Reentrant phase transition and network parameters of hydrophobically modified poly[2-(diethylamino)ethylmethacrylate-co-N-vinyl-2-pyrrolidone/octadecyl acrylate] hydrogels

Hydrophobically modified poly[2-(diethylamino)ethylmethacrylate-co-N-vinyl-2-pyrrolidone/octadecyl acrylate] [P(DEAEMA-NVP/OA)] hydrogels with different OA content were prepared by free-radical crosslinking copolymerization of corresponding monomers in tert-butanol. The swelling equilibrium of the hydrogels was investigated as a function of temperature and hydrophobic comonomer content in pure water. An interesting feature of the swelling behavior of the P(DEAEMA-NVP/OA) hydrogels was the reentrant phase transition where the hydrogels collapse once and reswell as temperature increased. The average molecular mass between crosslinks and polymer-solvent interaction parameter (χ) of the hydrogels were calculated from equilibrium swelling values. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter for the hydrogels were determined by using the Flory-Rehner theory. It was observed that the experimental swelling data of the hydrophobic hydrogels at different temperature agreed with the Flory-Rehner theory, that provided that the sensitive dependence of χ parameter on both temperature and polymer concentration is taken into account.     

Organoclay modified with lignin as a new adsorbent for removal of Pb2+ and UO2 2+

This study investigated a new adsorbent prepared from lignin modified organoclay for the removal of Pb²⁺ and UO₂ ²⁺ from aqueous solutions. The characterization of new adsorbent was performed by FT-IR and XRD. Adsorption of Pb²⁺ and UO₂ ²⁺ species in aqueous solution as a function of ion concentration, pH, temperature and time of adsorption was investigated in detail. The adsorption data were analyzed by using the Langmuir, Freundlich and Dubinin-Radushkevich models. The monolayer adsorption capacities of organoclay–lignin were 0.12 mol kg^?1 and 0.42 mol kg^?1 for Pb²⁺ and UO₂ ²⁺, respectively. The experimental kinetic data were analyzed by using pseudo-second-order kinetic and intra-particle diffusion models. The proposed adsorption mechanism follows a pseudo-second-order kinetic and endothermic because of increasing disorderliness at adsorbate/adsorbent interface.     

Synthesis,Spectral Characterization and Antimicrobial Activity of Some Transition Metal Complexes of 1,3‐Bis(1H‐benzimidazol‐2‐yl)‐2‐oxapropane

1,3‐Bis(1H‐benzimidazol‐2‐yl)‐2‐oxapropane ( L ) complexes with Fe(NO₃)₃, CoCl₂, Co(NO₃)₂, Ni(NO₃)₂, CuCl₂, Cu(ClO₄)₂, PdCl₂, CdI₂, Hg(NO₃)₂ were synthesized and characterized by elemental analysis, molar conductivity, magnetic moment, TGA, FT‐IR, NMR, ESI‐MS, fluorescence spectroscopy. Also, the crystal structure of 1,3‐bis(1H‐benzimidazol‐2‐yl)‐2‐oxapropane]dichlorocobalt(II), [Co( L )Cl₂], complex is reported that it has distorted trigonal bipyramidal geometry. Antibacterial activities of the compounds were evaluated using the disk diffusion method against six bacteria and Candida albicans. The Hg(II) complex shows superior activity toward S. epidermidis and E. coli whereas the other complexes are ineffective except the Co(NO₃)₂ complex: it showed weak activity toward all of the microorganisms.     

Investigation of structure–spectroscopy–function relationship of two-dimensional J-aggregates of tetrachlorobenzimidazolocarbocyanine preferentially oriented in poly-vinyl-alcohol thin films

The structure–spectroscopy–function relationship of 1,1′,3,3′-tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine (TTBC) aggregates is studied using a combination of experimental and theoretical techniques. The aggregates are macroscopically aligned in poly-vinyl-alcohol thin films by vertical spin coating. Angular dependence of the UV–Vis spectra is measured at eleven different orientations between the electric field polarization and the macroscopic alignment axis. The aggregates are characterized by a pair of Davydov split bands with opposite polarization behaviors: an H-band (505 nm) and a J-band (594 nm) polarized respectively, close to being parallel and perpendicular to the alignment axis. Spectral response is interpreted via simulations within the Frenkel exciton formalism. TTBC aggregates are shown to assume very similar internal molecular packing (herringbone) and dynamics of excited states (phonon-assisted intraband and interband relaxations) in ionic aqueous solution and in thin films. The general conclusions on the structure–spectroscopy–function relationship are expected to hold for other cyanine aggregates with the same generic spectral features.     

