Mn位掺杂钙钛矿结构化合物LaSr2Mn2-xNixO7的磁性和电性的研究

The effect of Ni substitution for Mn on magnetic and transport properties has been investigated for layered manganese oxides LaSr₂Mn_2-xNi_xO₇. Nickel doping hampered the canted antiferromagnetic (AFM) exchange at low temperature and their Neel temperature (T_N) decreased from 138 K (x=0) to 102 K (x=0.3). Meanwhile, spin glass, charge ordering and metal-insulator transition are suppressed by Ni addition. The resistivity increases obviously with increasing x due to double exchange interaction channel broken by Ni²⁺ addition. The resistivity of all samples in low temperature range fits to the Mott′s variable rang hopping (VRH) model, while it fits to nearest neighbor hopping of small polarons model in high temperature range.     

The relative reactivities of various unsaturated compounds towards diisopropyloxy(η-cyclopentene)titanium

Competition experiments were performed by adding pre-formed solutions of diisopropyloxy(η²-cyclopentene)titanium in diethyl ether to various mixtures of unsaturated compounds at low temperature, establishing the following reactivity scale: aldehyde > nitrile > ketone > terminal alkyne > internal alkyne > terminal alkene > ester, carbonate.     

Sorption properties of freshly precipitated alumogels

The influence of the pH of precipitation and the ionic medium nature on the composition, surface charge, and kinetic sorption characteristics of aluminum oxyhydroxides formed by alkaline hydrolysis of an aqueous solution of aluminum nitrate was studied. The methods of drop titration with alkali, argentometric titration, point of zero charge, and indicator reactions of heterogeneous hydrolysis were used. The composition of the freshly precipitated hydrogels of aluminum(iii) oxyhydroxide, rate constants of heterogeneous hydrolysis of the IrCl₆ ^2– ions as indicator reactions, and the pH of the point of zero charge were determined. The rate of indicator reactions (as for other oxyhydroxide hydrogels) depends strongly on the pH of precipitation. However, it is lower than the rates characteristics of iron(iii) and chromium(iii) oxyhydroxides obtained under similar conditions. The pH of the point of zero charge for the alumogels in a chloride medium is 8.3 and that in a sulfate medium is 9.5.     

Genetic engineering to enhance the selectivity of protein separations

The ability to recover and purify natural and recombinant proteins, and the costs of doing so remain a major task in introducing the potential products of biotechnology. The bases for separation range from specific binding onto tailored reagents to solubility and partitioning behavior governed by a mixed bag of size, charge, and hydrophobicity. In most cases, a combination of methods is used in sequence, and improvements in the selectivity at an early stage can enhance the effectiveness of subsequent (and usually more costly) steps. Genetic engineering provides a means of improving the selectivity within the context of existing separation methods. By this strategy, improvements in selectivity are sought by bestowing a distinctive property on the protein of interest. The primary sequence of amino acids is altered, such that the protein can be selectively removed from other components of the multicomponent mixture in which such products are commonly found. In this article, the range of these “distinctive properties” and their pairing with various separation methods will be reviewed. Specific examples from our work, in which a distinctive charge is provided via a polypeptide “purification” fusion tail, will be discussed. Separation methods we have used with these fusion proteins are precipitation, two-phase aqueous extraction, reversed micellar extraction, and ion exchange using both resins and membranes.     

SYNTHESIS OF THE NOVEL CHIRAL POLYMERS WITH MULTIDENTATE LIGAND AND RESOLUTION OF DL-AMINO ACIDS

A new way for synthesizing styrenic type of chiral resins grafting to multidentate ligand has been found. The synthetic scheme is proved to be practical by means of elemental anaysis, IR spectra and metal adsorbility. The resolving power of the new chiral ligand resins coordinated with copper (Ⅱ) as stationary phases has been discussed based on HPLC, and some points of view about the compositions of mobil phase and mechanism of resolution are presented.     

Ab initio study of the complexes of halogen-containing molecules RX (X=Cl, Br, and I) and NH3: towards understanding the nature of halogen bonding and the electron-accepting propensities of covalently bonded halogen atoms

Ab initio calculations have been performed on a series of complexes formed between halogen-containing molecules and ammonia to gain a deeper insight into the nature of halogen bonding. It appears that the dihalogen molecules form the strongest halogen-bonded complexes with ammonia, followed by HOX; the charge-transfer-type contribution has been demonstrated to dominate the halogen bonding in these complexes. For the complexes involving carbon-bound halogen molecules, our calculations clearly indicate that electrostatic interactions are mainly responsible for their binding energies. Whereas the halogen-bond strength is significantly enhanced by progressive fluorine substitution, the substitution of a hydrogen atom by a methyl group in the CH(3)X...NH(3) complex weakened the halogen bonding. Moreover, remote substituent effects have also been noted in the complexes of halobenzenes with different para substituents. The influence of the hybridization state of the carbon atom bonded to the halogen atom has also been examined and the results reveal that halogen-bond strengths decrease in the order HC triple bond CX > H(2)C=CHX approximately O=CHX approximately C(6)H(5)X > CH(3)X. In addition, several excellent linear correlations have been established between the interaction energies and both the amount of charge transfer and the electrostatic potentials corresponding to an electron density of 0.002 au along the R-X axis; these correlations provide good models with which to evaluate the electron-accepting abilities of the covalently bonded halogen atoms. Finally, some positively charged halogen-bonded systems have been investigated and the effect of the charge has been discussed.     

Validation of the thermodynamic model of inorganic arsenic in non polluted river waters of the Basque country (Spain)

The thermodynamic model of inorganic arsenic was validated by comparing the predicted As(III) concentration with the experimentally determined one in several river waters samples of the Basque Country (Spain) collected in two sampling campaigns: spring and autumn 2000. This model takes into account the acid-base equilibria of As(III) and As(V) together with the redox equilibria between the H₃AsO₃ and H₃AsO₄ species. A correct prediction of As(III) concentration requires the knowledge of the total concentration of arsenic, pH, redox potential (referred to hydrogen electrode), and ionic strength values of the solution. The estimation of the activity coefficients of the arsenic species was performed by means of the Modified Bromley’s Methodology (MBM).In order to perform the experimental As(III) determination, an analytical method was implemented by using an ion exchange separation of As(III)/As(V) on a continuous FIA-IE-HG-AAS system. The total arsenic concentration was determined together with total concentration of the main alkaline or alkaline-earth metals and anions in the natural waters. Temperature compensated measurements of the pH and redox potentials were made in-situ at the sampling sites.For both seasonal campaigns, the agreement between predicted and experimental As(III) is really high for those samples belonging to non polluted river waters.