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PubMed2004

A review of factors affecting the release and bioavailability of contaminants during sediment disturbance events.

The factors affecting the release and bioavailability of contaminants present in sediments during natural and anthropogenic disturbance events are discussed and our current state of understanding of these processes reviewed. Published data are focused on the distribution of contaminants within undisturbed sediment, their affinities to the various solid-phase fractions of sediment and the interaction of contaminants between sediment and pore water. Sediment disturbance can lead to changes in the chemical properties of sediment that stimulate the mobilisation of contaminants. Research shows that changes in both redox potential (Eh) and pH can accelerate desorption, partitioning, bacterial degradation and the oxidation of organic contaminants. However, these processes are both sediment- and compound-specific. By affecting the affinity of contaminants to sediments, disturbance events in turn can have a significant effect on their bioavailability. Few studies have examined this phenomenon, and it is clear from the data available that there are gaps in our understanding in a number of key areas when assessing the release of contaminants from sediments: the fate of contaminants in undisturbed sediments and those that are not subjected to major disturbances, the kinetic processes that regulate metal release during changes in redox potential, the release of organometallic compounds from sediments during resuspension, the bioavailability of organic and organometallic compounds and the processes affecting contaminant release.

Animals↗
PubMed1999

Analysis of the environment of beryllium, magnesium and alkaline earth atoms in oxygen-containing compounds.

About 2100 inorganic and organometallic compounds containing beryllium, magnesium and alkaline earth atoms (M) were investigated with Voronoi-Dirichlet polyhedra (VDPs). It is shown that the coordination numbers (CNs) of the M atoms in MO(n) coordination polyhedra can be determined by means of VDPs without crystal-chemical radii. The distributions of the M-O distances in the coordination spheres of the M atoms are bimodal for M = Be or Mg and monomodal for the other alkaline earth metals. Beryllium and magnesium coordination polyhedra containing weak M-O contacts were classified by variants of their distortions. It is found that the volume of the domains of the Mg, Ca, Sr and Ba atoms is independent of their CNs at CN >/= 6 (up to 16 for barium). The possibility of using the model of deformable spheres to describe the crystal structure of the compounds investigated is suggested.

Journal Article↗
PubMed1997

Monomeric, Four-Coordinate Group 4 Metal Complexes with Chelating Bis(tert-butylamido)cyclodisilazane Ligands: Syntheses and Molecular Structures of {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2) and {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MMe(2), M = Zr, Hf.

The interaction of (MeSiN(t)Bu)(2)(N(t)BuLi)(2) with MCl(4) in hot toluene produces {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2,) M = Zr (1), Hf (2), in good yields. The light-yellow and colorless solids are isostructural and crystallize in the monoclinic crystal system, space group P2(1)/n, with four molecules in the unit cell. The unit cell dimensions for 1 (293 K) are a = 9.174(6) Å, b = 18.027(13) Å, c = 16.515 Å, beta = 98.81(6) degrees, and those for 2 (213 K) are a = 9.1871(1) Å, b = 17.8553(2) Å, c = 16.4770(3) Å, beta = 99.339(1) degrees. The metal atoms are pseudotetrahedrally coordinated by cyclodisilazane and chloride ligands but have one additional weak bonding interaction with a cyclodisilazane ring-nitrogen atom. Treatment of 1 or 2 with 2 equiv of MeMgCl in ether affords the corresponding dimethyl species {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MMe(2), M = Zr (3), Hf (4). These isostructural, colorless organometallic compounds are remarkably stable to atmospheric oxygen and moisture. They crystallize in the monoclinic space group C2/c, Z = 4. The cell parameters for 3 (298 K) are a = 18.867(2) Å, b = 9.361(1) Å, c = 18.059(3) Å, beta = 119.49(1) degrees, and those for 4 (212 K) are a = 18.8066(4) Å, b = 9.3208(2) Å, c = 17.8725(3) Å, beta = 119.508(1) degrees. The dimethyl species are structurally very similar to the dichloro complexes 1 and 2, with the notable exception that the metal centers in these organometallic compounds are truly four-coordinate.

Journal Article↗
PubMed1997

Coupling chemical derivatization reactions with supercritical fluid extraction.

Coupling chemical derivatization reactions with supercritical fluid extraction for the determination of trace levels of organic and organometallic compounds in liquid and solid matrices is reviewed. Derivatization is used to increase the solubility of analytes in supercritical carbon dioxide, to increase analyte volatility for gas chromatographic analysis and to integrate sample preparation steps in order to reduce analysis time and costs. Reactions that are covered in this review derivatize analytes possessing carboxyl, hydroxyl, sulfonic and amino groups to their alkyl, acyl and silyl derivatives. Derivatization is also used to derivatize active matrix sites to facilitate the release of analytes. Approaches used to couple derivatization with supercritical fluid extraction include reactions conducted prior to extraction, under in-site supercritical fluid conditions, or off-line under injection port conditions. Examples of applications are given for organic and organometallic compounds in environmental, pharmaceutical and agricultural product samples.

