Synthesis and characterisation of p-diethylaminomethylthiacalix[4]arene for selective recovery of platinum from automotive catalyst residue

The ability of chloroform solutions of p-diethylaminomethylthiacalix[4]arene 1 to extract platinum from HCl media was tested. As an ion-pair extractant, compound 1 had the highest platinum extraction ability among all the thiacalix[n]arene derivatives tested in this study. Compound 1 was a highly specific extractant for Pt(IV) ions from single-metal solutions and platinum-group metal solutions from automotive catalyst residue. Various conditions such as contact time, pH, concentration of 1, effect of chloride ions, effect of acidity and Pt(IV) concentration were studied. The distribution ratio of platinum ions (D) was calculated. The platinum complex stoichiometry ratio was obtained using slope analysis. The 1–Pt(IV) complex was characterised using X-ray photoelectron spectroscopy, FT-IR and ¹H NMR. Finally, the Pt(IV) extraction percentage of compound 1 was compared with that of previously reported thiacalix[n]arene-based extractants.     

Tolerance,bioaccumulation and biotransformation of arsenic in freshwater prawn (Macrobrachium rosenbergii)

Tolerance bioaccumulation and biotransformation of arsenic compounds by a freshwater prawn (Macrobrachium rosenbergii) were investigated. M. rosenbergii was exposed to 10, 20, 30 and 35 μg As cm⁻³ of disodium arsenate [abbreviated as As(V)], 25, 50, 100 and 120 μg As cm⁻³ of methylarsonic acid (MMAA), or 100,200, 300 and 350 μg As cm⁻³ of dimethylarsinic acid (DMAA). Tolerances (50% lethal concentration: LC₅₀) of the prawn against As(V), MMAA, and DMAA were 30, 100, and 300 μg As cm⁻³, respectively. The prawn accumulated arsenic compounds directly from aqueous phase and biotransformed them in part. Both methylation and demethylation of the arsenicals were observed in vivo. Highly methylated and less toxic arsenicals were less accumulated in M. rosenbergii.     

Shrinkage estimators for large covariance matrices in multivariate real and complex normal distributions under an invariant quadratic loss

The problem of estimating large covariance matrices of multivariate real normal and complex normal distributions is considered when the dimension of the variables is larger than the number of samples. The Stein–Haff identities and calculus on eigenstructure for singular Wishart matrices are developed for real and complex cases, respectively. By using these techniques, the unbiased risk estimates for certain classes of estimators for the population covariance matrices under invariant quadratic loss functions are obtained for real and complex cases, respectively. Based on the unbiased risk estimates, shrinkage estimators which are counterparts of the estimators due to Haff [L.R. Haff, Empirical Bayes estimation of the multivariate normal covariance matrix, Ann. Statist. 8 (1980) 586–697] are shown to improve upon the best scalar multiple of the empirical covariance matrix under the invariant quadratic loss functions for both real and complex multivariate normal distributions in the situation where the dimension of the variables is larger than the number of samples.     

New mu-opioid receptor agonists with phenoxyacetic acid moiety

New muq-opioid receptor (MOR) agonists containing 4-hydroxypiperidine, piperidine and piperazine moieties were synthesized and evaluated to find a peripheral opioid analgesic. Among the synthesized compounds, 12-[1-[3-(N,N-dimethylcarbamoyl)-3,3-diphenylpropyl]-4-hydroxypiperidin-4-yl]phenoxy]acetic acid (8: SS620) having phenoxyacetic acid and 4-hydroxypiperidine moieties showed the highest agonist potency on the MOR in an isolated guinea-pig ileum preparation, and it also had selectivity to the human MOR expressed in Chinese hamster ovary (CHO)-K1 cells compared with the same types of delta- and kappa-opioid receptors (DOR and KOR). In addition, compound 8 showed a 10 times more potent MOR agonist activity than loperamide. Furthermore, compound 8 showed a peripheral analgesic activity in vivo screening on rat.     

Synthese makrocyclischer Lactone durch Ringerweiterung. Vorläufige Mitteilung

Synthesis of Macrocyclic Lactones by Ring Enlargement Reaction Treatment of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) prepared by Michael addition of 2-nitrocyclohexanon and acrylaldehyde with methyltri (2-propoxy)tita-nium yielded a mixture of 2 and 3 which was converted into 6-nitro-9-decanolide ( 4 ).     

Structural investigations of polymer liquid-crystalline solutions: Aromatic polyamides,hydroxy propyl cellulose,and poly(γ-benzyl-L-glutamate)

A comparative structural investigation of the characteristics of polymer liquid-crystalline solutions including Kevlar® (PPD-T)/sulfuric acid, poly(Cl-p-phenylene terephthalamide) (Cl-PPD-T)/sulfuric acid, poly(γ-benzyl-L-glutamate) (PγBLG)/dioxane, and hydroxypropyl cellulose (HPC)/water was undertaken. Experimental procedures included polarized light microscopy, light scattering, absorption spectra, and x-ray diffraction on solutions at various concentrations and temperatures. Both the two-phase region at the onset of liquid-crystal formation and the wholly anisotropic phase were investigated. Each solution exhibited distinctive characteristics. The PPD-T and Cl-PPD-T solutions were nematic, and the PγBLG and HPC solutions were cholesteric. In the two-phase region the PPD-T, Cl-PPD-T, and PγBLG (but apparently not the HPC) exhibited negatively birefringent spherulites and aggregates of spherulites. The HPC solutions only exhibited spherulitic structures in the single-phase anisotropic system. The structures and orientations in the anisotropic phase for the various polymer solutions is considered. The helicoidal structural characteristics of the PγBLG and HPC solutions are contrasted.     

Ruthenium catalyzed addition reaction of carboxylic acid across olefins without beta-hydride elimination

The cationic ruthenium catalyst (Cp*RuCl2)2/AgOTf/Ligand promotes the addition reaction of carboxylic acids across olefins without beta-hydride elimination.     

Ruthenium(II)-catalyzed selective intramolecular [2 + 2 + 2] alkyne cyclotrimerizations

In the presence of a catalytic amount of Cp*RuCl(cod), 1,6-diynes chemoselectively reacted with monoalkynes at ambient temperature to afford the desired bicyclic benzene derivatives in good yields. A wide variety of diynes and monoynes containing functional groups such as ester, ketone, nitrile, amine, alcohol, sulfide, etc. can be used for the present ruthenium catalysis. The most significant advantage of this protocol is that the cycloaddition of unsymmetrical 1,6-diynes with one internal alkyne moiety regioselectively gave rise to meta-substituted products with excellent regioselectivity. Completely intramolecular alkyne cyclotrimerization was also accomplished using triyne substrates to obtain tricyclic aromatic compounds fused with 5-7-membered rings. A ruthenabicycle complex relevant to these cyclotrimerizations was synthesized from Cp*RuCl(cod) and a 1,6-diyne possessing phenyl terminal groups, and its structure was unambiguously determined by X-ray analysis. The intermediary of such a ruthenacycle intermediate was further confirmed by its reaction with acetylene, giving rise to the expected cycloadduct. The density functional study on the cyclotrimerization mechanism elucidated that the cyclotrimerization proceeds via oxidative cyclization, producing a ruthenacycle intermediate and subsequent alkyne insertion initiated by the formal [2 + 2] cycloaddition of the resultant ruthenacycle with an alkyne.