Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers

Molecular growth processes utilizing a beta-octamolybdate synthon and {Ag2} dimers are described and the directing influence of "encapsulating" cations and coordinating solvent is also demonstrated. The growth of two 1D chains, (nBu4N)2n[Ag2Mo8O26]n (1) and (nBu4N)2n[Ag2Mo8O26(CH3CN)2]n (2), is achieved when nBu4N+ ions are used, and the diameter of the chains can be expanded by the coordination of CH3CN solvent (2). The formation of a type of gridlike structure in which 1D chains are crossed-over each other in alternatively packed layers is achieved in DMSO as the solvent; DMSO acts as a linking group to give (nBu4N)2n[Ag2Mo8O26(dmso)2]n (3), which, similar to 1 and 2, still incorporates the Bu4N+ ions that exert an "encapsulating" influence. However, in (HDMF)n[Ag3(Mo8O26)(dmf)4]n (4) the relatively bulky Bu4N+ ions are exchanged for protonated DMF cations, thereby allowing the chains to condense to a 2D array. The building block concept is further enforced by the isolation of a "monomeric" unit (Ph4P)2[Ag2Mo8O26(dmso)4] (5), which is isolated when the Ph4P+ ions are so "encapsulating" as to prevent aggregation of the {Ag-Mo8-Ag} building blocks. The nature of the AgAg dimers in each of the compounds 1-4 is examined by DFT calculations and the interplay between these Ag-Ag interactions and the structure types is described.     

Synthesis of monofluorinated 1-(naphthalen-1-yl)piperazines

A series of regioisomerically monofluorinated 1-(naphthalen-1-yl)piperazines is described.     

Micelle studies using a metal ion/murexide indicator system

Summary Complex formation between divalent metal ions and the hydrophilic murexide anion in the presence of anionic micelles has been employed to study aspects of micelle formation, the binding of divalent metal ions to micelles, and the kinetics of metal-complex formation in the presence of micelles.

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Zusammenfassung Die Komplexbildung zweiwertiger Metallionen mit dem hydrophilen Indikator Murexid wurde in Gegenwart anionischer Mizellen untersucht. Die Indikatorreaktion wurde benutzt, um Aussagen über Mizellbildung, Bindung zweiwertiger Metallionen an Mizellen und die Kinetik der Metallkomplexbildung bei Anwesenheit von Mizellen zu erhalten.

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With 8 figures and 1 table

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Dedicated to Prof.G. Rehage on the occasion of his 60th birthday.     

Chemo-enzymatic synthesis of (−)-epipentenomycin I

A chemo-enzymatic synthesis of (−)-epipentenomycin I is reported using a lipase-catalysed kinetic resolution of the racemic pentacyclic alcohol 8. Flash vacuum pyroloysis of (−)-8 so obtained gave (−)-(4R)-4-hydroxy-5-methylene-2-cyclopentenone. Epoxidation of this compound with dimethyldioxirane followed by hydrolytic ring-opening of the resulting epoxide gave (−)-epipentenomycin I.     

Synthesis of titanium(IV) guanidinate complexes and the formation of titanium carbonitride via low-pressure chemical vapor deposition

The mono(guanidinato) complex [Ti(NMe2)2Cl{i-PrNC[N(SiMe3)2]N-i-Pr}] (1) was prepared by reaction of [Ti(NMe2)2Cl2] with 1 or 2 equiv of the lithium guanidinate salt [Li{i-PrNC[N(SiMe3)2]N-i-Pr}]. Compound 1 has been characterized by X-ray crystallography. Treatment of TiCl4 with 2 equiv of [Li{i-PrNC[N(SiMe3)2]N-i-Pr}] resulted in the formation of dark red crystals. X-ray crystallography showed that these crystals consist of a 70:30 mixture of two bis(guanidinato) complexes, namely, [TiCl2{i-PrNC[N(SiMe3)2]N-i-Pr}{i-PrNC(N=CMe2)N-i-Pr}] (2) and [TiCl2{i-PrNC[N(SiMe3)2]N-i-Pr}{i-PrNC[N(H)-i-Pr]N-i-Pr}] (3). Both compounds 2 and 3 possess a transformed guanidinate ligand. Low-pressure chemical vapor deposition of either compound 1 or [TiCl2{i-PrNC(NMe2)N-i-Pr}] (4) at 600 degrees C results in thin films of titanium carbonitride.     

Determination of 2-mercaptopropionylglycine and its metabolite, 2-mercaptopropionic acid, in plasma by ion-pair reversed-phase high-performance liquid chromatography with post-column derivatization.

A simple and fast high-performance liquid chromatographic method was developed for the simultaneous measurement of 2-mercaptopropionylglycine (Tiopronine) and its metabolite (2-mercaptopropionic acid) in human plasma after the administration of a pharmaceutical dosage form (Acadione). The sample treatment before high-performance liquid chromatographic analysis consisted of the reduction of the corresponding disulphides by tri-n-butylphosphine and protein precipitation with ethanol. Separation was achieved by ion-pair high-performance liquid chromatography on a reversed-phase column (LiChrospher RP 18e) with cetrimonium bromide as counter ion and detection by fluorimetry after post-column derivatization with a selective thiol reagent, i.e. pyrenemaleimide. The high frequency of the analyzed samples and validation results make the method suitable for pharmacokinetic studies, and this was demonstrated by the first results obtained after the administration of an oral dose of 500 mg of Tiopronine to two healthy subjects.     

Uptake of weathered p,p′-DDE by plant species effective at accumulating soil elements

Ten plant species previously shown to accumulate inorganic elements effectively from natural solids were grown under field conditions in p,p′-dichlorodiphenyldichloroethane (p,p′-DDE) contaminated soil. The plant species, which included rye, mustard, canola, vetch, pigeonpea, clover, peanut, and 3 cultivars of white lupin, represented both monocots and dicots, as well as two major families within the dicots: the Brassicaceae and the Fabaceae. The plants varied widely in their ability to phytoextract and translocate weathered p,p′-DDE. The percentage of contaminant phytoextracted ranged from 0.06% (white lupin) to 0.22% (clover, vetch), and the translocation factors (TF; contaminant concentration ratio of stems to roots) ranged from 0.04 (clover, white lupin) to 0.37 (canola). An inverse relationship exists between the amount of contaminant in the roots as measured by the root BCF (bioconcentration factor; dry weight contaminant concentration ratio of root to soil) and the TF. Duplicate mounds of each species were periodically amended with nitrogen (N), phosphorus (P), nitrogen and phosphorus together (N/P); a minus phosphorus treatment involved the addition of AlSO₄ to the soil prior to planting. The effect of nutrient regime on plant biomass, p,p′-DDE uptake and translocation, and inorganic element content varied greatly among the 10 plant species. For some species (rye, vetch, pigeonpea, clover, white lupin), reductions or non-significant changes in p,p′-DDE uptake were observed under the nutrient treatments and were not correlated with plant biomass effects. For mustard, canola, and peanut, the percentage of p,p′-DDE phytoextracted in the various treatments was more than doubled and was directly correlated with a two-fold increase in total plant biomass. Although it is generally assumed that fertilizer amendments will enhance the phytoremediation of organic and inorganic pollutants, the data here suggest that such effects are highly species specific and in some cases may actually decrease remediation potential.