Volumetric properties and viscosities of the 2-pyrrolidone + 1,2-propanediol + water ternary system and its binary constituents at T = 313.15 K

Densities and viscosities of ternary mixtures of 2-pyrrolidone + 1,2-propanediol + water and corresponding binary mixtures of 1,2-propanediol + water, 2-pyrrolidone + water and 2-pyrrolidone + 1,2-propanediol have been measured over the whole composition range at 313.15 K. From the obtained data, the excess molar volumes (V^E), the deviations in viscosity (Δη) and the excess Gibbs free energy of activation (ΔG^?E) have been calculated. The V^E, Δη and ΔG^?E results were correlated and fitted by the Redlich–Kister equation for binary mixtures and by the Cibulka equation for ternary mixtures, as a function of mole fraction. Several predictive empirical relations were applied to predict the excess molar volumes of ternary mixtures from the binary mixing data.     

Development of air‐assisted dispersive micro‐solid‐phase extraction‐based supramolecular solvent‐mediated Fe3O4@Cu–Fe–LDH for the determination of tramadol in biological samples

A simple method, air‐assisted dispersive micro‐solid‐phase extraction‐based supramolecular solvent was developed for the preconcentration of tramadol in biological samples prior to gas chromatography–flame ionization detection. A new type of carrier liquid, supramolecular solvent based on a mixture of 1‐dodecanol and tetrahydrofuran was combined with layered double hydroxide coated on a magnetic nanoparticle (Fe₃O₄@SiO₂@Cu–Fe–LDH). The supramolecular solvent was injected into the solution containing Fe₃O₄@SiO₂@Cu–Fe–LDH in order to provide high stability and dispersion of the sorbent without any stabilizer agent. Air assisted was applied to enhance the dispersion of the sorbent and solvent. A number of analytical techniques such as Fourier transform‐infrared spectrometry, field emission scanning electron microscope, energy‐dispersive X‐ray spectroscopy and X‐ray diffraction measurements were applied to assess the surface chemical characteristics of Fe₃O₄@SiO₂@Cu–Fe–LDH nanoparticles. The effects of important parameters on the extraction recovery were also investigated. Under optimized conditions, the limits of detection and quantification were obtained in the range of 0.9–2.4 and 2.7–7.5 μg L^?1 with preconcentration factors in the range of 450–472 in biological samples. This method was used for the determination of tramadol in biological samples (plasma, urine and saliva samples) with good recoveries.     

Study of the effect of the ligand structure on the catalytic activity of Pd@ ligand decorated halloysite: Combination of experimental and computational studies

Taking advantage of computational chemistry, the best diamine for the synthesis of a multi‐dentate ligand from the reaction with 3‐(trimethoxysilyl) propylisocyanate (TEPI) was selected. Actually, predictive Density Functional Theory (DFT) calculations provided the right diamino chain, i.e. ethylenediamine, capable to sequester a palladium atom, together with the relatively polar solvent toluene, and then undergo the experiments as a selective catalytic agent. The ligand was then prepared and applied for the decoration of the halloysite (Hal) outer surface to furnish an efficient support for the immobilization of Pd nanoparticles. The resulting catalyst exhibited high catalytic activity for hydrogenation of nitroarenes. Moreover, it showed high selectivity towards nitro functional group. The study of the catalyst recyclability confirmed that the catalyst could be recycled for several reaction runs with only slight loss of the catalytic activity and Pd leaching. Hot filtration test also proved the heterogeneous nature of the catalysis.     

CuI‐functionalized halloysite nanoclay as an efficient heterogeneous catalyst for promoting click reactions: Combination of experimental and computational chemistry

Amine‐functionalized halloysite nanotubes (HNTs‐2 N) were prepared and further modified by introduction of salicylaldehyde and formation of imine functionality (HNTs‐2 N‐Sal). The latter was subsequently used for immobilization of CuI and formation of CuI@HNTs‐2 N‐Sal, which could effectively promote click reactions of terminal alkynes, sodium azide and α‐haloketones or alkyl halides in aqueous media and under mild reaction conditions to afford 1,2,3‐triazoles in relatively short reaction times. Notably, the catalyst could be recycled in up to six reaction runs with negligible loss of catalytic activity and CuI leaching. Also, the geometry of CuI adsorption on the modified HNTs surface was explored by molecular simulation with density functional theory. Furthermore, topographic steric maps of possible coordination modes were obtained using the recently released SambVca2 web application tool. Based on obtained results, a catalytic site with superior performance was suggested.     

