Highly Efficient Copper(II) Ion Sorbents Obtained by Calcium Carbonate Mineralization on Functionalized Cross‐Linked Copolymers

A new type of Cu^II ion sorbents is presented. These are obtained by CaCO₃ mineralization from supersaturated solutions on gel‐like cross‐linked polymeric beads as insoluble templates. A divinylbenzene–ethylacrylate–acrylonitrile cross‐linked copolymer functionalized with weakly acidic, basic, or amphoteric functional groups has been used, as well as different initial inorganic concentrations and addition procedures for CaCO₃ crystal growth. The morphology of the new composites was investigated by SEM and compared to that of the unmodified beads, and the polymorph content was established by X‐ray diffraction. The beads, before and after CaCO₃ mineralization, were tested as sorbents for Cu^II ions. The newly formed patterns on the bead surface after Cu^II sorption were observed by SEM, and the elemental distribution on the composites and the chemical structure of crystals after interaction with Cu^II were investigated by EDAX elemental mapping and by FTIR‐ATR spectroscopy, respectively. The sorption capacity increased significantly after CaCO₃ crystals growth on the weak anionic bead surface (up to 1041.5 mg Cu^II/g sample) compared to that of unmodified beads (491.5 mg Cu^II/g sample).     

Dissolution of Cellulose and Lignin with Biobased Ionic Liquids

Journal of Solution Chemistry - Choline-based ionic liquids, involving various alkyl chains lengths and carboxylates derived from biobased acids, have been synthetized with high yields through a...     

New PP/PLA/cellulose composites: effect of cellulose functionalization on accelerated weathering behavior (accelerated weathering behavior of new PP/PLA/cellulose composites)

Polylactic acid (PLA) was used as partial replacement for conventional thermoplastic matrix, new composites comprising cellulose, polypropylene (PP), and PLA being realized. In order to obtain a compatible interface between cellulosic pulp and polymeric matrix, two chemical modifications of cellulose with stearoyl chloride and toluene di‐isocyanate (TDI) were performed, structural changes being evidenced by X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The composite materials were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic scanning calorimetry, impact, tensile and melt rheological tests, surface tension, and dynamic vapor sorption. Because promising results for impact strength and Young modulus were recorded when replacing 15% of PP with PLA in blends of PP with the same cellulosic pulp load, the aim of our study was to assess the behavior to accelerate weathering of composites comprising PP, cellulosic pulp, and PLA. Although the slight decrease in the mechanical properties was recorded after accelerated weathering, the use of functionalized cellulose successfully prevented the deterioration of surface materials, especially for composite comprising stearoyl chloride treated cellulose pulp. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,characterization of nanosized CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and its electrocatalytic activity for enhanced sensing application

Nanosized cobalt aluminate (CoAl₂O₄) was prepared by thermolysis of heteronuclear coordination compound, namely [Al₂Co(C₂O₄)₄(OH₂)₆]. The synthesized precursor was characterized by chemical analysis, vibrational spectra and thermal analysis. The cobalt aluminate obtained after a heating treatment of the precursor at 700 °C was characterized by IR, XRD, TEM coupled with SAED measurements. Two types of carbon-based electrodes, glassy carbon and boron-doped diamond electrodes were decorated with the obtained cobalt aluminate in order to enhance the electroanalytical performance for the tetracycline (TC) detection in the aqueous solutions. Cyclic voltammetry technique was used to determine the effect of the nanosized CoAl₂O₄ on the electrochemical oxidation of TC and as consequence, for TC detection at both carbon-based electrodes. The obtained cobalt aluminate exhibited the electrocatalytic activity toward TC detection in direct relation with the type of the carbon substrate, which allowed enhancing the electroanalytical parameters of TC detection in the aqueous solution.     

A simple method for the preparation of colloidal polymer-supported silver nanoparticles

Polysulfone?silver composite nanoparticles have been prepared by combining polymer nanoprecipitation and redox synthesis of silver, in the presence of a glucose-modified cyclosiloxane as stabilizing agent. Based on previous kinetic investigations and on model reactions, we concluded that the reducing agent in this case is the tetrahydrofuran (THF) used as solvent for polysulfone. Dynamic light scattering measurements on the obtained polymer-silver composite particles indicated particle average diameter of 176 nm with a polydispersity index of 0.25. The UV–vis spectrum exhibited the silver plasmon resonance. By different microscopic methods (atomic force microscopy—AFM, high resolution transmission electron microscopy—HRTEM, and scanning electron microscopy—SEM), larger polymer particles coated with silver nanoprticles were observed. The Energy Dispersive X-Ray analysis—EDX; confirmed the presence of Ag on the surface of the particles, while the selected area electron diffraction showed single crystalline silver nanospheres with face-centered cubic structure.     

