Adsorption of Metanil Yellow Azoic Dye from Aqueous Solution onto Mg‐Fe‐NO3 Layered Double Hydroxide

We report the preparation and characterization of a layered double hydroxide (LDH) adsorbent for azoic dye, metanil yellow (yellow GX; YGX) removal. The nanoparticles of Mg‐Fe‐LDH‐NO₃ adsorbent were prepared with Mg/Fe molar ratio of 3:1 by a hydrothermal process and coprecipitation method at pH 9.5 and were characterized by X‐ray powder diffraction (XRPD), thermal gravimetric analysis (TGA), elemental analysis, and Fourier transform infrared spectroscopy (FT‐IR). The size and morphology of nanoparticles were examined by scanning electron microscopy (SEM). The XRD patterns indicate that the intercalation of YGX between the LDH layers has not occurred and surface adsorption has happened. In the adsorption experiments, the Gibbs free energy ΔG⁰ values, the enthalpy ΔH⁰, and entropy ΔS⁰ was determined. The isotherms showed that the adsorption of YGX by Mg‐Fe‐LDH‐NO₃ was both consistent with Langmuir and Freundlich equations.     

Thermal Decomposition Kinetics of Ethane Halides and Derivatives（C_2H_（6-n）X_n（n = 1～3）;X = F,Cl,Br）：DFT Study and NBO Analysis

A theoretical study of the thermal decomposition kinetics of ethane halides(C2H6-nXn(n = 1～3);X = F,Cl,Br) has been carried out at the B3LYP/6-31++G** and B3PW91/631++G** levels of theory.Among these methods and comparison of activation parameters with available experimental values,the B3PW91/6-31++G** method is in good agreement with the experimental data.The analysis of bond order and natural bond orbital(NBO) charges,bond indexes,and synchronicity parameters suggest the elimination of HX in reactions 1～9(HF:compounds 1～3,HCl:compounds 4～6,and HBr:compounds 7～9) occur through a concerted and slightly asynchronous four-membered cyclic transition state type of mechanism.     

Hollow fiber liquid phase microextraction as a preconcentration and clean-up step after pressurized hot water extraction for the determination of non-steroidal anti-inflammatory drugs in sewage sludge

A method for the quantitative determination of non-steroidal anti-inflammatory drugs (NSAIDs) in sewage sludge was developed and validated. The target compounds were extracted using pressurized hot water extraction (PHWE) and then purified and preconcentrated by three-phase hollow fiber liquid phase microextraction (HF-LPME) followed by LC–ESI-MS analysis. The PHWE was optimized with regard to the pH of solvent as well as other operational parameters. The optimum conditions were 0.01 M NaOH as the extraction solvent, temperature of 120 °C, pressure of 100 bar, static time 5 min, 5 cycles, flush volume 90% and purge time 60 s. Spike recoveries for sludge samples spiked at 200 ng g⁻¹ were in the range of 101–109% but for the native drugs in non-spiked sludge samples, recoveries were 38.9%, 59.8%, 90.3% and 47.8% for ketoprofen, naproxen, diclofenac and ibuprofen, respectively. Donor phase pH, ionic strength and extraction time were optimized for HF-LPME after PHWE. The optimum conditions were 2 h extraction at pH 1.5 without salt addition. Enrichment factors in the range of 947–1213 times were achieved (extraction recoveries were 23.6–30.3%) for HF-LPME after PHWE. The matrix effect on the ionization of drugs in LC–ESI-MS was also investigated. The results show that there is a smaller matrix effect (−8.9% to +14.6%) in comparison with other published values obtained using solid phase extraction (SPE) for clean-up after pressurized liquid extraction (PLE). Method detection limits (MDLs) and method quantification limits (MQLs) for different drugs were in the range of 0.4–3.7 ng g⁻¹ and 1.5–12.2 ng g⁻¹ in dried sludge samples, respectively. The characteristics of the proposed method were compared with those of other published works. The considerably lower ion suppression/enhancement and minimum use of organic solvents (a few microliters of di-n-hexyl ether) in the sample preparation step are two highlighted advantages of the proposed method in comparison with previously published works. The method was applied to determine NSAIDs in sewage sludge from Källby wastewater treatment plant (Lund, Sweden) in April, June, August and October 2010. The highest concentration level was recorded for ibuprofen in the April sewage sludge sample (588 ng g⁻¹) and all of the selected NSAIDs were detected in all the samples analyzed.     

