Phosphonate electrochemical recognition by molecularly imprinted deposited film

In this paper, thin films of titanium oxide imprinted with O,O-dimethyl-(2,4-dichlorophenoxyacetoxyl)(3′-nitrobenyl) methinephosphonate (Phi-NO₂) were prepared via liquid phase deposition (LPD) method on a glassy carbon electrode. The imprinted molecular in the films was removed by treatment with immersion in CH₂Cl₂. X-ray diffraction (XRD) and electrochemical methods were introduced to show the evidence of the molecular imprinting phenomenon. It was also found that the recognition ability of the sensor depended on the substituents associated with tridimensional structures of the nitro-compounds. Under the optimized condition, the sensor showed better sensitivity, selectivity and reproducibility to the imprinted molecule and the linear relationship between the current and the concentration of analyte in the range of 0.1-50 μM was obtained. LPD proved to be a powerful method for imprinting titanium oxide thin sense films.     

Synthesis and kinetic evaluation of 4-deoxy-4-phosphonomethyl-d-erythronate, the first hydrolytically stable and potent competitive inhibitor of ribose-5-phosphate isomerase

4-deoxy-4-Phosphonomethyl-d-erythronate, an isosteric and hydrolytically stable analogue of the known ribose-5-phosphate isomerase inhibitor 4-deoxy-4-phospho-d-erythronate, was obtained by a 14-step synthesis from d-arabinose through an highly improved synthesis of the precursor 5-deoxy-5-phosphonomethyl-d-arabinose. The title compound appears as the first stable and potent competitive inhibitor of the enzyme catalyzed isomerization of ribose-5-phosphate to d-ribulose-5-phosphate (K_i=74 μM, K_m/K_i=100), exhibiting only a 3-fold weaker inhibitory activity than its phosphate analogue.     

Synthesis and Characterization of Copper(II)–Phosphonate Coordination Chain Array of Metallocages

Reaction of CuCl₂ ·2H₂O and 2,4,6‐tris(phosphorylmethyl)mesitylene (H₆tpmm) in H₂O?DMF solution at room temperature afforded green crystals of [Cu₆(H₂tpmm)₃(H₂O)₉]·3H₂O ( 1 ), which were characterized by Fourier transform infrared (FT‐IR), thermogravimetric (TG) analysis, and powder X‐ray diffraction (PXRD). The solid‐state structure of 1 reveals a one‐dimensional chain array of M₄L₂ ‐metallocages constituted by the connection of two kinds of metallocage units, namely MC‐A (phosphonate/water‐bridged) and MC‐B (phosphonate‐bridged only), via μ₂‐O(phosphonate)? Cu bonds in ABAABA order. The tris‐phosphonate ligand H₆tpmm is partially deprotonated to form H₂tpmm^4?, which displays a cis,cis,cis conformation to bridge six Cu(II) centers via two monodentate phosphonate groups in a η ⁰:η ⁰:η ¹‐bonding mode and one tridentate phosphonate group in a μ₄, η ¹:η ¹:η ²‐bondingng mode.     

Synthesis and characterization of water-soluble palladium(II)-functionalized diphosphine complexes

Water-soluble functionalized bis(phosphine) ligands L (a–h) of the general formula CH₂(CH₂PR₂)₂, where for a: R = (CH₂)₆OH; b–g: R = (CH₂)_nP(O)(OEt)₂, n = 2–6 and n = 8; h: R = (CH₂)₃NH₂ ( Scheme 1), have been prepared photochemically by hydrophosphination of the corresponding 1-alkenes with H₂P(CH₂)₃PH₂. Water-soluble palladium complexes cis-[Pd(L)(OAc)₂] (1–8) were obtained by the reaction of Pd(OAc)₂ with the ligands a–h in a 1:1 mixture of dichloromethane:acetonitrile. The water-soluble phosphine ligands and their palladium complexes were characterized by IR, ¹H and ³¹P NMR. A crystallographic study of complex 1 shows that the Pd(II) ion has a square planar coordination sphere in which the acetate ligands and the diphosphine ligand deviate by less than 0.12 Å from ideal planar.     

