New functional chiral P-based ligands and application in ruthenium-catalyzed enantioselective transfer hydrogenation of ketones

Metal-catalyzed asymmetric transfer hydrogenation is a powerful and practical method for the reduction of ketones to produce the corresponding secondary alcohols, which are valuable building blocks in the pharmaceutical, perfume, and agrochemical industries. Hence, a series of novel chiral β-amino alcohols were synthesized by chiral amines with regioselective ring opening of (S)-propylene oxide or reaction with (S)-(+)-2-hydroxypropyl p-toluenesulfonate by a straightforward method. The chiral ruthenium catalytic systems generated from [Ru(arene)(μ-Cl)Cl]₂ complexes and chiral phosphinite ligands based on amino alcohol derivatives were employed in asymmetric transfer hydrogenation of ketones to give the corresponding optically active alcohols; (2S)-1-{[(2S)-2-[(diphenylphosphanyl)oxy]propyl][(1R)-1-phenylethyl]amino}propan-2-yldiphenylphosphinitobis[dichol-oro(η⁶-benzene)ruthenium(II)] acts an excellent catalyst in the reduction of α-naphthyl methyl ketone, giving the corresponding alcohol with up to 99% ee. The substituents on the backbone of the ligands were found to have a remarkable effect on both the conversion and enantioselectivity of the catalysts. Furthermore, this transfer hydrogenation is characterized by low reversibility under these conditions.     

Microencapsulated oleic–capric acid/hexadecane mixture as phase change material for thermal energy storage

Journal of Thermal Analysis and Calorimetry - Thermal energy storage systems provide efficiency in order to have better utilization of energy sources while protecting the environment. Thermal...     

Preparation and Characterization of Activated Carbon from Microwave and Conventional Heated Almond Shells Using Phosphoric Acid Activation

Activated carbon production from almond shells using phosphoric acid activation agent was achieved by applying both conventional heating and microwave heating in succession. The morphology and surface properties of activated carbon were studied using thermogravimetric and differential gravimetric analysis, Fourier-transform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller analysis. A surface area of 1128 m²/g was achieved by optimizing the microwave power (500?W), microwave application time (15?minutes), conventional heating time (45?minutes), conventional heating temperature (500?°C), and the phosphoric acid:sample ratio (0.7:1). An adsorption capacity of methylene blue of 148?mg/g and an iodine value of 791?mg/g was obtained for the prepared activated carbon.     

Effect of reactive and nonreactive surface modifications and compatibilizer use on mechanical and flame-retardant properties of linear low-density polyethylene filled with huntite and hydromagnesite mineral

Journal of Thermal Analysis and Calorimetry - In the current study, huntite and hydromagnesite (HH) was used as flame-retardant additive in linear low-density polyethylene (LLDPE). The effect of HH...     

Ru(III), Cr(III), Fe(III) complexes of Schiff base ligands bearing phenoxy Groups: Application as catalysts in the synthesis of vitamin K3

Two polydentade Schiff base ligands and their Ru(III), Cr(III) and Fe(III) complexes were synthesized and characterized by elemental analysis (C, H, N), UV/Vis, FT IR, ¹H and ¹³C NMR, LC–MS/MS, molar conductivity and magnetic susceptibility techniques. The absorption bands in the electronic spectra and magnetic moment measurements verified an octahedral environment around the metal ions in the complexes. The thermal stabilities were investigated using TGA. The synthesized complexes were used in the catalytic oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone; vitamin K₃, menadione, 2MNQ; using hydrogen peroxide, acetic acid and sulfuric acid. L₁-Fe(III) complex showed very efficient catalytic activity with 58.54% selectivity in the conversions of 79.11%.     

Electrochemical DNA biosensor for the determination of benzo[a]pyrene–DNA adducts

The metabolites of the environmental pollutant, benzo[a]pyrene (BaP) are carcinogenic and mutagenic agents. Thus, the determination of additional products (adducts) of the interaction between DNA and BaP, attracts great interest in cancer research.

In this study, the determination of interaction between BaP and calf thymus double-stranded DNA (dsDNA) was performed by using differential pulse voltammetry (DPV) and constant current chronopotentiometric stripping analysis (PSA) in connection with carbon paste electrode (CPE) or glassy carbon electrode (GCE). As a result of interaction of BaP with dsDNA, the signal obtained from the oxidation of guanine decreased and a new adduct signal at a more positive potential appeared. This new peak is attributed to the formation of an adduct from the interaction of guanine with BaP. The chemically prepared anti-7,8,9,10-tetrahydrobenzo[a]pyrene-7,8-diol-9,10-epoxide (BPDE) adduct by using iodine oxidation was analyzed and the electrochemical signal of the adduct was observed. When the dsDNA modified GCE was immersed into various concentrations of BaP solution, the oxidation peak of guanine decreased and the adduct peak increased with the increasing BaP concentration. The partition coefficient was also obtained from the peak of BaP with dsDNA. The results revealed that the formation of adducts could be determined by using electrochemical DNA biosensors, which are fast, simple and cost-effective devices. Furthermore, this study promises that the analysis of other important adducts would benefit from the introduction of electrochemical methods.     

