A new polymeric phthalocyanine containing 16-membered tetrathia macrocyclic moieties by microwave irradiation: Synthesis and characterization

Tetranitrile monomer (3) was synthesized by nucleophilic aromatic substitution of 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1) onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile monomer with 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile in 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I)-phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the chlorides of Ni(II), Co(II) and Cu(I) in DMAE. Zn(II)-phthalocyanine polymer was prepared by the reaction of the tetranitrile compound with the acetates of Zn(II) in DMAE. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectral data.     

Synthesis and metal-ion binding properties of new N2S4- and N2S5-donor macrocycles

Synthetic procedures for new N₂S₄- and N₂S₅-donor macrocycles (2 and 4) were given. The ligands were prepared by the reaction of NaBH₄ with the appropriate macrocyclic diamide in the presence of boron trifluoride ethyl etherate in dry tetrahydrofuran (THF). Solvent extraction method was used to evaluate metal-ion binding properties of the new ligands. The solvent extraction experiments suggested that the reduced macrocycles have Ag⁺ and Hg²⁺ selectivities compared to Pb²⁺, Co²⁺, Zn²⁺, Ni²⁺, Cu²⁺, Mn²⁺ and Cd²⁺ ions. The extraction constants (log K _ex) and complex compositions were determined for Ag⁺ and Hg²⁺ complex of compound (4).     

Microwave assisted synthesis and characterization of novel metal-free and metallophthalocyanines containing four pyridyl groups

The novel tetrasubstituted metal-free phthalocyanine (4) and metallophthalocyanines (5, 6, 7 and 8) bearing four pyridyl group moieties on peripheral positions have been synthesized by cyclotetramerization of the phthalonitrile derivative (3) in a multi-step reaction sequence. The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r., i.r., U.V.–vis and m.s. spectral data.     

The synthesis and characterization of a porphyrazine bearing aza-15-crown-5 moieties in the peripheral positions and its cobalt(II) complex

The synthesis of novel metal-free (H₂-Pz) and metalloporphyrazines (MgPz and CoPz), peripherally substituted with eight aza-15-crown-5 moieties, is described. The novel compounds were characterized by elemental analysis, i.r, ¹H and ¹³C-n.m.r, UV–vis and m.s. spectral data.     

A novel metal-free and metallophthalocyanines containing four 19-membered dithiadiazadioxa macrocycles by microwave irradiation: Synthesis and characterization

The novel tetrasubstituted metal-free phthalocyanine (5) and metallophtalocyanines (6, 7 and 8) bearing four 19-membered dithiadiazadioxa macrocyclic moieties on peripheral positions have been synthesized by cyclotetramerization reaction of phthalonitrile derivative (4) in a multi-step reaction sequence. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectral data.     

Synthesis and electropolymerization studies of non-aggregated (4-{3-[3-(dimethylamino,diethylamino)phenoxy]propoxy}phenyl)propanoxy substituted silicon naphthalocyanines

In this study, 3-(4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propan-1-ol, 3-(4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propan-1-ol and axially disubstituted silicon naphthalocyanines (SiNc) bearing electropolymerizable bis-[(4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propanoxy] and bis-[(4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propanoxy] units were synthesized for the first time. Aggregation behavior of SiNcs was examined in different solvents and concentrations in DMSO. In all solvents and concentrations, SiNcs were non-aggregated. Also, electrochemical studies of SiNcs were investigated by cyclic and square wave voltammetry. While SiNcs gave only naphthalocyanine-based reduction process during the cathodic potential scans, they were electropolymerized on the working electrode during the anodic potential scan because of the oxidative electropolymerization of (4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propanoxy and (4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propanoxy groups on the substituents of the complexes.     

Pyridine substituted BODIPYs: synthesis,characterization and cholinesterease, α-glucosidase inhibitory,DNA hydrolytic cleavage effects

In this study, the synthesis of new monostyryl (BDPY-2) and distyryl BODIPY dyes (BDPY-4, BDPY-5) containing pyridine groups has been reported for the first time. The acetylcholinesterase from Electrophorus electricus (AChE), butyrylcholinesterase from equine serum (BuChE), α-glucosidase from Saccharomyces cerevisiae and DNA hydrolytic cleavage actions of BDPY-2, BDPY-4, BDPY-5 were investigated using various techniques. The results indicated that the compounds had varying inhibition properties against AChE, BuChE, and α-glucosidase. BDPY-4 was the most potent compound on AChE with IC₅₀ of 54.78 ± 4.51 µM, and Lineweaver–Burk plots indicated that the compound is bound to a site other than the active site as a noncompetitive inhibitor. The compound-protein binding experiment showed that BDPY-4 changed the microenvironment around AChE. On the other hand, the compounds showed lower α-glucosidase inhibition than the positive control. The DNA hydrolytic cleavage effects were not observed on supercoiled plasmid DNA in the presence of the compounds as compared to negative controls. These findings suggested that BDPY-4 might be a promising compound to treat Alzheimer’s diseases.     

Spectrophotometric determination of Hg(II) in water samples by dispersive liquid liquid microextraction with use ionic liquid after derivatization with a water soluble Fe(II) phthalocyanine

This study reports the synthesis of water soluble iron(II) phthalocyanine and a facile method for spectrophotometric determination of Hg(II) in environmental water samples by ionic liquid based dispersive liquid–liquid microextraction (IL-DLLME). In the method, 1-heptyl-3-methylimidazolium hexafluorophosphate (250 µL) as extraction solvent, acetonitrile (750 µL) as dispersive solvent and Triton X-100 (200 µL) as anti-sticking agent were used. After the extraction of the Hg(II) complex (Hg(II):q-Fe(II)-Pc) into thin droplets of ionic liquid, the sample was centrifuged for 4 min at 2000 rpm. The upper aqueous phase was removed and the residue diluted to 250 µL with methanol and transferred to a 250 µL cell for spectrophotometric detection at 280 nm. The linear range of the method is 0.05–1 µg/mL. The limits of detection and quantification is 0.01 and 0.03 µg/mL, respectively. The RSD for the developed method was calculated as 0.78% at 0.50 µg/mL Hg(II).     

Obtaining a secure and efficient key agreement protocol from (H)MQV and NAXOS

LaMacchia, Lauter and Mityagin recently presented a strong security definition for authenticated key agreement strengthening the well-known Canetti-Krawczyk definition. They also described a protocol, called NAXOS, that enjoys a simple security proof in the new model. Compared to MQV and HMQV, NAXOS is less efficient and cannot be readily modified to obtain a one-pass protocol. On the other hand MQV does not have a security proof, and the HMQV security proof is extremely complicated. This paper proposes a new authenticated key agreement protocol, called CMQV (‘Combined’ MQV), which incorporates design principles from MQV, HMQV and NAXOS. The new protocol achieves the efficiency of HMQV and admits a natural one-pass variant. Moreover, we present a relatively simple and intuitive proof that CMQV is secure in the LaMacchia-Lauter-Mityagin model.