Synthesis, characterization of a new polyacrylic acid superabsorbent, some heavy metal ion sorption, the adsorption isotherms, and quantum chemical investigation

Poly(acrylic acid/Kryptofix 23-Dimethacrylate) superabsorbent polymer [P (AA/Kry23-DM) SAP] was synthesized by solution polymerization to remove Co, Ni, Cu, Cd, Mn, Zn, Pb, Cr, and Fe ions in water and improve the quality of the water. Kry23-DM cross-linker (1,4,7,13,16-Pentaoxa-10,19 diazo cyclohexene icosane di methacrylate) was synthesized using Kry23 and methacryloyl chloride. The characterization of the molecules was done by FTIR, TGA, DSC, and SEM techniques. The effects of parameters such as pH, concentration, and the metal ion interaction on the heavy metal ions uptaking of SAP was investigated. It was observed that P (AA/Kry23-DM) SAP has maximum water absorption, and the absorption increases with the pH increase. Adsorption rates and sorption capacity, desorption ratios, competitive sorption (qcs), and distribution coefficient (log D) of P(AA/Kry23-DM) SAP were studied as a function of time and pH with the heavy metal ion concentration. Langmuir and Freundlich isotherms of the P (AA/Kry23-DM) SAP were investigated to verify the metal uptake. Molecular mechanic (MM2), Assisted Model Building with Energy Refinement (AMBER), and optimized potentials for liquid simulations (OPLS) methods. were used in quantum chemical calculations for the conformational analysis of the cross-linker and the SAP. ∆H0 f calculations of the cross-linker and the superabsorbent were made using Austin Model 1(AM1) method. © 2020 by the authors. Licensee MDPI, Basel, Switzerland

Synthesis and Characterization of ABA-Type Triblock Copolymers Using Novel Bifunctional PS, PMMA, and PCL Macroinitiators Bearing <i>p</i>-xylene-bis(2-mercaptoethyloxy) Core

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

Effect of mesh size in monofilament and multifilament gillnets on catch efficiency in the Black Sea whiting (<i>Merlangius merlangus</i>) fishery

Gillnets are widely used fishing gear for targeting various fish species. Gillnet fisheries use different gear configurations such as different mesh sizes and number of netting twines (mono- or multifilament) depending on the species targeted. Gillnet fishery targeting whiting (Merlangius merlangus) is one of the economically important year-round fisheries in the Black Sea. However, large bycatch of whiting below minimum landing size (MLS) has led to a stock decrease, questioning sustainability of this fishery. This study evaluated how netting twine construction and mesh size can affect the capture probability of whiting. The results showed that changes in gillnet mesh size significantly affect the capture probability with increased mesh size reducing the average capture probability of undersized whiting from around 60%–5%. The results showed no significant differences in the average catch efficiency between monofilament and multifilament gillnets of the same mesh sizes; however, monofilament gillnets showed an increased catch efficiency for some length classes of whiting &gt; MLS. Based on these results, use of 32 or 34 mm mesh size monofilament gillnets is advisable for sustainable whiting fisheries management in the Black Sea