In vitro study on the competitive reactions between arsenite and selenite with glutathione

Exposure to arsenic can cause various biological effects by increasing the production of reactive oxygen species (ROS). Selenium acts as a beneficial element by regulating ROS and limiting heavy metal uptake and translocation. There are studies on the interactive effects of As and Se in plants, but the antagonistic and synergistic effects of these elements based on their binding to glutathione (GSH) molecules have not been studied yet. In this study, we aimed to investigate the antagonistic or synergistic effects of As and Se on the binding mechanism of Se and As with GSH at pH 3.0, 5.0, or 6.5. The interaction of As and Se in Se(SG)₂ + As(III) or As(SG)₃ + Se(IV) binary systems and As(III) + Se(IV) + GSH ternary system were examined depending on their ratios via liquid chromatography diode array detector/electrospray mass spectrometry (LC-DAD/MS) and liquid chromatography–electrospray ionization–tandem mass spectrometry (LC-ESI-MS/MS). The results showed that the formation of As(GS)₃ was not detected in the As(III) + Se(SG)₂ binary system, indicating that As(III) did not affect the stability of Se(SG)₂ complex antagonistically. However, in the Se(IV) + As(SG)₃ binary system, the addition of Se(IV) to As(SG)₃ affected the stability of As(SG)₃ antagonistically. Se(IV) reacted with GSH, disrupting the As(SG)₃ complex, and consequently, Se(SG)₂ formation was measured using LC-MS/DAD. In the Se(IV) + GSH + As(III) ternary system, Se(SG)₂ formation was detected upon mixing As(III), Se(IV), and GSH. The increase in the concentration of As(III) did not influence the stability of the Se(SG)₂ complex. Additionally, Se(IV) has a higher affinity than As(III) to the GSH, regardless of the pH of the solution. In both binary and ternary systems, the formation of the by-product glutathione trisulfide (GSSSG) was detected using LC-ESI-MS/MS.     

Synthesis,structural characterization,and anion interactions of new triazole-linked urea derivative fully substituted cyclotriphosphazene compounds

Three novel fully substituted urea derivative cyclotriphosphazene compounds 5–7 were synthesized by alkyne-azide 1,3-dipolar cycloaddition reaction of propargyl substituted ureas 2–4 with hexaazide substituted cyclotriphosphazene 1 in the presence of Cu(I) catalyst. All compounds were characterized with spectroscopic techniques such as FT-IR, ¹H, ¹³C, and ³¹P nuclear magnetic resonance and mass spectroscopy. Also, the usefulness of compounds 5–7 as anion carriers was investigated by ¹H NMR spectroscopy. For this purpose, ¹H NMR spectra of compounds 5–7 were recorded in the presence of tetrabutylammonium fluoride in DMSO-d₆. It was determined, that the urea protons in the compounds interact with fluoride.     

Fabrication of SERS active gold nanorods using benzalkonium chloride,and their application to an immunoassay for potato virus X

The authors report on a robust method for the synthesis of gold nanorods (AuNRs) with tunable dimensions and longitudinal surface plasmon resonance. The method relies on seed-mediated particle growth in the presence of benzalkonium chloride (BAC) in place of the widely used surfactant cetyltrimethyl ammonium bromide (CTAB). Uniform AuNRs were obtained by particle growth in solution, and BAC is found to stabilize the AuNRs for >1 year. The SERS activity of the resulting AuNRs is essentially identical to that of CTAB-protected nanorods. The SERS activity of the BAC protected nanorods was applied to the quantitative analysis of potato virus X (PVX). The calibration plot for PVX is linear in the 10 to 750 ng?mL^?1 concentration range, and the detection limit is 2.2 ng?mL^?1.

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Graphical abstract SERS-active gold nanorods (AuNRs) have been prepared by using benzalkonium chloride as stabilization agent. Effects of chemical parameters on AuNRs have been explored and AuNRs were used in quantitative analysis of potato virus X (PVX).

     

Fabrication and characterization of calix[4]arene Langmuir–Blodgett thin film for gas sensing applications

Microwave irradiation has been found to be a highly efficient method for etherification of p-tert-butylcalix[4]arene with alkyl bromides or ditosylate. The corresponding products were obtained as a pure form in modest yield within short reaction time when the reactions were performed under microwave irradiation.