Study of the Effects of N Fertilization and Plant Density on the Essential Oil Composition and Yield of Cuminum cyminum L. Seeds by HS–SME

Headspace-solvent microextraction (HS–SME) with sample ultrasound irradiation was successfully used for the study of the influence of nitrogen fertilization and plant density on the essential oil yield and composition of cumin (Cuminum cyminum L.) seeds. The components were collected into a single microdrop of n-heptadecane and directly injected into a GC–MS injection port for analysis. A simplex method was used for fast optimization of the extraction parameters. The experiments were executed as split-plot based on randomized complete block design. Nitrogen fertilization as the main factor (in four levels) and plant density as subsidiary factor (in three levels) were applied. It was shown that the total GC peak areas of the HS–SME extract, is proportional to the essential oil yield of the cumin seeds obtained by a hydrodistillation method. Furthermore, similar trends in the concentrations of cuminaldehyde and most other volatile components were obtained by the two methods.     

Acetaldehyde oxidation at elevated pressure

A detailed chemical kinetic model for oxidation of CH₃CHO at intermediate to high temperature and elevated pressure has been developed and evaluated by comparing predictions to novel high-pressure flow reactor experiments as well as shock tube ignition delay measurements and jet-stirred reactor data from literature. The flow reactor experiments were conducted with a slightly lean CH₃CHO/O₂ mixture highly diluted in N₂ at 600–900 K and pressures of 25 and 100 bar. At the highest pressure, the oxidation of CH₃CHO was in the NTC regime, controlled to a large extent by the thermal stability and reactions of peroxide species such as HO₂, CH₃OO, and CH₃C(O)OO. Model predictions were generally in good agreement with the experimental data, even though the predicted temperature for onset of reaction was overpredicted at 100 bar. This discrepancy was attributed mainly to uncertainties in the CH₃C(O)OO reaction subset. Predictions of ignition delays in shock tubes and species profiles in JSR experiments were also satisfactory. At temperatures above the NTC regime, acetaldehyde ignition and oxidation is affected mainly by the competition between dissociation of CH₃CHO and reaction with the radical pool, and by reactions in the methane subset.     

ACE-Inhibitory and Antioxidant Activities of Peptide Fragments Obtained from Tomato Processing By-Products Fermented Using <Emphasis Type="Italic">Bacillus subtilis</Emphasis>: Effect of Amino Acid Composition and Peptides Molecular Mass Distribution

The effects of amino acid composition and peptide molecular mass on ACE-inhibitory and antioxidant activities of protein fragments obtained from tomato waste fermented using Bacillus subtilis were evaluated. The addition of B. subtilis increased the relative amounts of aromatic and positively-charged amino acids which have been described to influence the biological activities of peptide fragments. IC₅₀ values of hydrolysates for ACE-inhibitory and 2, 2′-diphenyl-1-picrylhydrazyl (DPPH) scavenging activities were found to be 1.5 and 8.2 mg/mL, respectively. Size-exclusion chromatography (SEC) pattern of the hydrolysate indicated the breakdown of parent proteins to smaller peptides with molecular weights mainly below 1400 Da. MALDI-TOF mass spectrometry analysis revealed that the highest ACE-inhibitory activity was due to peptides showing molecular mass range 500–800 Da, while the most active antioxidant peptides were found to be mainly at the two different peptide weight ranges 500–800 Da and 1200–1500 Da.     

Synthesis of 2-mercaptobenzothiazole/magnetic nanoparticles modified multi-walled carbon nanotubes for simultaneous solid-phase microextraction of cadmium and lead

This study describes the successful sequential modification of multi-walled carbon nanotube (MWCNT) by Fe₃O₄ magnetic nanoparticles and 2-mercaptobenzothiazole (MBT) followed by its application as a novel sorbent for simultaneous magnetic solid phase microextraction of lead and cadmium. Fourier transform infrared spectroscopy and scanning electron microscopy were employed to confirm the chemical surface modification of the MWCNT. The ions retained on the 2-MBT/magnetic nanoparticles modified MWCNTs were eluted with 1.0 mL of nitric acid (0.8 mol L^?1) in methanol solution and determined by the flame atomic absorption spectrometry. All parameters affecting the extraction condition were thoroughly investigated and optimised. Under the optimised condition preconcentration factor of 150.0, enhancement factors of 149.0 and 149.2 and limits of detection of 0.21 and 0.01 µg L^?1 were achieved for lead and cadmium, respectively. Using the prepared magnetic nanocomposite, the possible interference of other common ions associated with lead and cadmium determination was effectively avoided and the method was successfully applied to the simultaneous determination of the target ions in various environmental water samples.     

GC–MS study of thermochemical conversion of guaifenesin in the presence of 1-butyl-3-methylimidazolium-based ionic liquids

Research on Chemical Intermediates - Thermochemical conversion of guaifenesin was performed in the presence of 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] ionic liquid at...     

