A Six-Coordinate Picrate Nickel(II) Complex Based on the V-Shaped Ligand 1,3-Bis (1-Benzylbenzimidazol-2-yl)-2-Thiapropane: Synthesis,Crystal Structure,Biological Activities

Abstract

A six-coordinate picrate nickel(II) complex based on the V-shaped ligand 1,3-bis(1-benzylbenzimidazol-2-yl)-2-thiapropane (L), with the composition [Ni(L)₂](pic)₂, has been synthesized and characterized systematically. The crystal structure of the Ni(II) complex is a six-coordinated octahedron, which is considerably close to ideal octahedral geometry with N₄S₂ donors of the two ligands. Biological activities of compounds were investigated using electronic absorption spectroscopy, fluorescence spectroscopy, and viscosity measurements. The results suggested that both ligand L and Ni(II) complex bind to DNA in an intercalative binding mode, and DNA-binding affinity of the Ni(II) complex is stronger than that of ligand L.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional figures.]     

Raman and Infrared Spectroscopic Characterization of the Phosphate Mineral Lithiophilite—LiMnPO4

Abstract

The metal lithium is very important in industry, including lithium batteries. An important source of lithium besides continental brines is granitic pegmatites as in Australia. Lithiophilite is a lithium and manganese phosphate with chemical formula LiMnPO₄ and forms a solid solution with triphylite, its Fe analog, and belongs to the triphylite group that includes karenwebberite, natrophilite, and sicklerite. The mineral lithiophilite was characterized by chemical analysis and spectroscopic techniques. The chemical is: Li_1.01(Mn_0.60, Fe_0.41, Mg_0.01, Ca_0.01)(PO₄)_0.99 and corresponds to an intermediate member of the triphylite-lithiophilite series, with predominance of the lithiophilite member. The mineral lithiophilite is readily characterized by Raman and infrared spectroscopy.     

Synthesis of some novel 5-substituted benzamido-6-arylamino-pyrazolo[3,4-D]pyrimidin-4-one derivatives for herbicidal activity

Abstract

Sixteen novel 3-methylthio-5-substituted benzamido-6-arylamino-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H)-one derivatives (4a–p) were successfully synthesized from iminophosphoranes, aryl isocyanate, and substituted benzoylhydrazine. The structures of the title compounds were elucidated by FT-IR, ¹H NMR, ¹³C NMR, and HRMS. Herbicidal activity of the compounds 4a–p against Brassica napus (rape), Echinochloa crusgalli (barnyard grass), Cucumis sativus (cucumber), and Triticum aestivum (wheat) were determined. The results showed that 5-(2-chlorobenzamido)-6-phenylamino-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H)-one (4c) displayed remarkable inhibition activity against the stalk and root of rape with 100% inhibition rate at the dosages of 10?mg/L and 100?mg/L, and 5-(4-nitrobenzamido)-6-phenylamino-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H) -one (4d) exhibited excellent activity against the stalk and root of barnyard grass with 100% inhibition rate at the same dosages.     

Detection of Chemical Warfare Nerve Agents via a Beckmann Fragmentation of Aldoxime

Abstract

A new (E)-pyrene-1-carbaldehyde O-tert-butyldimethylsilyl oxime 3 was synthesized for the detection of chemical warfare nerve agents, O-isopropyl methylphosphonofluoridate (GB) and O-pinacolyl methylphosphonofluoridate (GD). ¹H NMR spectrum showed that the tert-butyldimethylsilyl (TBDMS) group was deprotected using TBAF and the oximate supernucleophile was made. Upon addition of chemical warfare agents (GB and GD) (50 mol%), the reaction was completely finished within 5 min and also the color change of reaction mixture was observed under a hand-held UV lamp with the naked eye.     

