Co(II) and Fe(II) phthalocyanines: synthesis,investigation of their catalytic activity towards phenolic compounds and electrochemical behaviour

4‐[(1‐Benzylpiperidin‐4‐yl)oxy]‐substituted cobalt(II) and iron(II) phthalocyanine complexes were synthesized and their catalytic activity towards various phenolic compounds was investigated. Converting from environmentally harmful phenolic compounds into less harmful oxidation products using phthalocyanines makes this study attractive. This catalysis is feasible and time‐saving in terms of procedure and the best oxidation conditions determined. Electrochemical studies were also carried out using cyclic voltammetry and square wave voltammetry techniques. Voltammetric analyses of the synthesized phthalocyanine complexes supported their proposed structures. Copyright © 2015 John Wiley & Sons, Ltd.     

How to Separate Kinase Inhibition from Undesired Monoamine Oxidase A Inhibition—The Development of the DYRK1A Inhibitor AnnH75 from the Alkaloid Harmine

The β-carboline alkaloid harmine is a potent DYRK1A inhibitor, but suffers from undesired potent inhibition of MAO-A, which strongly limits its application. We synthesized more than 60 analogues of harmine, either by direct modification of the alkaloid or by de novo synthesis of β-carboline and related scaffolds aimed at learning about structure–activity relationships for inhibition of both DYRK1A and MAO-A, with the ultimate goal of separating desired DYRK1A inhibition from undesired MAO-A inhibition. Based on evidence from published crystal structures of harmine bound to each of these enzymes, we performed systematic structure modifications of harmine yielding DYRK1A-selective inhibitors characterized by small polar substituents at N-9 (which preserve DYRK1A inhibition and eliminate MAO-A inhibition) and beneficial residues at C-1 (methyl or chlorine). The top compound AnnH75 remains a potent DYRK1A inhibitor, and it is devoid of MAO-A inhibition. Its binding mode to DYRK1A was elucidated by crystal structure analysis, and docking experiments provided additional insights for this attractive series of DYRK1A and MAO-A inhibitors.     

New peripherally tetra-[trans-3,7-dimethyl-2,6-octadien-1-ol] substituted metallophthalocyanines: synthesis,characterization and catalytic activity studies on the oxidation of phenolic compounds

In this paper, we elucidated the synthesis, characterization, and investigation of catalytic activity studies of new metallophthalocyanines 4 and 5 as the catalyst for phenolic compounds oxidation by trying different types of oxygen sources. The structural characterization of the products was made by a combination of elemental analysis, FT-IR, LC-MS/MS (for phthalonitrile derivative 3), MALDI-TOF mass spectral data (for metallophthalocyanines 4–7), UV–vis spectroscopy (for metallophthalocyanines 4–7), ¹H NMR and ¹³C NMR spectroscopies (for compounds 3 and 6). The synthetic routes for the (trans-3,7-dimethyl-2,6-octadien-1-ol) substituted phthalonitrile derivative 3 and corresponding metallophthalocyanines 4–7 are outlined in Scheme 1. The MPc complexes 4–7 were synthesized via cyclotetramerization of compound 3 in the presence of the corresponding anhydrous metal salts (CoCl₂ for 4, CuCl₂ for 5, Zn(CH₃COO)₂ for 6 and MnCl₂ for 7) in dry n-pentanol as solvent and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as strong base at reflux temperature under nitrogen gas. Phthalocyanines and their metal complexes, in general, display poor solubility in most of the organic solvents, however, the synthesized metallophthalocyanine complexes 4–7 were highly soluble in common organic solvents because of the introduction of the methyl groups on alkyl chains of peripheral arms. The catalytic activity of compounds 4 and 5 was evaluated for the oxidation of phenolic compounds such as 4-nitrophenol, o-chlorophenol, 2,3-dichlorophenol, and p-methoxyphenol. CoPc 4 displayed good catalytic performance with a full oxidation of 4-nitrophenol into the corresponding benzoquinone and hydroquinone with the highest TON and TOF values within 3 h.     

Experimental and theoretical studies of acridine orange as corrosion inhibitor for copper protection in acidic media

The corrosion process commonly limits the use of copper in practical applications. The use of corrosion inhibitors is one of the effective methods to reduce the corrosion rate of copper. In this research, the inhibition effect of acridine orange (3,6-bis(dimethylamine)acridine) (AcO) for the protection of copper in 0.5 ?M ?H₂SO₄ solution was studied. For this aim, the change of open circuit potential with exposure time (E_ocp-t), electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), anodic and cathodic potentiodynamic polarization measurements (PP) and chronoamperometry (CA) techniques were used. Some quantum chemical parameters (E_HOMO, E_LUMO and dipole moment) were calculated and discussed. The AcO film formed over the copper surface was examined by SEM, EDX, AFM and contact angle measurements. The electrochemical data showed that AcO is an effective corrosion inhibitor even at low concentrations (ranging between 99.1% and %99.4 ?at concentrations from 0.01 ?mM to 1 ?mM). The corrosion rate of copper decreases in the presence of the inhibitor by reducing both anodic and cathodic rates, which is depended on its concentration. This compound behaves as mixed-type corrosion inhibitors with predominantly cathodic type. Its adsorption on the copper surface obeys Langmuir adsorption isotherm. The value of adsorption equilibrium constant (K_ads) and the standard free energy of adsorption were ΔG_ads 1.298 x 10³ ?M^?1 and -27.71 ?kJ/mol in the case of 0.5 ?M ?H₂SO₄ solution containing 1.0 ?mM AcO, which shows the adsorption is high and spontaneous. The adsorbed inhibitor film over the metal increase contact angle of the surface, which suggests the more hydrophobic properties of the surface are increasing coming from the orientation of hydrophobic sites to the electrolyte. The zero charge potential (E_pzc) studies showed that the surface charge of the metal is positive in the corrosive media containing the inhibitor. Quantum chemical calculations showed that the binding of inhibitor molecules to the metal surface takes place through N atoms of the inhibitor.     

