Application of HPLC to measure vanadium in environmental,biological and clinical matrices

Vanadate and vanadium compounds exist in many environmental, biological and clinical matrices, and despite the need only limited progress has been made on the analysis of vanadium compounds. The vanadium coordination chemistry of different oxidation states is known, and the result of the characterization and speciation analysis depends on the subsequent chemistry and the methods of analysis. Many studies have used a range of methods for the characterization and determination of metal ions in a variety of materials. One successful technique is high performance liquid chromatography (HPLC) that has been used mainly for measuring total vanadium level and metal speciation. Some cases have been reported where complexes of different oxidation states of vanadium have been separated by HPLC. Specifically reversed phase (RP) HPLC has frequently been used for the measurement of vanadium. Other HPLC methods such as normal phase, anion-exchange, cation-exchange, size exclusion and other RP-HPLC modes such as, ion-pair and micellar have been used to separate selected vanadium compounds. We will present a review that summarizes and critically analyzes the reported methods for analysis of vanadium salts and vanadium compounds in different sample matrices. We will compare various HPLC methods and modes including sample preparation, chelating reagents, mobile phase and detection methods. The comparison will allow us to identify the best analytical HPLC method and mode for measuring vanadium levels and what information such methods provide with regard to speciation and quantitation of the vanadium compounds.     

Darstellung und Kristallstruktur der Pnictidoxide Na2Ti2As2O und Na2Ti2Sb2O

Preparation and Crystal Structure of the Pnictide Oxides Na₂Ti₂As₂O and Na₂Ti₂Sb₂O Na₂Ti₂As₂O and Na₂Ti₂Sb₂O were synthesized in form of very easily hydrolysed metallic-grey powders by reaction of Na₂O and TiAs resp. TiSb in sealed tantalum tubes under argon. The tetrahedral bodycentered crystallizing compounds from a modified anti-K₂NiF₄ structure type [1] (also called Eu₄As₂O-type [2,3]), space group I4/mmm (no. 139), with the lattice constants for Na₂Ti₂As₂O: a = 407.0(2) pm, c = 1528.8(4) pm and for Na₂Ti₂Sb₂O: a = 414.4(0) pm, c = 1656.1(1) pm. Magnetic measurements of powder samples of Na₂Ti₂Sb₂O show antiferromagnetic interaction within the Ti—O-layers. Superconductivity was not found by ac-shielding method down to 4 K.     

Can semi-empirical models describe HCl dissociation in water?

We discuss the failure of commonly used AM1 and PM3 semiempirical methods to correctly describe acid dissociation. We focus our analysis on HCl because of its physicochemical importance and its relevance in atmospheric chemistry. The structure of non-dissociated and dissociated HCl – (H₂O) _n clusters is accounted for. The very bad results obtained with PM3 (and also with AM1) are related to large errors in gas-phase proton affinity of water and gas-phase acidity of HCl. Indeed, estimation of pKa values shows that neither AM1 nor PM3 are able to predict HCl dissociation in liquid water since HCl is found to be a weaker acid than H₃O⁺. We have proposed in previous works a modified PM3 approach (PM3-MAIS) adapted to intermolecular calculations. It is derived from PM3 by reparameterization of the core–core functions using ab initio data. Since parameters for H–Cl and O–Cl core–core interactions were not yet available, we have carried out the corresponding optimization. Application of the PM3-MAIS method to HCl dissociation in HCl–(H₂O) _n clusters leads to a huge improvement over PM3 results. Though the method predicts a slightly overestimated HCl acidity in water environment, the overall agreement with ab initio calculations is very satisfying and justifies efforts to develop new semiempirical methods.     

Fluoridolyse von Diphosphorylverbindungen

Fluoridolysis of Diphosphoryl Compounds The behaviour of diphosphoryl compounds [X₂(O)P]₂Y in fluoridolysis reactions is decisively determined by the nature of the bridging group Y. In the cases of Y = NH and CH₂ and X = Cl [F₂P(O)]₂N^? and [F₂P(O)]₂CH₂ are obtained quantitatively. For Y = NPh, O, and CH₂ the formation of phosphorylated pentafluorophosphates [F₅P? Y? POX₂]^? is observed. Amido and ester derivatives containing fluorine (see table 2) are obtained from the corresponding chloro compounds by Cl/F exchange. Fluoridolysis of the azadiphosphetidine 19 results in the formation of acyclic 19 a .     

Molecular Chains in the Crystals of a Calcium(II) Complex with Pyridine-3,5-Dicarboxylate (Dinicotinate) and Water Ligands

The crystal of pentaqua (catena-pyridine-3,5-dicarboxylato-O,O) calcium(II) contain zigzag molecular chains composed of Ca ions linked by two bridging oxygen atoms, each donated by one carboxylate group [Ca-O1 2.353(2) Å, Ca-O3^III 2.334(1) Å]. The Ca ions, the ligand molecules and one water oxygen atom coordinated by each metal ion [Ca-O5 2.410(2) Å] are coplanar. The coordination of the Ca ion is completed by four other water oxygen atoms situated above and below the plane of the chain [Ca-O6 2.475(1) Å, Ca-O7 2.371(2) Å]. The coordination number of the calcium(II) ion is seven. The water molecules act as donors in a system of hydrogen bonds.     

富羧酸基团的共轭微孔聚合物:结构单元对孔隙和气体吸附性能的影响

Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m²·g^-1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO₂ capture capabilities of 2.17 and 2.63 mmol·g^-1 (at 273 K and 1.05 × 10⁵ Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO₂ capture capabilities of 1.66 and 2.28 mmol·g^-1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.     

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.     

Synthesis of Tetrahydrobenzazepinesulfonamides and Their Rearrangement to Diarylsulfones

A new class of diarylsulfones, in which tetrahydrobenzazepine comprises one of the aromatic moieties, has been synthesized via the acid‐catalyzed rearrangement of several substituted benzazepinesulfonamides. The rearrangement is normally ortho but in at least one case a para isomer is also formed. Sulfones of this type have been shown to possess potent anti‐HIV activity.     

Biparametric multicommutated flow analysis system for determination of human serum phosphoesterase activity

A multicommutated flow analysis (MCFA) system constructed of microsolenoid valves and pumps offering simultaneous determination of activity of acid phosphatase (ACP) and alkaline phosphatase (ALP) in human serum samples has been developed. The MCFA system is based on optoelectronic flow-through detector made of two light emitting diodes and operating according to paired emitter detector diode (PEDD) principle. This photometric PEDD device has been dedicated for detection of p-nitrophenol (NP) generated in the course of enzymatic hydrolysis of p-nitrophenyl phosphate and optimized for the determination of NP in human serum samples. The developed PEDD-based MCFA system allows independent optimization of conditions for reaction and detection steps of photometric ACP and ALP bioassays. Moreover, it allows elimination of photometric interferences from serum matrix components according to two-points kinetic mode of measurement. The single measurement cycle takes 12 min, consists of four measurements (two for each phosphoesterase) and enables determination of serum ACP and ALP activities at physiological and pathological levels. The real analytical utility of the developed MCFA system has been confirmed by analysis of control sera as well as real human serum samples from healthy persons and oncological patients.