Photocatalytically-assisted electrochemical degradation of <Emphasis Type="Italic">p</Emphasis>-aminophenol in aqueous solutions using zeolite-supported TiO<Subscript>2</Subscript> catalyst

This paper reports the results of an investigation into enhancement of the electrochemical oxidation of p-aminophenol (4-AP) in an aqueous solution with a boron-doped diamond (BDD) electrode, assisted by photocatalysis using a zeolite-supported TiO₂ (Z-TiO₂) catalyst. The BDD electrode was characterised in 0.1 M Na₂SO₄-supporting electrolyte and the presence of 4-AP by open-circuit potential behaviour (OCP) and cyclic voltammetry (CV). The electrode behaviour was investigated in the dark and following UV irradiation and in the absence/presence of the Z-TiO₂ catalyst. The electro-oxidation process was carried out using chronoamperometry (CA) and multiple-pulsed amperometry (MPA) at the selected potential under potentiostatic conditions. The electrochemical degradation process of 4-AP on the BDD electrode was improved by the application of a pulsed potential, which allowed both in-situ electrochemical cleaning of the electrode and indirect oxidation of 4-AP by oxygen evolution. The application of photocatalysis using Z-TiO₂ in the 4-AP electrochemical degradation exhibited an enhanced effect when the anodic potential was set at +1.25 V vs. Ag/AgCl in the water stability region, close to the oxygen evolution potential.     

DNA-assisted decoration of single-walled carbon nanotubes with gold nanoparticles for applications in surface-enhanced Raman scattering imaging of cells

Single-walled carbon nanotubes (SWNTs) are 1D nanostructures with distinct physical and chemical properties that have shown great promise for applications in many fields, including biomedicine. Since for biomedical application the water solubility is crucial and SWNTs have low solubility, various methods (including polymer and biopolymer wrapping, chemical modifications) have been developed to solubilize and disperse them in water. Due to their unique optical properties such as photoluminescence in the NIR and strong resonant Raman signatures, they can be used as nanoprobes in biomedical imaging and phototherapies. Furthermore, decoration of SWNTs with noble metal nanoparticles will induce an excellent surface-enhanced Raman scattering (SERS) effect of the nanoparticles-SWNTs composites, with applications in cell imaging. Herein, we present a new and facile strategy for the DNA-assisted decoration of SWNTs with gold nanoparticles (AuNPs) and their application in SERS imaging. By ultrasonication at room temperature of SWNTs with AuNPs functionalized with synthetic DNA, SWNT-AuNPs nanocomposites with enhanced Raman signal were obtained. Among the important advantages of the proposed method are the presence of the free DNA overhangs around the SWNT-AuNPs suitable for post-synthetic modification of nanocomposite through hybridization of complementary DNA strands containing molecules of interest attached by well-developed bio-conjugation chemistry.

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On the Monge–Ampère equation with boundary blow-up: existence,uniqueness and asymptotics

We consider the Monge–Ampère equation det D ² u = b(x)f(u) > 0 in Ω, subject to the singular boundary condition u = ∞ on ?Ω. We assume that \(b\in C^\infty(\overline{\Omega})\) is positive in Ω and non-negative on ?Ω. Under suitable conditions on f, we establish the existence of positive strictly convex solutions if Ω is a smooth strictly convex, bounded domain in \({\mathbb R}^N\) with N ≥ 2. We give asymptotic estimates of the behaviour of such solutions near ?Ω and a uniqueness result when the variation of f at ∞ is regular of index q greater than N (that is, \(\lim_{u\to \infty} f(\lambda u)/f(u)=\lambda^q\) , for every λ > 0). Using regular variation theory, we treat both cases: b > 0 on ?Ω and \(b\equiv 0\) on ?Ω.     

Synthesis and Biological Evaluation of Some New N1‐[4‐(4‐Chlorophenylsulfonyl)benzoyl]‐N 4‐(aryl)‐thiosemicarbazides and Products of Their Cyclization

In the present study, new 1,2,4‐triazoles, 1,3,4‐thiadiazoles, and acylthiosemicarbaz‐ides derived from 4‐(4‐chlorophenylsulfonyl)benzoic acid hydrazide were synthesized and screened for their antimicrobial and analgesic activities. Acylthiosemicarbazides 2–4 were synthesized by a reaction of 4‐(4‐chlorophenyl‐sulfonyl)benzoic acid hydrazide 1 with different arylisothiocyanates.4,5‐Disubstituted‐2,4‐dihydro‐3H‐1,2,4‐triazol‐3‐thiones 5–7 and 2,5‐disubstituted‐1,3,4‐thiadiazoles 8–10 were obtained by dehydrative cyclization of corresponding acylthiosemicarbazide derivatives 2–4 in basic media (8% aqueous sodium hydroxide) and in acidic media (sulfuric acid or phosphorous oxychloride), respectively. The structures of the newly synthesized compounds have been confirmed on the basis of elemental analysis and spectral studies (IR, ¹H NMR, ¹³C NMR, MS). Their antimicrobial activities against some bacteria and yeasts were investigated. The analgesic activity of all compounds was performed with two pharmacological tests: the writhing test induced with acetic acid and hot‐plate test. The results showed that triazole 7 had the best antimicrobial activity against Bacillus cereus. In the chemical stimulus test, triazoles 6 and 7 were the most active compounds whereas in the hot‐plate test thiadiazoles 9 and 10 exhibited the highest analgesic activity.