Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems

Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl₂?4H₂O, CoCl₂?6H₂O or FeCl₃?6H₂O salts in basic condition in dimethylformamide. Fourier transform infrared, ¹H NMR, ¹³C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H₂O₂ combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd.     

Feasibility Exploration of Laser‐based Techniques for Characterization of a Flashing Jet

Two‐phase flows hold an interest in many areas of science and engineering. In the safety field, one such topic is the accidental release of flammable and toxic pressure‐liquefied gases. In case of such a release, a flashing vapor explosion takes place resulting in a very dense two‐phase cloud. If the released substance is flammable, this cloud can be combustible and can lead to deflagration or detonation. For understanding the source processes of flashing and risk assessment, data related to cloud characteristics (i.e. droplet size, velocity etc.) is needed especially in the near region of the release. Due to the non‐equilibrium nature of the near field regions accurate data measurement is not possible with intrusive techniques. Therefore, laser‐based optical techniques (like Particle Image Velocimetry (PIV), Particle Tracking Velocimetry and Sizing (PTVS), Phase Doppler Anemometry (PDA) etc.) present the only possibility to obtain information for particle diameter and velocity evolution in this harsh environment.     

Stabilization ofEscherichia coli penicillin G acylase by polyethylene glycols against thermal inactivation

The effects of five polyethylene glycol (PEG) compounds of different molecular weight on the thermal stability of penicillin G acylase (PGA) obtained from a mutant ofEscherichia coli ATCC 11105 have been investigated. The molecular weights of PEG compounds were 400, 4000, 6000, 10,000, and 15,000. The thermal inactivation mechanisms of both native and PEG-containing PGA were considered to obey first order inactivation kinetics during prolonged heat treatments. Optimal concentrations of PEGs at molecular weights of 400,4000, 6000,10,000, and 15,000 were found to be 250,150,150,100, and 50 mM, respectively. The greatest enhancement of thermostability was observed with PEG 4000 and PEG 6000, as a nearly 20-fold increase above 50°C. PGA showed almost the same temperature activity profile and optimal temperature values both in the presence and absence of PEG. The addition of PEGs did not cause any change in the optimal temperature value of PGA, but the parametersV _m ,K _m , the activation energy, and thek _cat values of enzyme were markedly decreased because of the mixed inhibition by PEG compounds. The type of inhibition was found to be hyperbolic uncompetitive.     

(Liquid + liquid) equilibria of (water + propionic acid + methyl isoamyl ketone or diisobutyl ketone or ethyl isoamyl keton) at T = 298.2 K

(Liquid + liquid) equilibrium (LLE) data for (water + propionic acid + solvent) were measured at T = 298.2 K and atmospheric pressure. The solvents were methyl isoamyl ketone (5-methyl-2-hexanone), ethyl isoamyl ketone (5-methyl-3-heptanone) and diisobutyl ketone. The tie-line data were correlated by means of the NRTL and UNIQUAC equation, and compared with results predicted by the UNIFAC method. A comparison of the extracting capabilities of the solvents was made with respect to distribution coefficients, separation factors, and solvent free selectivity bases.     

Chiral 2-(2-hydroxyaryl)alcohols (HAROLs) with a 1,4-diol scaffold as a new family of ligands and organocatalysts

Efficient and modular syntheses of chiral 2-(2-hydroxyaryl)alcohols (HAROLs), novel 1,4-diols carrying one phenolic and one alcohol hydroxyl group, have been developed which led to generation of a small library of structurally diverse HAROLs in enantiomerically pure form. Of the different HAROLs examined, a HAROL based on the indan backbone exhibited the highest activity and enantioselectivity in the 1,2-addition of certain organometallic compounds to aldehydes in the presence of Ti(OⁱPr)₄ (up to 97% y, 88% ee) and performed as a hydrogen-bond donor organocatalyst in the Morita-Baylis-Hillman reaction, promoted by trialkylphosphines.     

