Studies on thermal degradation of acrylonitrile–butadiene–styrene copolymer (ABS-Br) containing brominated flame retardant

The thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS-Br; 10 g) containing brominated flame retardant (Br: 9.59 wt.%) was carried out at 450 °C using a semi batch operation using two different temperature programs. The heating rate was found to affect the quality of the degradation oil and yield of products (liquid, gas and residue). Data on the effect of the temperature program on the accumulation of liquid products was presented. It was found that the majority of the bromine was concentrated in the carbon residue and while majority of the nitrogen accumulates in the liquid products irrespective of degradation mode. The use of a one step constant heating rate process (I) produced a higher liquid yield (39%), than a two step process (29%). Differences were also noted in the Br and N contained in the liquids produced by the two processes.     

Transamidation of Amides and Amidation of Esters by Selective N–C(O)/O–C(O) Cleavage Mediated by Air- and Moisture-Stable Half-Sandwich Nickel(II)–NHC Complexes

The formation of amide bonds represents one of the most fundamental processes in organic synthesis. Transition-metal-catalyzed activation of acyclic twisted amides has emerged as an increasingly powerful platform in synthesis. Herein, we report the transamidation of N-activated twisted amides by selective N–C(O) cleavage mediated by air- and moisture-stable half-sandwich Ni(II)–NHC (NHC = N-heterocyclic carbenes) complexes. We demonstrate that the readily available cyclopentadienyl complex, [CpNi(IPr)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), promotes highly selective transamidation of the N–C(O) bond in twisted N-Boc amides with non-nucleophilic anilines. The reaction provides access to secondary anilides via the non-conventional amide bond-forming pathway. Furthermore, the amidation of activated phenolic and unactivated methyl esters mediated by [CpNi(IPr)Cl] is reported. This study sets the stage for the broad utilization of well-defined, air- and moisture-stable Ni(II)–NHC complexes in catalytic amide bond-forming protocols by unconventional C(acyl)–N and C(acyl)–O bond cleavage reactions.     

1,5-Benzothiazepine Derivatives: Green Synthesis,In Silico and In Vitro Evaluation as Anticancer Agents

Considering the importance of benzothiazepine pharmacophore, an attempt was carried out to synthesize novel 1,5-benzothiazepine derivatives using polyethylene glycol-400 (PEG-400)-mediated pathways. Initially, different chalcones were synthesized and then subjected to a cyclization step with benzothiazepine in the presence of bleaching clay and PEG-400. PEG-400-mediated synthesis resulted in a yield of more than 95% in less than an hour of reaction time. Synthesized compounds 2a–2j were investigated for their in vitro cytotoxic activity. Moreover, the same compounds were subjected to systematic in silico screening for the identification of target proteins such as human adenosine kinase, glycogen synthase kinase-3β, and human mitogen-activated protein kinase 1. The compounds showed promising results in cytotoxicity assays; among the tested compounds, 2c showed the most potent cytotoxic activity in the liver cancer cell line Hep G-2, with an IC₅₀ of 3.29 ± 0.15 µM, whereas the standard drug IC₅₀ was 4.68 ± 0.17 µM. In the prostate cancer cell line DU-145, the compounds displayed IC₅₀ ranges of 15.42 ± 0.16 to 41.34 ± 0.12 µM, while the standard drug had an IC₅₀ of 21.96 ± 0.15 µM. In terms of structural insights, the halogenated phenyl substitution on the second position of benzothiazepine was found to significantly improve the biological activity. This characteristic feature is supported by the binding patterns on the selected target proteins in docking simulations. In this study, 1,5-benzothiazepines have been identified as potential anticancer agents which can be further exploited for the development of more potent derivatives.     

Redox-active ionic-liquid-assisted one-step general method for preparing gold nanoparticle thin films: applications in refractive index sensing and catalysis

We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.     

Synthesis of Chiral Ionic Polymers Containing Quaternary Ammonium Sulfonate Structure and their Catalytic Activity in Asymmetric Alkylation

Repeated reaction between chiral quaternary ammonium dimer and disodium disulfonate gave the ionic polymer, which contains chiral quaternary ammonium sulfonate structure as a repeating unit. This chiral ionic polymer showed an excellent catalytic activity in asymmetric alkylation reaction. With the chiral ionic polymer catalysts, high level of enantioselectivities up to 97% ee were attained.     