Extraction of antidepressant drugs in biological samples using alkanol‐based nano structured supramolecular solvent microextraction followed by gas chromatography with mass spectrometric analysis

In the present study, a supramolecular solvent was formed from reverse micelle aggregates of octanol. The proposed supramolecular solvent was used for rapid extraction of some antidepressants drugs including amitriptyline, imipramine, desipramine, maprotiline, sertraline, and doxepin from biological samples. Alkanol‐based supramolecular solvents have a unique array of physicochemical properties, making them a very attractive alternative to replace organic solvents in analytical extractions. The parameters affecting the extraction of target analytes (i.e., the volume of tetrahydrofuran and octanol as the major components comprising the supramolecular solvent, chain length of alkanols, sample solution pH, salt addition, and ultrasonic time) were investigated and optimized by factor by factor optimization method. Under the optimum conditions, preconcentration factors of 470, 490, 460, 385, 370, and 430 were obtained for amitriptyline, doxepin, imipramine, desipramine, maprotiline, and sertraline, respectively. The linear ranges and coefficients of determination (R²) were obtained in the range of 0.01–100 μg/L and 0.9974–0.9991, respectively. Also the limits of detection (S/N = 3) of 0.003–0.03 μg/L, and precisions (n = 5) of 4.9–8.9% were calculated. Finally, the method was successfully applied for the extraction of antidepressant drugs in biological samples, and relative recoveries in the range of 91–102% were obtained.     

An efficient and one-pot green synthesis of novel 6-oxo-7-aryl-6,7-dihydrochromeno pyrano[2,3-b]pyridine derivatives

A simple and efficient protocol has been developed for the construction of novel 6-oxo-7-aryl-6,7-dihydrochromenopyrano[2,3-b]pyridine derivatives using one-pot, three-component cyclocondensation of 4-hydroxycoumarin, various aromatic aldehydes and 2-aminoprop-1-ene-1,1,3-tricarbonitrile using 10?mol % guanidine hydrochloride as the organocatalyst under solvent-free conditions at 90?°C for the first time. The significant features of this protocol are operational simplicity, provide good to high yields, avoidance of toxic solvents, straightforward work-up, no column chromatographic purification and atom-economy which is considered to be relatively environmentally benign.     

Synthesis,X-ray crystal structure and DFT studies of cobalt(II) and vanadium(V) complexes with N,N,O-tridentate aroyl-hydrazone based ligand

A new aroyl-hydrazone, 2-pyridine carboxaldehyde-derived hydrazone ligand and its cobalt(II) (1) and vanadium(V) (2) complexes were prepared. The structures of these compounds were investigated using elemental analysis, spectral (IR, UV), and X-ray diffraction measurements. The electrochemical properties of the complexes were studied by cyclic voltammetry. The hydrazone ligand acted as tridentate and coordinated to vanadium and cobalt via N-imine, N-pyridine, and O-benzohydrazide atoms. The Co(II) complex crystallizes in the monoclinic system, space group P2₁/c, and has a binuclear structure. Chloride ions behave as the linking bridge and a tridentate hydrazine ligand HL and water as the terminal capping ligands. The central Co(II) ion has distorted octahedral geometry. The vanadium(V) complex crystallizes in the monoclinic crystal system, space group P2₁/n, and can be described as having highly distorted trigonal-bipyramidal coordination. The geometries and electronic properties of the complexes were also obtained using DFT and TD-DFT calculations.     