Synthesis and characterization of poly(2‐methacryloyloxyethyl phosphorylcholine) onto graphene oxide

The polyzwitterionic brushes comprised of poly(2‐methacryloyloxyethyl phosphorylcholine) (pMPC) segments, which are used for surface modification of polymers and biocompatible coatings, were investigated. In this work, reverse surface‐initiated atom transfer radical polymerization (RATRP) of zwitterionic 2‐methacryloyloxyethyl phosphorylcholine (MPC) is employed to tailor the functionality of graphene oxide (GeneO) in a well‐controlled manner and produce a series of well‐defined hemocompatible hybrids (termed as GeneO‐g‐pMPC). The complexes were characterized by FT‐IR, XRD, and Raman. Results show that MPC has been coordinated on the graphene oxide sheet. Thermal stability of the nanocomposites in comparison with the neat copolymer is revealed by thermogravimetric analysis and differential thermal analysis. Scanning electron microscopy and transmission electron microscope images of the nanoconposite displays pMPC chains were capable of existing on GeneO sheet by RATRP. The biocompatibility properties were measured by plasma recalcification profile tests, hemolysis test, and MTT assays, respectively. The results confirm that the pMPC grafting can substantially enhance the hemocompatibility of the GeneO particles, and the GeneO‐g‐pMPC hybrids can be used as biomaterials without causing any hemolysis. With the versatility of RATRP and the excellent hemocompatibility of zwitterionic polymer chains, the GeneO‐g‐pMPC nanoparticles with desirable blood properties can be readily tailored to cater to various biomedical applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization of Nitro-Substituted Polybenzimidazole Synthesized by the Reaction with Nitric Acid

Abstract

Nitro-substituted poly[2,2′-(m-phenylene)-5,5′-bibenzimidazole]s (PBIs) were synthesized by the reaction of PBI with nitric acid in sulfuric acid under various conditions. The number of nitro groups substituted on the aromatic ring of PBI per polymeric unit varied from 1.44 to 3.55 according to the reaction conditions. An increase in reaction temperature and concentration of the nitric acid increased the degree of substitution. The inherent viscosity of the substituted polymer increased as the reaction temperature decreased. When the reaction temperature was 30°C, the inherent viscosity of the polymer increased as the concentration of nitric acid increased. The nitro-substituted PBI exhibited polyelectrolyte behavior in formic acid. The nitro groups substituted on PBI were dissociated when the polymer was heated to 450°C, displaying exothermic behavior, and the decomposition of polymer was proportional to its nitro group content. All nitro-substituted PBIs showed better solubilities in polar aprotic and acidic solvents, such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, formic acid, sulfuric acid, and trifluoromethanesulfonic acid.     

Rates of Sulfonation of Bead Copolymers of Styrene Cross - Linked with Mixtures of m- and p-Divinylbenzene

Abstract

The rate of sulfonation of bead copolymers of styrene cross-linked with 8 mole % divinylbenzene (mixed isomers) is remarkably sensitive to the isomeric (para/meta) composition of the mixture of divinylbenzenes. The rate is enhanced by a factor of 4 for compositions containing 20–40% para isomer.     

Synthesis and enantioselective fluorescent sensors for amino acid derivatives based on BINOL

Four novel derivatives of 1,1′-bi-2-naphthol have been prepared and the structures of these compounds characterised by IR, MS, ¹H and ¹³C NMR spectroscopy and elemental analysis. The enantioselective recognition of these sensors has been studied by fluorescence titration and ¹H NMR spectroscopy. The sensors exhibited different chiral recognition abilities towards N-Boc-protected amino acid anions and formed 1:1 complexes between the host and the guest. Sensors exhibit excellent enantioselective fluorescent recognition ability towards the amino acid derivatives.     

Room Temperature Phosphorescence of 1-Bromo-4-(bromoacetyl)naphthalene Induced by Sodium Deoxycholate

Sodium deoxycholate (NaDOC) can induce 1-bromo-4-(bromoacetyl)naphthalene (BBAN) to undergo strong room temperature phosphorescence (RTP) without the removal of dissolved oxygen from the solution. RTP spectra, phosphorescence polarization and ¹³C NMR results, along with the molecular modeling calculations, supported the conclusion that BBAN molecule was combined in a sandwich with two NaDOC molecules by a “back-to-back” hydrophobic interaction arising from the apolar faces of the NaDOC molecules, which provided BBAN with a rigid enough microenvironment to produce RTP.     

Two Thiourea-based Colorimetric Sensors for Anions: Structure and Binding Study

Two colorimetric thiourea-based chemsensors with two relatively rigid arms, 2A and 2B, were synthesized. Their binding abilities with halide anions, AcO^?, [Formula: See Text] were studied by UV-Vis spectroscopy in DMSO. The two sensors showed a notable selective color response to F^? anion from colorless to green-yellow in recognition. The structures of the two sensors and their binding behaviors are discussed. The association constants were calculated by nonlinear fittings of 1:1, 1:2 or 1:1 to 1:2.