A simple,rapid and sensitive method based on modified multiwalled carbon nanotube for preconcentration and determination of lead ions in aqueous media in natural pHs

In this study, multiwalled carbon nanotube (MWCNT) was modified by the pyridine group using a silane agent and characterized by infrared spectroscopy (IR), thermal analysis (TG/DTA), and elemental analysis (CHN) and scanning electron microscopy (SEM). The application of this sorbent was investigated in determination of lead ions in aqueous samples, using flame atomic absorption spectrometry (FAAS). Through this study, different parameters such as pH and sample flow rate on adsorption process and eluent concentration, volume and flow rate were optimized. The limit of detection (LOD), the relative standard deviation and the recovery of the method were 2 ng mL^?1, 1.3% and 99.7%, respectively. Two standard reference materials (NIST 1571 and NIST 1572) were used to verify accuracy of this method. Finally, the sorbent was successfully applied for extraction and determination of low levels of Pb(II) ions in aqueous samples.     

Microwave‐assisted polycondensation of 4‐octylaniline with dibromoarylene

The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542     

Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956     

Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s

The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329     

Buffering effects on the solution behavior and hydrolytic degradation of poly(β-amino ester)s

With a vast, synthetically accessible compositional space and highly tunable hydrolysis rates, poly(β-amino ester)s (PBAEs) are an attractive degradable polymer platform. Leveraging PBAEs in a wide range of applications hinges on the ability to program degradation, which, thus far, has been frustrated by multiple confounding phenomena contributing to the degradation of these charged polyesters. Basic conditions accelerate hydrolysis, yet reduce solubility, limiting water access to amines and esters. Further, the high buffering capacity of PBAEs can render buffers ineffective at controlling solution pH. To unify understanding of PBAE degradation and solution properties, this study examines PBAE hydrolysis as a function of pH and buffer concentration as well as polymer hydrophobicity. At low buffer concentrations, the PBAE amines and the acid produced during hydrolysis control solution pH. Meanwhile, at high buffer concentrations that afford relatively constant pH, hydrolysis rate increases with pH, despite the reduced PBAE solubility. Increasing the hydrophobic content of PBAEs eventually hinders the capacity of the polymer to accept protons from solution, limiting the pH increase and slowing hydrolysis. These studies showcase the role of buffering on the pH-dependent degradation and solution properties of PBAEs, providing guidance for programming degradation in applications ranging from drug delivery to thermosets.     

A molecular fluorophore in citric acid/ethylenediamine carbon dots identified and quantified by multinuclear solid-state nuclear magnetic resonance

The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by ¹³C, ¹³C{¹H}, ¹H─¹³C, ¹³C{¹⁴N}, and ¹⁵N solid-state nuclear magnetic resonance (NMR) experiments. ¹³C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. ¹⁵N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved ¹³C NMR peaks, including an unusual ═CH signal at 84 ppm (¹H chemical shift of 5.8 ppm) and ═CN₂ at 155 ppm, and two distinctive ¹⁵N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a ¹H─¹³C HETCOR spectrum with brief ¹H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative ¹³C and ¹⁵N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in ¹³C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

Polymer nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface

Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO₂‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO₂ bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO₂ bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO₂/N₂‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO₂‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO₂‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156     

Formation of porous polymer morphology by microsyneresis during divinylbenzene polymerization

This article describes the investigation of the importance of various reaction conditions on microsyneretic pore formation during polymerization of divinylbenzene (DVB) under so‐called “solvothermal” conditions. To induce microsyneretic pore formation, the most important parameter is an unusually high dilution of monomers with a “good” porogen solvating the polymer chains. High dilution and solvation of the growing poly(DVB) chains promote the prolongation of the polymer chains rather than their interconnection by crosslinking. Consequently, when the polymer gel density reaches the point where syneresis starts, the polymer network is geometrically too extensive to be broken up into precipitating entities and, instead, porogen droplets are formed within the continuous polymer gel. The pore geometry created by microsyneresis offers high surface area in wide mesopores and hence, high capacity for supporting functional groups or reactions with much better accessibility than narrow pores between polymer microspheres produced by macrosyneresis in conventional styrenic polymer supports. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 774–781     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526