Chromatography, Gas↗
PubMed2000

Speciation of alkyllead and inorganic lead by derivatization with deuterium-labeled sodium tetraethylborate and SPME-GC/MS.

A method for full speciation and determination of alkyllead and inorganic lead(II) in aqueous samples was developed. This was accomplished by in situ derivatization with deuterium-labeled sodium tetraethylborate NaB(C2D5)4 (DSTEB). The derivatization was carried out directly in the aqueous sample and the derivatives were extracted from the headspace by a solid-phase microextraction (SPME) fiber. The extracted analytes were then transferred to a GC/MS or a GC/FID for separation and detection. The research presented demonstrates that SPME and the derivatization reagent DSTEB can be used successfully for the speciation of Pb2+, Pb(CH3)3+, Pb(C2H5)3+, and Pb(C2H5)4 in water samples. All derivatives, Pb(C2D5)4, (CH3)3Pb(C2D5), (C2H5)3Pb(C2D5), and Pb(C2H5)4, are separated using an SBP-5 column. This method was applied to monitor degradation of tetraethyllead in water. This is the first report of ethylation by DSTEB for full speciation of methyllead, ethyllead, and inorganic lead compounds. This approach can be extended to other organometallic compounds as demonstrated for ethyltin speciation. This full speciation method will aid in monitoring occurrence, pathways, toxicity, and biological effects of these compounds in the environment. It is easily adopted for field analysis.

Borates↗
PubMed1997

Tributyltin potentiates 3,3',4,4',5-pentachlorobiphenyl-induced cytochrome P-4501A-related activity.

Induction of cytochrome P-4501A protein and induction of related enzyme activity are hallmark physiological responses following exposure to planar halogenated aromatic hydrocarbons (HAHs) such as 3,3',4,4',5-pentachlorobiphenyl (PCB 126; PeCB). Environments contaminated by HAHs are often contaminated by mixtures of anthropogenic contaminants, including organometallic compounds. Both HAHs and organometallics easily bioconcentrate and bioaccumulate in aquatic food chains that may ultimately be linked to humans through seafood consumption. Tributyltin (TBT), a marine biocide, has been detected in many aquatic environments due to its primary use as a marine antifoulant agent. Exposure to TBT, as well as several PCBs, has been associated with immunotoxicity, neurotoxicity, and endocrine disruption. Recently TBT has been shown to inhibit cytochrome P-4501A activity in vitro, but information concerning these effects in vivo and in combination with classical inducers of P-4501A, such PeCB, is lacking. We exposed female B6C3F1 mice to 0.01, 0.1, and 1.0 mg/kg PeCB, TBT, or both in combination, with corn oil (CO) serving as a carrier control. Cytochrome P-4501A protein levels and related benzo[a]pyrene hydroxylation (BaP-OHase) activity were measured following a single acute intraperitoneal (ip) dose or seven daily injections. Body, thymus, and liver weights were used to monitor general physiological responses following exposure. P-4501A levels and BaP-OHase activity were significantly elevated in mice exposed to PeCB alone. This effect was enhanced by coexposure to low levels of TBT; PeCB-induced P-4501A-related activity was potentiated at the low range of each. The highest dose of TBT, however, inhibited these activities when given in combination with PeCB. Thymic atrophy was evident only in mice exposed daily to 0:1 and 1.0 mg/kg PeCB alone, or to a combination of the lowest and highest dose of PeCB and TBT, respectively. Because environmental levels of TBT are not expected to be as high as the highest level used in our toxicological studies, we conclude that environmental exposure to TBT may potentiate, rather than inhibit, the activity of environmental levels of HAHs that are associated with P-4501A induction.

Animals↗
PubMedDate not supplied

Differential effects of organometallic tin compounds on Na+/K+-ATPase activity.

In vitro effects of six dibenzyltin dichloride (A-series) and another six dibenzyltin diisothiocyanate (B-series) complexes on Na+/K+-ATPase were studied. The rat brain synaptic membranes were prepared and significant ATPase inhibition was observed with all the complexes in a dose-dependent manner. The order of potency on Na+/K+-ATPase activity of the chloride complexes was found to be higher than that of the isothiocyanate complexes. The IC50 values range from 64 microM to 252 microM for the chloride complexes and from 132 microM to 399 microM for the isothiocyanate complexes. A structure-activity relationship could be derived for the chloride complexes.

