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.     

Eigenvalues of Two Parameter Polynomial Operator Pencils of Waveguide Type

The spectral structure of two parameter unbounded operator pencils of waveguide type is studied. Theorems on discreteness of the spectrum for a fixed parameter are proved. Variational principles for real eigenvalues in some parts of the root zones are established. In the case of n = 1 (quadratic pencils) domains containing the spectrum are described (see Fig. 1–3). Conditions in the definition of the pencils of waveguide type arise naturally from physical problems and each of them has a physical meaning. In particular a connection between the energetic stability condition and a perturbation problem for the coefficients is given.     

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.     

A Method for the Acetylation of Alcohols Catalyzed by Heteropolyoxometallates

Summary. Esterifications of acetic acid with some linear, secondary, tertiary, and benzylic alcohols mediated by catalytic amounts of Keggin, Wells–Dawson, and Preyssler type heteropolyacids were carried out under reflux at mild reaction conditions with good to excellent yields. Among the examined catalysts, H₃PW₁₂O₄₀ and H₁₄NaP₅W₃₀O₁₁₀ revealed better results than other heteropolyacids. This work was performed with the aim of simplifying the esterification process by omitting any solvents and mineral acid catalysts. Easy work-up, low cost, and acidic waste reduction, which are all important features from the environmental and economical points of view, are distinct aspects of this protocol. Heteropolyacid catalysts could be separated after a simple work-up and reused for several times.     

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.     

Metal complexes of a homopolymer system containing diethanolamine side group: synthesis and dielectrical behaviors

In this work, 4-diethanolaminomethyl styrene (DEAMSt) monomer was prepared by modification of 4-chloromethyl styrene with diethanolamine. The homopolymerization of styrene modificated was carried out by free radical polymerization method at 60?°C in presence of 1,4-dioxane and AIBN. The metal complexes were prepared by reaction of the homopolymer used as ligand P(DEAMSt)L^l and Ni(II), Co(II) metal ions in presence of ethanol and dilute NaOH at 65?°C for 48?h in pH 6.

The structure of modificated monomer, homopolymer used as ligand and polymer-metal complexes were characterized by (FT-IR), ¹H-NMR, ¹³C-NMR, Raman spectroscopy tecniques, elemental analysis, SEM, XRD and magnetic measurements. Their geometric structures according to magnetic measurements of Co(II) and Ni(II) complexes were estimated that have a tetrahedral structure. P(DEAMSt)L^l polymer has a transition state between amorphous and crystalline, whereas metal complexes (Co(II) and Ni(II) are with a large crystal structure. The molecular weight of P(DEAMSt)L¹ homopolymer was determined by gel permeation chromatography (GPC). The glass transition temperature (Tg) of homopolymer was measured by differantial scanning calorimeter (DSC). The thermal behaviors of both ligand and polymer-metal complexes were investigated by thermogravimetric analysis (TGA) and (DTA). The results obtained were compared with each other. Then, the dielectrical measurements (dielectric constant, dielectric loss and conductivity) of the ligand and polymer-metal complexes were investigated as a function of temperature and frequency. The activation energies (Ea) of the ligand and metal complexes were determined from the conductivity measurements.     

Thermosensitive mucoadhesive gel formulation loaded with 5-Fu: cyclodextrin complex for HPV-induced cervical cancer

Human Papilloma Virus (HPV) infections are the major cause of cervical cancers. To achieve a better therapeutic efficacy and patient compliance in the treatment for HPV-induced cervical cancers, anticancer agent 5-fluorouracil has been formulated in a vaginal gel using the thermosensitive polymer Pluronic^® F127 together with alternative mucoadhesive polymers e.g., hyaluronic acid, Carbopol 934 and hydroxypropylmethylcellulose. To increase its aqueous solubility and to achieve the complete release of 5-FU from the gel, the drug was incorporated as its inclusion complex with 1:1 molar ratio with either β-cyclodextrin or hydroxypropyl-β-cyclodextrin. Following the characterization of drug:CD complexes, thermosensitive gel formulations containing different mucoadhesive polymers and the drug in free or complexed form were characterized in vitro by determining the gelation temperature and the rheological behavior of different formulations along with the in vitro release profiles of these formulations in pH 5.5 citrate buffer. It was observed that complexation with cyclodextrin accelerated the release of 5-FU with the exception of formulation containing Carbopol 934 as mucoadhesive polymer. As far as rheological properties are concerned, favorable thermosensitive in situ gelling properties were obtained with formulations containing HPMC as mucoadhesive polymer. Complete release of 5-FU from gels were obtained with both complexes of β-CD and HP-β-CD and cytotoxicity studies against HeLa human cervical carcinoma cells demonstrated that 1% 5-FU:CD complexes were equally effective as 1% free 5-FU indicating better therapeutic efficacy with lower dose.     

(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.