Reactions of [HOs3(CO)8{µ3-Ph2PCH(R)P(Ph)C6H4}] (R = H,Me) with Bu3SnH: synthesis and structure of bimetallic Os-Sn clusters

Reactions of unsaturated [HOs₃(CO)₈{µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] (R?=?H, Me) with Bu₃SnH are examined. [HOs₃(CO)₈{µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] reacts with Bu₃SnH at room temperature to afford [H₂Os₃(CO)₈(SnBu₃){µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] (1) via oxidative addition of the Sn?H bond to the parent cluster. Heating 1 in refluxing toluene leads to the formation of [H₂Os₃(CO)₇(SnBu₃){µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] (2) through decarbonylation. Cluster 2 exists in two isomeric forms in solution which has been probed by VT NMR spectroscopy. The new Os-Sn bimetallic clusters have been characterized by a combination of analytical and spectroscopic data together with single-crystal X-ray diffraction analysis.

Graphic abstract

     

Networks of periodic orbits in the circular restricted three-body problem with first order post-Newtonian terms

The motivation of this article is to numerically investigate the orbital dynamics of the planar post-Newtonian circular restricted problem of three bodies. By numerically integrating several large sets of initial conditions of orbits we obtain the basins of escape. Additionally, we determine the influence of the transition parameter on the orbital structure of the system, as well as on the families of simple symmetric periodic orbits. The networks and the stability of the symmetric periodic orbits are revealed, while the corresponding critical periodic solutions are also identified. The parametric evolution of the horizontal and the vertical stability of the periodic orbits are also monitored, as a function of the transition parameter.

     

First Synthesis of Continuous Mesoporous Copper Films with Uniformly Sized Pores by Electrochemical Soft Templating

Although mesoporous metals have been synthesized by electrochemical methods, the possible compositions have been limited to noble metals (e.g., palladium, platinum, gold) and their alloys. Herein we describe the first fabrication of continuously mesoporous Cu films using polymeric micelles as soft templates to control the growth of Cu under sophisticated electrochemical conditions. Uniformly sized mesopores are evenly distributed over the entire film, and the pore walls are composed of highly crystalized Cu.     

Synthesis and antibacterial activity of versatile substrate‐coated biocidal material via catechol chemistry

We report a potential coating material showing durable and significant antimicrobial activity for preserving the surfaces of a broad range of materials. The structure of the prepared antimicrobial adhesive material features a catechol moiety of dopamine hydrochloride conjugated to 4‐bromobutanoyl chloride as an adhesive material. Antimicrobial properties against a wide range of microorganism species are achieved by quaternizing a long hydrophobic chain (N,N'‐dimethyldecylamine) onto 3,4‐dihydroxyphenylalanine (Dopa) to afford the prepared material (Dopa‐decyl). The successful formation of Dopa‐decyl is confirmed by hydrogen nuclear magnetic resonance (¹H‐NMR) and attenuated total reflectance‐infrared (ATR‐IR) measurements. The chemical composition of the quaternized adhesive material (Dopa‐decyl) is characterized by X‐ray photoelectron spectroscopy (XPS). Investigation of the antimicrobial activity of the Dopa‐decyl‐coated film against both gram‐positive Staphylococcus aureus (S. aureus) and gram‐negative Escherichia coli (E. coli) stains reveals a highly efficient antimicrobial effect under both normal and extreme stress conditions due to the biocidal effect of the quaternized amine when the materials are applied on the surface of various substrates. Copyright © 2014 John Wiley & Sons, Ltd.     

Photo‐ and pH‐Tunable Multicolor Fluorescent Nanoparticle‐Based Spiropyran‐ and BODIPY‐Conjugated Polymer with Graphene Oxide

We report a stimuli‐responsive fluorescent nanomaterial, based on graphene oxide coupled with a polymer conjugated with photochromic spiropyran (SP) dye and hydrophobic boron dipyrromethane (BODIPY) dye, for application in triggered target multicolor bioimaging. Graphene oxide (GO) was reduced by catechol‐conjugated polymers under mildly alkaline conditions, which enabled to formation of functionalized multicolor graphene nanoparticles that can be induced by irradiation with UV light and by changing the pH from acidic to neutral. Investigation of these nanoparticles by using AFM, fluorescence emission, and in vitro cell and in vivo imaging revealed that they show different tunable colors in bioimaging applications and, more specifically, in cancer‐cell detection. The stability, biocompatibility, and quenching efficacy of this nanocomposite open a different perspective for cell imaging in different independent colors, sequentially and simultaneously.