N‐Bromosuccinimide (NBS): A Novel and Efficient Catalyst for the Synthesis of 14‐Aryl‐14H‐dibenzo[a,j]xanthenes under Solvent‐Free Conditions

A novel procedure for the synthesis of 14‐aryl‐14H‐dibenzo[a,j]xanthenes through one‐pot condensation of naphthalen‐2‐ol with arenecarbaldehydes in the presence of N‐bromosuccinimide (NBS) as catalyst under solvent‐free conditions is described.     

Assessment of MRI issues for the Argus II retinal prosthesis

Objective

The objective was to evaluate magnetic resonance imaging (MRI) issues (magnetic field interactions, heating, artifacts and functional alterations) at 1.5 T and 3 T for the Argus II Retinal Prosthesis (Second Sight Medical Products, Sylmar, CA, USA).

Materials and Methods

Standardized protocols were used to assess magnetic field interactions (translational attraction and torque; 3 T, worst case), MRI-related heating (1.5 and 3 T), artifacts (3 T; worst case) and functional changes (1.5 and 3 T) associated with MRI.

Results

The magnetic field interactions were acceptable. MRI-related heating, which was studied at a relatively high, MR system-reported whole body averaged specific absorption rates, will not pose a hazard to the patient under the conditions used for testing. While artifacts were “moderate” in relation to the dimensions of the Argus II Retinal Prosthesis, optimization of MRI parameters can reduce the size of the artifacts. Exposures to MRI conditions at 1.5 and 3 T did not damage or alter the functional aspects of the Argus II Retinal Prosthesis.

Conclusions

In consideration of the test results, a patient with the Argus II Retinal Prosthesis may undergo MRI at 1.5 T or 3 T when specific guidelines and MRI conditions are followed, including those advised by the manufacturer.     

Combining click-multicomponent reaction: one-pot synthesis of triazolyl methoxy-phenyl indazolo[2,1-b]phthalazine-trione derivatives

[(1,2,3-Triazol-4-yl)methoxy-phenyl]-2H-indazolo[2,1-b]phthalazine-trione derivatives were synthesized in a simple and efficient method from the one-pot four-component condensation reaction of phthalhydrazide, aromatic propargyloxy aldehydes, active methylene compounds (dimedone and 1,3-cyclohexanedione), and azides in the presence of Cu(OAc)(2)/sodium ascorbate and p-toluenesulfonic acid as catalysts in good to excellent yields.     

An upper-bound analysis for frictionless TCAP process

Tubular channel angular pressing (TCAP) process was proposed recently as a novel severe plastic deformation technique for producing ultrafine grain and nanostructured tubular components. In this paper, an upper-bound approach was used to analyze the TCAP process. Deformation of the material during TCAP process is analyzed using upper-bound analysis to determine maximum required load. The effects of TCAP parameters such as channel and curvature angles, deformation ratio (R ₁/R ₂) and tube material on the process pressure were investigated. The results showed that an increase in the second channel angle and decrease in the ratio R ₁/R ₂ lead to lower process loads. In the first and third curvature angles ranging from 25 to 65°, the required load remains almost constant. The apparent punch load decrease when hardening exponent n is increased. To verify the theoretical results, the finite element (FE) modeling was employed. Good agreement was observed between the predicted pressure from upper-bound analysis and FE results.     

On-line solid phase extraction coupled to ICP-OES for simultaneous preconcentration and determination of some transition elements

An on-line solid phase extraction method coupled to ICP-OES was developed for the simultaneous determination of Ce(III), La(III), Sm(III), Y(III), Yb(III), Dy(III), Hf(IV), Zr(IV) and Th(IV) ions in aqueous samples. The ions forming hydrophobic complexes with 3,5,7,2?,4?-pentahydroxy flavone (morin) and were retained on an octadecyl silica (C₁₈) minicolumn. The adsorbed chelates were subsequently eluted from the column and directly transferred into the plasma with 80% (v/v) propanol:H₂O solution for the simultaneous determination of the metal ions. Different parameters affecting the ICP-OES signal intensities and extraction efficiency including pH of the solution, concentration of the chelating agent, flow rate and type of the eluent, loading rate and ionic strength were evaluated and optimized. The calibration graphs were linear in the range of 0.2–100 μg L^?1 and limit of detections for the extraction and determination of the ions in the aqueous sample (25 mL) were in the range 0.10–0.46 μg L^?1. The enhancement factors of the method for the metal ions obtained were in the range of 23 to 242 (V _Sample?=?25 mL) and the precision expressed as relative standard deviations (RSD %) was below 6.9%. Finally, the method was successfully applied to determine the target analytes in natural water samples.