New metal-free phthalocyanines fused in peripheral positions with eight N-monotosylated diaza-12-crown-4 macrocyclic moieties connected by diethylenethio groups have been synthesized by cyclotetramerization of a newly synthesized dicyano-substituted macrocycle. Metallophthalocyanines were also prepared by reaction of the dicyano-substituted macrocycle in the presence of corresponding metal salts and a strong organic base. The new compounds were characterized by a combination of elemental analysis, ¹H and ¹³C NMR, IR, electronic and mass spectroscopies.

Syntheses of novel bifunctional poly(methyl methacrylate) (PMMA)-, poly(styrene) (PS)-, and (poly ε-caprolactone) (PCL)-based atom transfer radical polymerization (ATRP) macroinitiators derived from p-xylene-bis(1-hydroxy-3-thia-propanoloxy) core were carried out to obtain ABA-type block copolymers. Firstly, a novel bifunctional ATRP initiator, 1,4-phenylenebis(methylene-thioethane-2,1-diyl)bis(2-bromo-2-methylpropanoat) (PXTBR), synthesized the reaction of p-xylene-bis(1-hydroxy-3-thia-propane) (PXTOH) with α-bromoisobutryl bromide. The PMMA and PS macroinitiators were prepared by ATRP of methyl methacrylate (MMA) and styrene (S) as monomers using (PXTBR) as the initiator and copper(I) bromide/N,N,N′,N″,N″-pentamethyldiethylenetriamine (CuBr/PMDETA) as a catalyst system. Secondly, di(α-bromoester) end-functionalized PCL–based ATRP macronitiator (PXTPCLBr) was prepared by esterification of hydroxyl end groups of PCL-diol (PXTPCLOH) synthesized by Sn(Oct)₂–catalyzed ring opening polymerization (ROP) of ε-CL in bulk using (PXTOH) as initiator. Finally, ABA-type block copolymers, PXT(PS-b-PMMA-b-PS), PXT(PMMA-b-PS-b-PMMA), PXT(PS-b-PCL-b-PS), and PXT(PMMA-b-PCL-b-PMMA), were synthesized by ATRP of MMA and S as monomers using PMMA-, PS-, and PCL-based macroinitiators in the presence of CuBr/PMDETA as the catalyst system in toluene or N,N-dimethylformamide (DMF) at different temperatures. In addition, the extraction abilities of PCL and PS were investigated under liquid–liquid phase conditions using heavy metal picrates (Ag⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺, and Zn²⁺) as substrates and measuring with UV-Vis the amounts of picrate in the 1,2–dichloroethane phase before and after treatment with the polymers. The extraction affinity of PXTPCL and PXTPS for Hg²⁺ was found to be highest in the liquid–liquid phase extraction experiments. Characterizations of the molecular structures for synthesized novel initiators, macroinitiators, and the block copolymers were made by spectroscopic (FT–IR, ESI–MS, ¹H NMR, ¹³C NMR), DSC, TGA, chromatographic (GPC), and morphologic SEM.

In this study, a new Schiff base (H₄TSTE) was synthesized and characterized by elemental analysis, FT-IR, NMR and MS spectral data. Liquid–liquid extraction process was performed for removal of Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) from aqueous solutions by means of H₄TSTE. The extractions were investigated depending on the concentration of picric acid, metal ion and H₄TSTE ligand. Response surface methodology (RSM) was first applied to optimize metal ion-binding properties of H₄TSTE. The extraction efficiency was estimated to be >98% for all metals by models. Under the same conditions, the extraction efficiency was experimentally found to be >97% with a relative standard deviation within ±0.10 (N = 4), indicating the suitability of the models.