Synthesis of novel 2,5-dihydro-1,5,2-diazaphosphinines from primary enamine phosphonates and from alkyl phosphonates

A simple method for the preparation of phosphorus-containing pyrimidine analogues such as 2,5-dihydro-2-ethoxy-1,5,2-diazaphosphinine 2-oxides 9, 12-15 and adducts 3, 10 is described. Dihydrophosphinines 9, 12-15 are prepared from primary enamine phosphonates and nitriles or from phosphonates and nitriles in the presence of base, while highly stable hydrogen-bonded amine-dihydro-diazaphosphinine adducts 3, 10 are obtained by the addition of amine to dihydrophosphinines 9 or by reaction of alkylphosphonates with nitriles in the presence of LDA.     

Layered metal phosphonates containing pyridyl groups: Syntheses and characterization of Mn2(2-C5H4NPO3)2(H2O) and Zn(6-Me-2-C5H4NPO3)

This paper reports the syntheses and characterization of two phosphonate compounds with layered structures, namely, Mn₂(2-C₅H₄NPO₃)₂(H₂O) (1) and Zn(6-Me-2-C₅H₄NPO₃) (2). In compound 1, double chains are found in which the {Mn₂O₂} dimers are linked by both aqua and O-P-O bridges. These double chains are connected through corner-sharing of {MnO₅N} octahedra and {CPO₃} tetrahedra, forming an inorganic layer. The pyridyl groups fill the inter-layer spaces. In compound 2, each {ZnO₃N} tetrahedron is vertex-shared with three {CPO₃} tetrahedra and vice versa, hence forming an inorganic honeycomb layer. The pyridyl groups reside between the layers. Magnetic studies show that weak antiferromagnetic interactions are mediated between the manganese ions in compound 1. Crystal data for 1: monoclinic, space group C2/c, , , , β=107.3(1)°. For 2: orthorhombic, space group Pbca, , , .     

Synthese de Nouveaux Derives Phosphones a Chaine Perfluoree et Leurs Proprietes Adhesives Sur Acier

Ce mémoire décrit la synthèse de phosphonates comportant une chaîne perfluorée. Ces composés sont obtenus par la télomérisation d'allylphosphonates de dialkyle en présence d'un agent de transfert fluoré de type mercaptan. Ensuite, nous employons deux méthodes de déalkylation menant sélectivement soit au monoacide soit au diacide phosphonique. Tous ces produits comprenant une extrémité de chaîne phosphonée, sous forme acide ou ester, ont été caractérisés et leur adhésion respective sur des plaques d'acier est étudiée. Ces tests montrent que le monoacide phosphonique est un excellent promoteur d'adhésion et qu'il est aussi efficace que le diacide. This article describes the synthesis of phosphonic derivatives bearing a perfluorinated chain. These compounds have been synthetized by telomerization of dialkyl allylphosphonate with a fluorinated transfer agent type mercaptan. Then two methods of dealkylation leading selectively were used to mono or to diacid phosphonic moieties. All the products bearing phosphonic end-groups, more or less acidic, have been characterized and their own adhesion on steel plates is studied. These tests show that phosphonic monoacid is an excellent adhesion promoter on steel, as efficient as the diacid compound.     

Efficient Method for The Synthesis of α-Amidophosphonates via the Michaelis-Arbuzov Reaction

Abstract

A new series of modified α-amidophosphonates (or β-ketophosphonate) was synthesized by an efficient method, starting from aminoesters and chloroacetyl chloride. We have established that chloroacetyl chloride is a suitable reagent allowing the introduction a halogen moiety for the Arbuzov reaction. The α-amidophosphonates were prepared in two steps (acetylation, phosphorylation).

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Rational Synthesis of Amorphous Iron-Nickel Phosphonates for Highly Efficient Photocatalytic Water Oxidation with Almost 100 % Yield

A simple solvent ligation effect was successfully used to disrupt the growth of a model compound, Fe[(OH)(O₃P(CH₂)₂CO₂H)]⋅H₂O (MIL-37), into an extended 2D structure by replacing water with dimethylformamide (DMF) as the solvent during the synthesis. Owing to the lack of −OH group, which provides the corner-sharing (binding) oxygen atoms for the octahedra, an amorphous and porous structure is formed. When Fe³⁺ is partially replaced by Ni²⁺, the amorphous structure remains and the resultant binary metal catalyst displays excellent photocatalytic oxygen evolution activity with almost 100 % yield achieved under visible light irradiation using [Ru(bpy)₃]²⁺ as the photosensitizer. This study opens up new possibilities of using the simple solvent effect to synthesize high surface area metal phosphonates for catalytic and other applications.