Animals↗
PubMed2003

Organometallic aluminum compounds derived from 2-(1,3,5-dithiazinan-5-yl)ethanol ligands.

The reactions of AlMe(2)Y (Y = Me or Cl) with new ligands 2-(1,3,5-dithiazinan-5-yl)ethanol (1), 2-(1,3,5-dithiazinan-5-yl)-1-methylethanol (2), and 2-(1,3,5-dithiazinan-5-yl)-1-phenylethanol (3) are described. The ligands are coordinated to aluminum atoms by nitrogen and oxygen atoms, with a nitrogen based spiranic structure. Equimolar reactions gave dimeric structures bearing pentacoordinated aluminum atoms O-(AlMeY)-2-(1,3,5-dithiazinan-5-yl)ethanolates (4-7) as well as monometallic compounds with tetracoordinated aluminum atoms O-(AlMeY)-2-(1,3,5-dithiazinan-5-yl)ethanolates (8-9). Reactions with 2 equiv of the aluminum reagents afforded tetracoordinated dialuminum complexes O-(AlMeY)-O-(AlMe(2)Y)-2-(1,3,5-dithiazinan-5-yl)ethanolate (10-18). The structures of the new compounds were determined by NMR ((1)H,(13)C, and (27)Al) and complemented by X-ray diffraction of compounds 4, 10, and 16-18. Relevant intermolecular interactions C-H...S, C-H...Cl, and C-H...pi found in the crystalline network are reported.

Journal Article↗
PubMed2005

A metallocene-complexed dibismuthene: Cp2Zr(BiR)2 (Cp = C5H5; R = C6H3-2,6-Mes2).

The zirconocene-complexed dibismuthene, Cp2Zr(BiR)2 (Cp = C5H5; R = C6H3-2,6-Mes2), was prepared by the reaction of sodium metal with Cp2ZrCl2 and RBiCl2. The air- and moisture-sensitive dark reddish/brown compound is the first organometallic compound containing Bi-Zr bonds and the only example of a ZrBi2 ring. Moreover, our computations on associated model systems offer insight into the nature of the interaction of the heaviest dipnictene with a metallocene center.

Journal Article↗
PubMed2005

On the nature of metal-carbon bonding: AIM and ELF analyses of MCH(n) (n = 1-3) compounds containing early transition metals.

Ab initio and DFT calculations have been performed on a series of organometallic compounds, according to the formula MCH(n), where M = K, Ca, Sc, Ti, V, Cr, or Mn and n = 1-3. Various theoretical methods are compared, the B3LYP level yielding the same agreement with the experimental geometries available as the correlated MP2 and CISD methods, with the 6-311++G(3df,2p) basis set for C and H and Wachter's (15s11p6d3f1g)/[10s7p4d3f1g] basis set for transition metals. The main geometric and electronic features of the molecules studied are described, analyzing the M-C bonding characteristics in terms of the atoms in molecules theory (AIM) and the electron localization function (ELF). Although multiple bonding is expected from the Lewis bonding scheme, the results indicate an almost pure ionic bond for all of the systems studied. The net charge transfer from the metal to the carbon atom ranges from 0.5 to 1 e(-), and the electronic structure of the CH(n)(-) moiety is unaltered after the interaction with the metal cation, showing little or no effect on the shape of the electron pairing. The bond paths corresponding to a possible alpha-agostic bond for these systems are not present.

Algorithms↗
PubMed2004

Effects of palladacycle complex on hematopoietic progenitor cells proliferation in vivo and in vitro and its relation with the inhibitory properties of this compound on the angiotensin-I converting enzyme activity.

In the present study, we introduce a new class of organometallic compound, the Biphosphinic Palladacycle Complex [Pd (C2, N-S(-)(dmpa)(dppf)] Cl (BPC), as an angiotensin-I converting-enzyme inhibitor (ACEI) with hematological regulation properties. When BPC was assayed as a competitive inhibitor over the hydrolysis of Abz-YRK (Dnp)-P-OH (Km = 7.0 microM), it showed a Kiapp = 0.2259 ng and a Ki value of 94.12 pg. Using murine long-term bone marrow cultures (LTBMCs) and clonal culture techniques, we also evaluated the capacity of this drug (1.18 microM) to module haematopoietic progenitor cells proliferation in vitro and in vivo. Our results demonstrated that BPC produces no toxicity to bone marrow cells, as determined by the unchanged cell number in the non-adherent layer at weeks 1, 2, and 8 and the increased number of adherent cells present in the BPC-treated LTBMCs. However, the proportion of CFU-Cs in the non-adherent cell layer was reduced at weeks 5, 6, 8, and 9. In vivo studies using the dose of 1 mg/kg of BPC, administered by subcutaneous route, presented similar result as those found in vitro, in the number of CFU-Cs. This latter finding may be explained by the inhibitory effects of this drug on the ACE activity, which probably result in increased levels of its substrate AcSDKP, a negative regulator of hematopoiesis.

