Adsorption recovery of thorium(IV) by Myrica rubra tannin and larch tannin immobilized onto collagen fibres

Novel adsorbents which can concentrate Th(IV) in aqueous solution were prepared by immobilizingMyrica rubra tannin and larch tannin onto collagen fibre matrices. The adsorption capacities of the immobilized tannins to Th(IV) are related to temperature and pH value of the adsorption process. For example, when the initial concentration of Th(IV) was 116.0 mg·l^-1 and the immobilized tannin was 100 mg, the adsorption capacities of immobilized Myrica rubra tannin and larch tannin were 55.98 mg Th(IV)·g^-1 and 13.19 mg Th(IV)·g^-1, respectively at 303 K, and 73.67 mg Th(IV)·g^-1 and 18.19 mg Th(IV)·g^-1 at 323 K. It was also found that the higher adsorption capacity was obtained at higher pH value. The adsorption equilibrium data of the immobilized tannins for Th(IV) can be well fitted by the Langmuir model and the mechanism of the adsorption was found to be a chemical adsorption. In general, the adsorption capacity of immobilized Myrica rubra tannin to Th(IV) is significantly higher than that of immobilized larch tannin, probably due to the fact that the B ring of Myrica rubra tannin has a pyrogallol structure which has higher reaction activity with metal ions. The breakthrough point of the adsorption column of immobilized Myrica rubra tannin was at 33 bed volumes for the experimental system. The mass transfer coefficient of adsorption column determined by Adams-Bohart equation was 1.61·10^-4 l·mg^-1.min^-1. The adsorption column can be easily regenerated by 0.1 mol·l^-1 HNO₃ solution, showing outstanding ability of concentrating Th(IV). This revised version was published online in July 2006 with corrections to the Cover Date.     

An efficient and general method for resolving cyclopropene carboxylic acids

A general method is described for the resolution of cycloprop-2-ene carboxylic acids via diastereomeric N-acyloxazolidines prepared from enantiomerically pure oxazolidinones. Although a number of oxazolidinones were shown to resolve cyclopropene carboxylic acids, the oxazolidinones of S-phenylalaninol, S-phenylglycine and (1S,2R)-cis-1-amino-2-indanol are optimal in terms of resolving power and cost effectiveness. Separations were performed using simple flash chromatography, and because there is typically a large difference in R_f values it is possible to separate gram quantities of pure diastereomers in a single chromatogram. The cycloprop-2-ene carboxylic acids that can be resolved include those that are substituted at the 1-position by H, Ph, α-naphthyl, CO₂Me, CH₂OMOM, and trans-styryl; alkene substituents include Me, n-alkyl, Ph and tethered alkynes. Remarkably, 2-methyl-3-propylcycloprop-2-ene carboxylic acid can also be resolved with ease. The relative configurations of four diastereomerically pure oxazolidines were determined by X-ray crystallography. Reduction of the N-acyloxazolidinones with LiBH₄ give enantiomerically pure derivatives of 3-hydroxymethylcyclopropene that react with either MeMgCl or vinylMgCl and catalytic CuI to give enantiomerically pure products of syn-addition.     

Synthesis and magnetic properties of trinuclear copper(II) complexes bridged by dimethylglyoximate groups

Summary New three Cu^II-Cu^II-Cu^II homotrinuclear complexes have been synthesized, namely [Cu(dmg)₂{CuL}₂](ClO₄)₂ [L = 5-nitro-1,10-phenanthroline (5-NO₂-phen), 4,4-dimethyl-2,2-bipyridiine (DMbpy), tetramethylenediamine (TMDA) and dimethylglyoximate ion (dmg)^2-]. The magnetic susceptibilities of complexes (1) (L = 5-NO₂-phen) and (2) (L = DMbpy) were measured in the 4.2–300 K range, giving the parameters,J = -335cm^-1 (1) andJ= -327.5cm^-1 (2). The results demonstrate a very strong antiferromagnetic exchange interaction between the adjacent copper(II) ions.     

Theory of solid solubility for rare earth metal based alloys

Both parabola and ellipse separating schemes are used to study the solid solubilities for the binary alloy systems based on the 13 rare earth metals. It has been found that the soluble elements can be separated from the insoluble ones by a parabolyy ₁=a?bx ₁ ² or an ellipse(x ₂?m)²/c²+(y₂?n)²/d²=1. The results show that the overall reliabilities of the solid solubilities for the 897 binary alloys based on the rare earth metals are 89.2% and 92.8% for the parabola and ellipse regularities respectively. The constants a and b in the parabola equation, andm, n, c andd in the ellipse equation are discussed, which can be related to some appropriate parameters for each host metal respectively.     

μ-phenoxo-bridged binuclear copper(II) complexes

Summary Two -phenoxo-bridged binuclear copper(II) complexes, [Fsal(GG)₂Cu₂Cl₃]·H₂O (1) containing an exogenous chloride-bridge and [Fsal(GG)₂Cu₂(OH)](ClO₄)₂·H₂O (2) containing an exogenous hydroxide-bridge, where {Fsal(GG)₂ = 2,6-bis[N-(acetylglycine)-imino-methylene]-4-methylphenol}, were synthesized. The complexes were characterized be several spectroscopic methods. According to variable temperature magnetic susceptibility measurements (4–300 K), the hydroxide-bridged complex (2) has a weak antiferromagnetic spin exchange integral (J =- 23.6 cm), while the chloride complex (1) has an unusual weak ferromagnetic spin exchange integral (J = + 30.9 cm); both complexes have similar optical spectra in the aqueous solutions.     

CHAOS FOR MIXING TRANSFORMATIONS

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Stochastic flows on the boundaries of SL(n,R)

Summary We study the asymptotic stability of the stochastic flows on a class of compact spaces induced by a diffusion process in SL(n, R) or GL(n, R). These compact spaces are called boundaries of SL(n, R), which include SO(n), the flag manifold, the sphereS ⁿ–1 and the Grassmannians. The one point motions of these flows are Brownian motions. For almost every, , we determine the set of stable points. This is a random open set whose complement has zero Lebesgue measure. The distance between any two points in the same component of this set tends to zero exponentially fast under the flow. The Lyapunov exponents at stable points are computed explicitly. We apply our results to a stochastic flow onS ⁿ–2 generated by a stochastic differential equation which exhibits some nice symmetry.Research supported in part by Hou Yin Dong Education Foundation of China On leave from Nankai University, Tianjin, China     

Dianion approach to chiral cyclopropene carboxylic acids

[reaction: see text] In this Letter, we describe a general method for preparing the dianions of cyclopropene carboxylic acids, and we show that their subsequent reactions with electrophiles provide a general means for selectively introducing diverse types of functional groups. This provides a general method for the synthesis of chiral 1,2-disubstituted cyclopropenes, and opens new avenues for the enantioselective preparation of cyclopropenes.