Crystallographic report: Bis{µ‐[O‐cyclopentyl(4‐methoxyphenyl) dithiophosphonato]1κ:S,2κ:S‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]1κ2S,S′} dizinc(II)

The centrosymmetric [Zn₂{CH₃OC₆H₄P(OC₅H₉)S₂}₄], features an eight‐membered Zn₂S₄P₂ ring as a result of two bidentate bridging thiolate ligands; the remaining ligands are chelating. Copyright © 2005 John Wiley & Sons, Ltd.     

Improving the appearance of all textile products from clothing to home textile using laser technology

Denim trousers, commonly known as “blue jeans”, have maintained their popularity for many years. For the purpose of supporting customers’ purchasing behaviour and to address their aesthetic taste, companies have been trying in recent years to develop various techniques to improve the visual aspects of denim fabrics. These techniques mainly include printing on fabrics, embroidery and washing the final product. Especially, fraying certain areas of the fabric by sanding and stone washing to create designs is a popular technique. However, due to certain inconveniences caused by these procedures and in response to growing demands, research is underway to obtain a similar appearance by creating better quality and more advantageous manufacturing conditions.

As is known, the laser is a source of energy which can be directed on desired objects and whose power and intensity can be easily controlled. Use of the laser enables us to cut a great variety of material from metal to fabric. Starting off from this point, we thought it would be possible to transfer certain designs onto the surface of textile material by changing the dye molecules in the fabric and creating alterations in its colour quality values by directing the laser to the material at reduced intensity.

This study mainly deals with a machine specially designed for making use of laser beams to transfer pictures, figures as well as graphics of desired variety, size and intensity on all kinds of surfaces in textile manufacturing such as knitted—woven fabrics, leather, etc. at desired precision and without damaging the texture of the material.

In the designed system, computer-controlled laser beams are used to change the colour of the dye material on the textile surface by directing the laser beams at a desired wavelength and intensity onto various textile surfaces selected for application. For this purpose, a laser beam source that can reach the initial level of power and that can be controlled by means of a computer interface; reflecting mirrors that can direct this beam at two axes; a galvanometer which comprised of an optical aperture; and a computer program that can transfer images obtained in standard formats to the galvanometer control card were used.

Developing new designs by using the computer and transferring the designs that are obtained on textile surfaces will not only increase and facilitate the production in a more practical manner, but also help you to create identical designs. This means serial manufacturing of the products at a standard quality and increasing their added values. Moreover, creating textile designs using laser will also contribute to the value of the product as far as the consumer is concerned because it will not cause any wearing off and deformation in the texture of the fabric unlike the sanding and stoning processes.

Another advantage of this system is that it gives a richer look to the product by causing the textile surfaces to get wrinkled and become three-dimensional by deformation as well as enabling you to create pictures and patterns on leather and synthetic fabrics by means of heat.

As for the results of the study, the first step was to prepare 40 pairs of denim trousers, half of which were prepared manually and the other half by using laser beam. Time studies were made at every step of the production. So as to determine the abrasion degrees of the trousers in design applications, tensile strength as well as tensile extension tests were conducted for all the trousers.     

Low-Cost Laser Scanning System Design

3D data is the main element of three-dimensional models that are commonly used in many different application areas such as architecture, archeology, medicine, film production, reverse engineering, etc. In this study, we discuss designing and utilizing opportunities for a low-cost triangulation-based laser scanner. To evaluate the system, a test object is specially designed, and the accuracy and operation of the system are verified by comparing the data output of the laser scanner with the terrestrial photogrammetric method. The designed system is also verified using different objects. At the end of the study, we calculate the precision of the scanned sample models to be 0.1–0.2 mm and RMS, 0.59 mm.     

Synthesis,characterization and electrochemistry of a new organosoluble metal-free and metallophthalocyanines

4-[2-(Phenylthio)ethoxy]phthalonitrile 3 was synthesized by nucleophilic displacement of nitro group in 4-nitrophthalonitrile with 2-(phenylthio)ethanol 1. The metal-free phthalocyanine 4 was prepared by the reaction of a dinitrile monomer with 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I) phthalocyanines 5, 7, 8 were prepared by reaction of the dinitrile compound with the chlorides of Ni(II), Co(II), Cu(I) in DMAE. Zn(II) phthalocyanine 6, was prepared by reaction of the dinitrile compound with the acetates of Zn(II) in DMAE. Electrochemical behaviours of novel metal-free, Co(II) and Zn(II) phthalocyanines were investigated by cyclic voltammetry, potential differential pulse voltammetry techniques. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis and MS spectral data.