Ultrasonic assistance syntheses of new nano-sized lead(II) coordination polymers: motifs for PbO preparation

Nanoparticles of two new coordination polymers, [Pb(5,5′-dm-2,2′-bpy)Cl₂] _n (1) and [Pb(5,5′-dm-2,2′-bpy)Br₂] _n (2), {5,5′-dm-2,2′-bpy = 5,5′-dimethyl-2,2′-bipyridine}, have been synthesized by ultrasonic assistance at different concentrations and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Metal oxide nanoparticles were prepared from thermal decomposition of compounds 1 and 2 at 600 °C under air atmosphere. Scanning electron microscopy images of the residue which are obtained from calcination of compounds 1, 2 show the formation of lead(II) oxide nanoparticles with an average diameter of about 80 and 90 nm for compounds 1 and 2, respectively.     

Application of SBA-Pr-SO<Subscript>3</Subscript>H in the synthesis of 2,3-dihydroquinazoline-4(1<Emphasis Type="Italic">H</Emphasis>)-ones: characterization,UV–Vis investigations and DFT studies

An efficient one-pot synthesis of 2,3-dihydroquinazoline-4(1H)-one derivatives 4a–l is described using SBA-Pr-SO₃H as a heterogeneous acid catalyst. The present methodology resulted in various derivatives of 2,3-dihydroquinazoline-4(1H)-one in good yield via a three-component reaction of isatoic anhydride, aldehydes and ammonium acetate. SBA-Pr-SO₃H played a significant role as an efficient mesoporous catalyst due to its pore size of 6 nm. Additionally, UV–Vis spectrum of the products was studied in order to investigate their application as UV absorbers.     

Experimental and theoretical studies of diethyl 2-(<Emphasis Type="Italic">ter</Emphasis>-butylimino)-2,5-dihydro-5-oxo-1-phenyl-1H-pyrrole-3,4-dicarboxylate using DFT calculations

In this study, diethyl 2-(ter-butylimino)-2,5-dihydro-5-oxo-1-phenyl-1H-pyrrole-3,4-dicarboxylate compound 1 is synthesized and characterized by FT-IR, ¹H and ¹³C NMR spectroscopy. The DFT calculations are carried out for compound 1 by B3LYP and PBE1PBE methods. The bond lengths, bond angles, dihedral angles, charge density on the atoms of 1 are calculated. A comparison of the DFT calculations indicate that the B3LYP method with the 6-311G++(d,p) basis set can give accurate results. The ¹³C NMR and ¹H NMR chemical shifts of 1 are calculated and compared with the available experimental data on the molecules. The nuclear independent chemical shift (NICS) calculations are utilized for the pyrrole ring in compound 1.     

Exploring the impacts of the vinylogous anomeric effect on the synchronous early and late transition states of the hydrogen molecule elimination reactions of cis-3,6-dihalocyclohexa-1,4-dienes

LC-ωPBE, B3LYP, and M06-2X methods with the 6–311+G** basis set on all atoms and natural bond orbital (NBO) interpretation were performed to investigate the roles and contributions of the effective factors on the potential energy surfaces of the hydrogen molecule elimination reactions of cyclohexa-1,4-diene (1) and its cis-3,6-dihalo derivatives [halogen=F (2), Cl (3), Br (4)] to hydrogen molecule and their corresponding aromatic rings. The ring puckering in compound 2 (which results from the repulsive electrostatic interactions between the natural bond orbital dipole moments of two C-F bonds) shortens the allylic hydrogen atoms’ distance, leading to the smaller barrier height in compound 2 compared to that in compound 1. The barrier heights of the hydrogen molecule elimination reactions increase from compounds 2 to 4 while their corresponding exothermic characters decrease. The variations of the advancements of transition state structures (δB _av) reveal that the hydrogen molecule elimination reactions of compounds 2–4 do not obey the Hammond-Leffler postulate. In compound 2, the ring puckering shortens the allylic hydrogen distance (d _H8-H10) while d _H8-H10 values increase going from compounds 2 to 4, leading to the increase of their corresponding hydrogen molecule elimination reactions barrier heights. Interestingly, the variations of the vinylogous hyperconjugative anomeric effects justify the directions of the rings puckering going from compounds 2 to 4. The increase of the activation exchange components [PETR _(TS)-PETR _(GS)] going from compounds 2 to 4 correlates well with their corresponding hydrogen molecule elimination process barrier heights.     

Optimization of modification condition of nano-kaoline as an adsorbent for textile dye removal

In this study, adsorption capacity of textile red dye on alkylated kaolin was investigated through batch mode. Accordingly, raw kaolin was alkylated via NaOH treatment. The work was carried out in two steps. At first step, the effect of various alkylation conditions of kaolin on its dye adsorption performance was studied using the model equation designed by 2-level factorial design. Three factors were changed in two level including NaOH solution temperature (45–75°C), mixing time (3–24 h), and NaOH solution concentration (0.1–2 M). The resultant model showed 91% of the variability in data used to fit dye adsorption capacity values. However, the analysis of variance revealed that the fitted model is high significant. Based on the predicting model, the optimal alkylation conditions with desirability factor of 0.911 were obtained at temperature of 75°C, NaOH concentration of 0.1 M and after 24 h mixing. At step two, chemical content, bonds and functional groups of the treated kaolin, which was prepared based on the optimum condition and compared with the raw kaolin via X-ray fluorescence (XRF) analysis and Fourier transform infrared analysis (FTIR). The results show slight reduction in SiO₂ content. Finally, the adsorption capacity of dye on both treated and raw kaolin was investigated.