Efficient eco-friendly syntheses of dithiocarbazates and thiosemicarbazones

ABSTRACT

Eight Schiff bases have been synthesized by conventional and three different eco-friendly methods, whereby two aromatic carbonyl compounds viz. 2-thiophenecarboxaldehyde and salicylaldehyde were reacted with S-methyl, S-benzyl, and S-n-octyl-dithiocarbazates and thiosemicarbazide. In order to evaluate the efficiency of the synthesis methods, the time to complete the reaction and the yield of the Schiff base synthezised by eco-friendly methods, such as solvent-free grinding, water as a solvent, and lemon juice as catalyst, were compared with those synthesized by the conventional method. The chemical structures of all the synthesized Schiff bases, where two of them are novel and reported for the first time, were fully characterized by a variety of physico-chemical, analytical, and spectroscopic techniques. The molecular and crystal structures of the Schiff bases especially those having 2-thiophene moiety were further elucidated by single crystal X-ray diffraction analyzes.     

Using enantioselective dispersive liquid–liquid microextraction for the microseparation of trans-cyclohexane-1,2-diamine enantiomers

A new chiral separation system effective for the enantioselective extraction of racemic trans-cyclohexane-1,2-diamine is presented. Enantioselective dispersive liquid–liquid microextraction has been used for the chiral microseparation of trans-cyclohexane-1,2-diamine, with a chiral azophenolic crown ether being identified as a versatile chiral selector. The influence of various process conditions on the extraction performance was studied experimentally. It was found that the operational selectivity in one extraction step is mainly related to the type and volume of the solvents, chiral selector concentration, extraction time, temperature of sample solution, and pH. At optimum conditions (300 μL of diethyl ether as the extraction solvent 1 mL of methanol as the disperser solvent, with 5 mmol L^?1 chiral selector concentration, pH of the sample equal to 4.5, 30 min extraction time and a temperature of 10 °C), the distribution ratio of (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine was 18.3 and 1.8, respectively, while the enantioselectivity value of 10.2 was found at the optimum condition.     

Rectangular-radial drawings of cubic plane graphs

Rectangular drawings and rectangular duals can be naturally extended to other surfaces. In this paper, we extend rectangular drawings and rectangular duals to drawings on a cylinder. The extended drawings are called rectangular-radial drawings and rectangular-radial duals. Rectangular-radial drawings correspond to periodic rectangular tilings of a 1-dimensional strip. We establish a necessary and sufficient condition for plane graphs with maximum degree 3 to have rectangular-radial drawings and a necessary and sufficient condition for triangulated plane graphs to have rectangular-radial duals. Furthermore, we present three linear time algorithms under three different conditions for finding a rectangular-radial drawing for a given cubic plane graph, if one exists.     

Iron Oxychloride/Bovine Serum Albumin Nanosheets as Chemodynamic Therapy Agents

Iron oxychloride (FeOCl) is known for reactive oxygen species (ROS) generation through Fenton chemistry. The activity of FeOCl is preserved in the slightly acidic pH value of the tumor microenvironment (pH 6.5−6.9). Such property can be advantageous in biobased systems, where ROS generation can be modulated in slightly acidic conditions, which is characteristic of the solid tumor microenvironment. In the present study, BSA-stabilized FeOCl nanosheets (NSs) are synthesized and characterized by transmission electron microscope, Fourier transform infrared spectroscopy, zeta potential analysis, dynamic light scattering, and UV–vis spectroscopy. The morphology of the nanoparticles is flake-like, and their hydrodynamic diameter is around 200 nm. MTT, apoptosis assay, and trypan blue staining evaluate the toxicity of FeOCl NSs toward the 4T1 cell line. It is found that the toxicity of the NSs is higher in physiological conditions of solid tumors (pH 6.5, H₂O₂ 100 × 10⁻⁶ m ) than in the conditions of healthy organs (pH 7.4). Specifically, cancer cells are in their late apoptotic stage by more than eight times higher at pH 6.5 than pH 7.4. The toxicity results are in agreement with the in vitro catalytic assay of the NSs. Therefore, the FeOCl NSs can be the building blocks for constructing chemodynamic therapy agents.     

Reversed-phase dispersive liquid-liquid microextraction with central composite design optimization for preconcentration and HPLC determination of oleuropein

A reversed-phase dispersive liquid-liquid microextraction (RP-DLLME) method was developed for the preconcentration and direct HPLC determination of oleuropein in olive's processing wastewater (OPW) and olive leaves extracts. In conventional DLLME, the sedimented phase is a micro-drop of a chlorinated organic solvent that is not compatible with RP-HPLC. Therefore, solvent evaporation and reconstitution with an appropriate solvent is often required. In RP-DLLME, this problem was overcome by overturning the solvent polarity in the ordinary DLLME and replacing the organic solvent with water. A central composite chemometrics design was used for multivariate optimization of the effects of five different parameters influencing the extraction efficiency of the method. In the optimized conditions, a mixture of 1.4 mL of an ethyl acetate extract of sample and 40 μL water (pH 5.0) was rapidly injected into 5.3 mL of cyclohexane. After centrifugation of the formed cloudy mixture, a micro-drop of the aqueous phase was sedimented at the conical bottom of the centrifuge tube. This phase, that contained the preconcentrated and partially purified analyte, was directly injected into an RP-HPLC column for analysis. A mean extraction recovery of 102.5 (±4.5) % with enrichment factors exceeding 38, was obtained for five replicated analysis. The detection limit of the method (3σ) for OE was 0.02 μg L⁻¹ for OPW and 2 × 10⁻³ mg kg⁻¹ for olive leaves samples. The results showed that, RP-DLLME is a promising technique which is quick, easily operated and can be directly coupled to HPLC.     

Annihilator Conditions on Polynomials over Modules

Let R be a ring with unity and M be a right R-module. The system M[x] forms a left near R[x]-module under addition and substitution operations. In this paper we extend the study of annihilator conditions on nearring of polynomials to left near R[x]-module M[x], when M is a reduced Baer module. Also, we give a characterization of reduced modules. As a corollary we obtain some results of Birkenmeier and Huang [3].     

A Novel Approach for the Synthesis of Furopyrimidine and Oxobenzofuran Derivatives

A novel, efficient one‐pot approach for the synthesis of furopyrimidine and oxobenzofuran derivatives 4 by a multicomponent reaction of an isocyanide, an aldehyde, and a CH‐acid compound in CH₂Cl₂ is reported (Scheme 1 and Table). The reactions were completed after 20 h at room temperature. This method has the advantages of high yields, simple methodology, and easy workup.     

An Alternative Mechanism of Non-contact Anterior Cruciate Ligament Injury During Jump-landing: In-vitro Simulation

In the United States, an estimated 100,000 anterior cruciate ligament (ACL) injuries occur every year. Despite decades of research, to this date, the mechanism or mechanisms of non-contact ACL injuries are not well understood. This is primarily because trials cannot be conducted on live subjects to understand the injury mechanism, and it is difficult to instrument a live human knee to measure the response of tissues during dynamic activities. In this paper, we present a dynamic knee injury simulator capable of in-vitro modeling of the ACL injury during jump-landing activity. This system was used to simulate jump-landing on cadaveric knees and to successfully test which conditions would result in isolated ACL injury. A restricted flexion of the hip (a hip that flexes minimally or not at all during landing), combined with low quadriceps and hamstring force levels during landing were found to be conducive to ACL injury. Elevated levels of quadriceps force prevented the injury from occurring even under restricted hip flexion conditions. The measured strain rates in the ACL tissue during injury causing activities were over 250%/s.