of detection was 0.01 ng/mL and all the relative standard deviations were less than 10%. The obtained sorption capacity (in mg/g) of this new sorbent was 124. Ultimately, this nanocomposite was successfully applied to the rapid extraction of trace quantities of Hg(II) ions in seafood samples and satisfactory results were obtained.