Angiotensin-Converting Enzyme Inhibitors↗
PubMed2000

Primordial carbonylated iron-sulfur compounds and the synthesis of pyruvate.

Experiments exploring the potential catalytic role of iron sulfide at 250 degrees C and elevated pressures (50, 100, and 200 megapascals) revealed a facile, pressure-enhanced synthesis of organometallic phases formed through the reaction of alkyl thiols and carbon monoxide with iron sulfide. A suite of organometallic compounds were characterized with ultraviolet-visible and Raman spectroscopy. The natural synthesis of such compounds is anticipated in present-day and ancient environments wherever reduced hydrothermal fluids pass through iron sulfide-containing crust. Here, pyruvic acid was synthesized in the presence of such organometallic phases. These compounds could have provided the prebiotic Earth with critical biochemical functionality.

Carbon Monoxide↗
PubMed2002

Current use and future potential of organometallic radiopharmaceuticals.

Contrary to common belief, organometallic compounds exhibit remarkable stability in aerobic and even diluted aqueous solutions. Technetium-sestamibi (Cardiolite) is one of the most prominent examples of this class of compounds routinely used in nuclear medicine. This review summarises the recent progress in labelling of biomolecules with organometallic complexes for diagnostic and therapeutic application in radiopharmacy and exemplifies in detail developments focussing on organometallic technetium- and rhenium-tricarbonyl technologies. The value of such technologies has been recognised and they have become a valuable alternative to common labelling methodologies. An increasing number of groups have started to employ an organometallic precursor for the purpose of radioactive labelling of various classes of biomolecules, and the advantages and limitations of this new technique are compared with those of other labelling methods. The synthetic access to appropriate precursors via double-ligand exchange or aqueous carbonyl kit preparation for routine application is described. Strategies and examples for the design of appropriate bifunctional chelating agents for the Tc/Re-tricarbonyl core are given. The functionalization of biomolecules such as tracers for the central nervous system (dopaminergic and serotonergic), tumour affine peptides (somatostatin receptors, neuroreceptors) and tumour binding single-chain antibody fragments is summarised. Where possible and appropriate, the in vitro and in vivo results in respect of these examples are compared with those obtained with classical (99m)Tc/(188)Re(V)- and (111)In-labelled analogues. The preclinical results show the in many ways superior characteristics of organometallic labelling techniques.

Immunoglobulin Fragments↗
PubMed2003

Heterodimetallic compounds assembled from ferrocenedicarboxylato and ferrocenecarboxylato ligands.

Heteropolynuclear organometallic compounds have been constructed by using two kinds of ferrocene-based ligands, 1,1'-ferrocenedicarboxylic acid (H(2)L(1)) and ferrocenecarboxylic acid (HL(2)). Reactions the ligand H(2)L(1) with copper(II) and nickel(II) salts, in the presence of pyridine, give a tetranuclear Cu(2)Fe(2) mixed-metallic box Cu(2)L(1)(2)(Py)(2)(DMF)(2)(H(2)O)(2) (1) and a tetranuclear heterobimetallic helix Ni(2)L(1)(2)(Py)(4)(H(2)O) (2), respectively. In these complexes, the ferrocene moieties show cisoid conformations which lead to the formation of the finite coordination geometry, i.e. to molecular complexes. Interactions of the ligand H(2)L(1) with lanthanide ions afford two-dimensional networks [La(2)L(1)(3)(CH(3)OH)(4)]( infinity ) (3), [Eu(2)L(1)(3)(H(2)O)(5)]( infinity ) (4), and [Gd(2)L(1)(3)(CH(3)OH)(2)(H(2)O)(3)]( infinity ) (5), respectively, in which transoid conformations of the ferrocene moiety provide opportunities to form infinite 2-D networks. It is suggested that the conformational freedom of the ferrocene moiety makes the ligand L(1) display different conformations and coordination modes in these complexes. In addition, the pi.pi interactions related to the ferrocene moieties were also found to stabilize the supramolecular architectures in the solid state. As a comparison, reaction of lanthanide ions with the ligand HL(2) resulted in three isostructural heterodinuclear windmill-shaped compounds Ln(2)L(2)(6)(CH(3)OH)(2)(H(2)O)(5) [Ln = La (6), Eu (7), and Gd (8)] by simply diffusing the solutions of lanthanide ions into the mixture of HL(2) and NaOH, respectively. Electrochemical properties of the ferrocene-containing complexes 1-8 are also investigated in the solution or solid state.