Development and validation of an LC‐MS/MS method for simultaneous quantitative analysis of free and conjugated bisphenol A in human urine

Bisphenol A (BPA) is an environmental endocrine‐disrupting chemicals that is widely used in common consumer products. There is an increasing concern regarding human exposure to BPA owing to the potential adverse effects associated with its estrogenic activity. For assessing environmental exposure to BPA, it is essential to have a sensitive, accurate and selective analytical method, especially one that can detect low BPA levels in complex sample matrices. In this study, we developed and validated an accurate, sensitive, and robust liquid chromatography–tandem mass spectrometry method for simultaneous quantification of free BPA and BPA β‐d ‐glucuronide (BPA‐gluc) concentrations in human urine with only a single injection. Calibration curves were linear over a concentration range of 1–100 ng/mL for BPA and 10–1000 ng/mL for BPA‐gluc. The levels of the analytes were determined quantitatively with HPLC/ESI‐MS/MS by using negative electrospray ionization in the select ion monitoring mode and a pentaflouraphenyl propyl column. The validated method was applied to the analysis of spot urine specimens collected from randomly selected healthy human subjects. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization and in vitro release kinetics of chitosan based biocomposites from Scotch Bonnets

The main aim of this study is to formulate the combination of the bioactive composite containing chitosan/β -tricalcium phosphate (CH/β-TCP) as potential drug delivery platforms for the sustained release of antibiotics. Herein the mode of amoxicillin (AMX) maintained in the β-TCP/chitosan composite was characterized using XRD, FT-IR to confirm the phase purity and functional groups. SEM was used to examine the size and shape of particles. The SEM images of the biocomposites after drug release confirmed that they are biodegradable. In vitro drug release experiments in PBS (pH 7.4) revealed a sustained release profile in a neutral medium. Drug release profiles were evaluated according to five different kinetic models including Zero Order, First Order, Higuchi, Hixon Crowel, and Korsmeyer-Peppas. The release profile was best expressed by the Korsmeyer Peppas model because the results showed high linearity. Overall, the positive effect of chitosan coating on the drug elution profile of β-TCP as carriers for the controlled delivery of antibiotics was regarded as biocompatible for the controlled drug delivery system.     

Synthesis, characterization and aggregation behaviour of novel peripherally tetra-substituted octacationic water soluble metal-free and metallophthalocyanines

In this study, a new phthalonitrile derivative 3 bearing 1,3-bis[3(dimethylamino)phenoxy]propan-2-ol 1, metal-free phthalocyanine (Pc) 4, metallophthalocyanines (MPcs) 5–7 and their quaternized derivatives 4a–7a were synthesized. Metal-free Pc 4 was prepared by cyclotetramerization of phthalonitrile derivate 3 and MPcs 5–7 were synthesized by heating 3 with NiCl₂, CoCl₂ and CuCl₂ in n-pentanol in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, respectively. Quaternization of the dimethylamino functionality produced quaternized octacationic water soluble metal-free, Ni, Co and Cu Pcs which were soluble in water, DMF, DMSO. The aggregation behaviour of these compounds were investigated in different concentrations of chloroform for metal-free, Ni, Co and Cu Pcs. The effect of solvents on absorption spectra were studied in various organic solvents. The novel compounds were characterized using IR, ¹H-, ¹³C NMR, UV–vis and MS spectral data.     

Electroanalytical characteristics of antipsychotic drug ziprasidone and its determination in pharmaceuticals and serum samples on solid electrodes

Ziprasidone is a psychotropic agent used for the treatment of schizophrenia. Its oxidation was investigated electrochemically at boron-doped diamond and glassy carbon electrodes using cyclic, differential pulse, and square wave voltammetry. The dependence of the peak current and peak potentials on pH, concentration, nature of the buffer, and scan rate were examined. The process was diffusion and adsorption controlled for boron-doped diamond and glassy carbon electrodes, respectively. The possible mechanism of oxidation was discussed with some model compounds that have indole and piperazine oxidations. A linear response was obtained between 8 × 10⁻⁷ and 8 × 10⁻⁵ M for the first peak in acetate buffer (pH 5.5) and between 2 × 10⁻⁶ and 2 × 10⁻⁴ M for the second peak in 0.1 M H₂SO₄ with boron-doped diamond electrode for differential pulse and square wave voltammetric techniques. The reproducibility and accuracy of the proposed methods were found between 0.31 and 1.20, 99.27 and 100.22, respectively. The recovery studies were also achieved to check selectivity and accuracy of the methods. The proposed methods were applied for the determination of ziprasidone from pharmaceutical dosage forms and human serum samples without any time-consuming extraction, separation, evaporation or adsorption steps prior to drug assay except precipitation of the proteins using acetonitrile. The results were statistically compared with those obtained through an established LC-UV technique, no significant differences were been found between the voltammetric and LC methods.