Synthesis, characterization, spectroscopic and thermodynamic studies of charge transfer interaction of a new water-soluble cobalt(II) Schiff base complex with imidazole derivatives

The water-soluble cobalt(II) tetradentate Schiff base complex [Co(II)L](ClO4)(2), L: (N,N'-bis(5-[(triphenylphosphonium)-methyl]salicylidine)-o-phenylenediamineperchlorate has been synthesized and characterized. This complex forms charge transfer (CT) complexes with imidazole and 1-methylimidazole. The formation constant, molar absorptivity (epsilon'), and thermodynamic parameters for charge transfer complexes formation of cobalt(II) Schiff base complexes with imidazole derivatives were determined by using UV-vis spectrophotometric method in aqueous solutions at constant ionic strength (I=0.2mol dm(-3) KNO3) at pH 6.0 and various temperatures between 292 and 315K.     

Scanning electrochemical microscopy. 59. Effect of defects and structure on electron transfer through self-assembled monolayers

Electron transfer (ET) rate kinetics through n-alkanethiol self-assembled monolayers (SAMs) of alkanethiols of different chain lengths [Me(CH2)nSH; n=8, 10, 11, 15] on Au and Hg surfaces and ferrocene (Fc)-terminated SAMs (poly-norbornylogous and HS(CH2)12CONHCH2Fc) on Au were studied using cyclic voltammetry and scanning electrochemical microscopy (SECM). The SECM results allow determination of the ET kinetics of solution-phase Ru(NH3)63+/2+ through the alkanethiol SAMs on Au and Hg. A model using the potential dependence of the measured rate constants is proposed to compensate for the pinhole contribution. Extrapolated values of koML for Ru(NH3)63+/2+ using the model follow the expected exponential decay (beta is 0.9) for different chain lengths. For a Fc-terminated poly-norbornyl SAM, the standard rate constant of direct tunneling (ko is 189+/-31 s(-1)) is in the same order as the ko value of HS(CH2)12CONHCH2Fc. In blocking and Fc SAMs, the rates of ET are demonstrated to follow Butler-Volmer kinetics with transfer coefficients alpha of 0.5. Lower values of alpha are treated as a result of the pinhole contribution. The normalized rates of ET are 3 orders of magnitude higher for Fc-terminated than for blocking monolayers. Scanning electron microscopy imaging of Pd nanoparticles electrochemically deposited in pinholes of blocking SAMs was used to confirm the presence of pinholes.     

One-pot access to new tetrahydrobenzo[a]xanthen-11-ones and naphthopyranopyrimidines using 2,3-dihydroxynaphthalene

A one-pot, three-component reaction of 2,3-dihydroxynaphthalene, aromatic aldehydes, and cyclic 1,3-dicarbonyl compounds in the presence of formic acid catalyst under solvent-free conditions provides access toward a new class of tetrahydrobenzo[a]xanthen-11-ones and naphthopyranopyrimidines. The scope of the process was explored under two different reaction conditions resulting in the generation of title compounds in high yields. Moreover, the key advantages of this process are cost effectiveness of catalyst, short reaction times, easy workup, and purification of products by nonchromatographic methods.     

Guanidine Hydrochloride: A Highly Efficient Organocatalyst for the Synthesis of 12‐Aryl‐8,9,10,12‐tetrahydrobenzo[a]xanthene‐11‐ones Under Solvent‐Free Conditions

A new green protocol has been developed for the synthesis of 12‐aryl‐8,9,10,12‐tetrahydrobenzo[a]xanthen‐11‐ones using guanidine hydrochloride as an organocatalyst under solvent‐free conditions. Operational simplicity, mild reaction conditions, enhanced rates, high isolated yields of the pure products, and purification of products by nonchromatographic methods are significant advantages of the protocol presented here.