Journal Article↗
PubMed2003

Stereospecific biocatalytic epoxidation: the first example of direct regeneration of a FAD-dependent monooxygenase for catalysis.

Catalysis for chemical synthesis by cell-free monooxygenases necessitates an efficient and robust in situ regeneration system to supply the enzyme with reducing equivalents. We report on a novel approach to directly regenerate flavin-dependent monooxygenases. The organometallic complex [CpRh(bpy)(H(2)O)](2+) catalyzes the transhydrogenation reaction between formate and isoalloxazine-based cofactors such as FAD and FMN. Coupling this FADH(2) regeneration reaction to the FADH(2)-dependent styrene monooxygenase (StyA) resulted in a chemoenzymatic epoxidation reaction where the organometallic compound substitutes for the native reductase (StyB), the nicotinamide coenzyme (NAD), and an artificial NADH regeneration system such as formate dehydrogenase. Various styrene derivatives were converted into the essentially optically pure (S)-epoxides (ee > 98%). In addition, StyA was shown to be capable of performing sulfoxidation reactions. The productivity of the chemoenzymatic epoxidation reaction using 6.5 microM StyA reached up to 6.4 mM/h, corresponding to approximately 70% of a comparable fully enzymatic reaction using StyB, NADH, and formate dehydrogenase for regeneration. The coupling efficiency of the nonenzymatic regeneration reaction to enzymatic epoxidation was examined in detail, leading to an optimized reaction setup with minimized quenching of the electron supply for the epoxidation reaction. Thus, up to 60% of the reducing equivalents provided via [CpRh(bpy)(H(2)O)](2+) could be channeled into epoxide rather than hydrogen peroxide formation, allowing selective synthesis with high yields.

Biomimetic Materials↗
PubMed1991

Two-week, repeated inhalation exposure of F344/N rats and B6C3F1 mice to ferrocene.

Ferrocene (dicyclopentadienyl iron; CAS No. 102-54-5) is a relatively volatile, organometallic compound used as a chemical intermediate, a catalyst, and as an antiknock additive in gasoline. It is of particular interest because of its structural similarities to other metallocenes that have been shown to be carcinogenic. F344/N rats and B6C3F1 mice were exposed to 0, 2.5, 5.0, 10, 20, and 40 mg ferrocene vapor/m3, 6 hr/day for 2 weeks. During these exposures, there were no mortality and no observable clinical signs of ferrocene-related toxicity in any of the animals. At the end of the exposures, male rats exposed to the highest level of ferrocene had decreased body-weight gains relative to the weight gained by filtered air-exposed control rats, while body-weight gains for all groups of both ferrocene- and filtered air-exposed female rats were similar. Male mice exposed to the highest level of ferrocene also had decreased body-weight gains, relative to controls, while female mice had relative decreases in body-weight gains at the three highest exposure levels. Male rats had a slight decrease in relative liver weight at the highest level of exposure, whereas no relative differences in organ weights were seen in female rats. Male mice had exposure-relative decreases in liver and spleen weights, and an increase in thymus weights, relative to controls. For female mice, relative decreases in organ weights were seen for brain, liver, and spleen. No exposure-related gross lesions were seen in any of the rats or mice at necropsy. Histopathological examination was done only on the nasal turbinates, lungs, liver, and spleen.(ABSTRACT TRUNCATED AT 250 WORDS)

Administration, Inhalation↗
PubMedDate not supplied

Organometallics and quaternary ammonium salts affect calcium ion desorption from lecithin liposome membranes.

The objective of the present work was to compare the effects of groups of tin and lead organometallic compounds and their mixtures with amphiphilic quaternary ammonium salts (QAS) on the process of calcium ion desorption from lecithin liposome membranes, as dependent on the properties of the hydrophilic and hydrophobic parts of QAS. In the investigations the method of radioactive labels was applied. Synergism and antagonism in the action of both groups of compounds were found. The effectiveness of the cooperation depended more on chain length of QAS compounds than on the size and polarity of their hydrophobic parts. The most effective of all compounds studied was a the mixture of benzyldimethylammonium chloride in a mixture with tripropyltin. Since the rate of calcium desorption proved to be a good measure of efficacy of biologically active surfactants, it seems that the conclusions reached in this paper may be useful for choosing compounds which are able to decontaminate the environment polluted with heavy metals.

Adsorption↗