Synthesis of photoactive single‐chain folded polymeric nanoparticles via combination of radical polymerization techniques and Menschutkin click chemistry

This contribution reports that synthesis of polystyrene based photoactive polymeric nanoparticles by radical copolymerization and Menschutkin Chemistry methodology. In the first step, poly(styrene‐co‐chloromethyl styrene) was achieved by thermally initiated radical copolymerizations and subsequently copolymers were reacted to commercially available Type II photoiniator (Michler's ketone) in dilute condition in order to achieve intramolecular crosslinked polymeric nanoparticles. After the characterization studies, polymeric nanoparticles were used for free radical photopolymerization of methacrylic formulations to determine the initiation efficiency. Upon UV irradiation, resulting polymeric nanoparticle lost its globular structure by releasing benzophenone part and transformed into linear copolymer analogue. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1998–2003     

Poly(ethylene glycol)‐thioxanthone prepared by Diels–Alder click chemistry as one‐component polymeric photoinitiator for aqueous free‐radical polymerization

Novel water‐borne macrophotoinitiator containing thioxanthone (TX) end group was successfully synthesized by using Diels–Alder (DA) [4 + 2] click chemistry strategy. For this purpose, thioxanthone‐anthracene (TX‐A) and maleimide end‐functionalized poly(ethylene glycol) (PEG‐MI) were reacted in toluene at reflux temperature for 48 h. The final polymer (PEG‐TX) and the intermediates were characterized in detail by spectral analysis. PEG‐TX possesses absorption characteristics similar to the parent TX. The one‐component photoinitiating nature of the photointiator was demonstrated by photopolymeization of several hydrophilic vinyl monomers, such as acrylic acid, acrylamide, 2‐hydroxyethyl acrylate, and 1‐vinyl‐2‐pyrrolidone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2109–2114, 2010     

Preparation of hydrogels by photopolymerization of acrylates in the presence of Type I and one-component Type II photoinitiators

Hydrogels were prepared by photoinduced polymerization of poly(ethylene glycol)monoacrylate (PEGMA) and poly(ethylene glycol)diacrylate (n = 200 and 700) (PEGDA) with Type I, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (I-2959) and one-component Type II initiators: (9-oxo-9H-thioxanthen-2-yloxy)-acetic acid (TXOCH₂COOH) and (9-oxo-9H-thioxanthen-2-yloxy)-sodium acetate (TXOCH₂COO^?Na⁺). The swelling properties of hydrogels were investigated and observed to be excellent. Smooth morphology and no phase separation were observed from SEM micrographs of the hydrogels.     

Synthesis,characterization, and biological evaluation of new copper complexes of naphthyl pyrazole ligands

Two naphthalene pyrazole ligands were synthesized using KOH/DMSO and Cu catalyst and characterized with FT-IR, ESI-MS, ¹H, and ¹³C NMR spectroscopies. The crystal structures of 1-(2-methylnaphthalen-1-yl)-1H-pyrazole (MeNap-Pz) ligand have been determined with X-ray crystal structure analysis. Reaction of the ligands with Cu(NO₃)₂x3.5H₂O gave two new complexes and characterized with magnetic susceptibility, molar conductance, FT-IR, LCMS-MS, ICP-OES, NMR, thermogravimetric analysis, and ESR spectra. The spectral data of the ligands are coordinated to the metal ion through the nitrogen atoms of the pyrazole ring. Consequently, it has been determined that [Cu(MeNap-Pz)₂(NO₃)]NO₃.2H₂O complex showed square planar geometry and [Cu(NapMe-Pz)₂(NO₃)₂].H₂O complex showed octahedral geometry. All compounds were screened for in vitro antibacterial activity and copper complexes have been shown to be effective on bacteria.     

Effect of κ-carrageenan on volume phase transition for polyacrylamide (PAAm) hydrogel using the fluorescence technique

Steady-state fluorescence (SSF) technique was employed for studying swelling of polyacrylamide (PAAm) gels with various content of κ-carrageenan (κC). Disc shaped composite hydrogels were prepared by free-radical crosslinking copolymerization of acrylamide (AAm) with various amounts κC. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as crosslinker and initiator, respectively. Pyranine was introduced as a fluorescence probe. Fluorescence intensity of pyranine was monitored during in situ swelling processes of composite gels. It was observed that fluorescence intensity values decreased as swelling is proceeded. Li–Tanaka equation was used to determine the swelling time constants, τ and cooperative diffusion coefficients, D from intensity variations during the swelling processes. It was shown that swelling time constants, τ decreased and diffusion coefficients, D increased as the κC content in the composites are increased.     

A fluorescence study for the critical behavior of polymethylmethacrylate doped by multiwalled carbon nanotube (PMMA–MWNT) composite bulk gel systems

Polymethylmethacrylate (PMMA) doped by multiwalled carbon nanotube (MWNT) bulk gels were prepared with different amounts of MWNTs varying in the range between 1 and 20 wt%. Free-radical cross-linking copolymerization of PMMA–MWNT composite bulk gels was characterized by the steady-state fluorescence technique. Ethylene glycol dimethacrylate (EGDM) and pyrene (P _y ) were introduced as cross linker and fluorescence probe, respectively. Changes in the viscosity of the pregel solutions due to glass formation dramatically increased the P _y fluorescent intensities, which were used to study the glass transition of PMMA–MWNT composite gels for various MWNT contents. The fluorescence intensity of P _y is proportional to the average size of the glassy regions below and to the strength of the infinite network above the glass transition point. Observations around the glass transition point show that there are three regimes for MWNT concentration in which the gel fraction exponent, β, and the weight average degree of polymerization exponent, γ, differ drastically from percolation results, given in three dimensions as β=0.41 and γ=1.80.