Phosphonate ligands in extended inorganic hybrids and as radical units in complexes

Phosphonatliganden in erweiterten anorganischen Hybridmaterialien undrnals Radikalträgern in KomplexenrnrnAnorganisch-organische Hybridmaterialien sind in der Regel extrem vielseitig. Die systematische Darstellung von niederdimensionalen Materialien (eindimensionale Kettenverbindungen oder zweidimensionalen Schichtverbindungen) mit einer Kontrolle über die Art der Verbindung,rnbietet neue Möglichkeiten im Bereich des molekularen Magnetismus. Hier im Fall von Metall-Phosphonat Verbindungen in erweiterten anorganischen Hybriden wurde der pH - Wert während der Reaktion eingestellt, wodurch der Grad der Protonierung des Phosphonatliganden kontrolliert wurde. Aufgrund der Tatsache, dass alle erhaltenen Metall Phosphonatverbindungen neutral waren, konnte das Ligand zu Metallverhältnis erstmals vorhergesagt werden. So wurden mehrere neue Metall–Phosphonat Verbindungen im Bereich von Null-dimensionalen (I0O0, Co-Kristallisation von M(H2O)6 mitrndeprotonierten Phosphonatligand), über eindimensionalen (I1O0, Kettenstrukturen) bis hin zu zweidimensionalen (I2O0, Schichtstrukturen) ausführlich diskutiert in Bezug auf ihr magnetisches Verhalten. Im Allgemeinen sind die erwarteten Austauschwechselwirkungen in einem erweiterten anorganischen Hybridmaterial stark, weil oft ein Superaustausch durch ein einzelnes Sauerstoffatom möglich ist. Hier waren oft mehrere konkurrierende Austauschwechselwirkungen vorhanden, so dass kompliziertere magnetische Verhalten beobachtet wurden.rnrnDarüber hinaus wurden drei neue Beispiele von Nitronyl-Nitroxidradikale dargestellt, in denen eine zusätzliche saure Funktionalität eingeführt war. Die Auswirkungen des sauren Charakters der zusätzlich eingeführten Sulfonsäure oder Phosphonsäure-Gruppe auf das Nitronyl-Nitroxidradikal wurden im Detail zum ersten Mal untersucht. Die mit der Phosphonsäure-Gruppe versehenen Nitronyl-Nitroxidradikale sind perfekte Proben für die Untersuchung einer Spin-Verschiebung in Nitronyl-Nitroxidradikale durch EPR-Spektroskopie, aufgrund des eingeführten Phosphors. Auch der Protonierungsgrad der zusätzlich eingeführten Phosphonsäure-Gruppe wurde berücksichtigt. In dieser Arbeit wurden die ersten Metallkomplexe der neuen substituierten sauren Nitronyl-Nitroxidradikale vorgestellt. Die Koordination von Nickel(II) Metallionen an die saure, zweite funktionelle Gruppe des Nitronyl–Nitroxid Radikal wurde beschrieben. Die magnetische Austauschwechselwirkung der Metallionen untereinander und die Metall-Radikal-Austauschwechselwirkungen wurden untersucht. rnrnIm Allgemeinen können interessante molekulare magnetische Materialien dadurch dargestellt werden, dass die Dimension der Metall-Phosphonat-Verbindungen als Beispiele für die erweiterten anorganischen Hybridmaterialien gesteuert werden kann. Mit Nitronyl-Nitroxidradikale als organische Liganden können in Zukunft noch mehr Spin-Träger in anorganisch-organischen Gerüstmaterialien integriert werden um die magnetischen Eigenschaften zu verbesseren.rn

Cyanide Compounds

Chapter 4, “Cyanide Compounds,” illustrates an explosively developing research theme in which the cyanide ligand is used as a linking agent for the designed assembly of polynuclear metal complexes. Syntheses of several basic building blocks, such as K3[Cr(CN)6],Cr(Me3tacn)(CN)3,K4[Mo(CN)8],Na[W(CO)5CN],K[CpFe(CO)(CN)2],[NEt4][Cp*Rh(CN)3],[Fe4(bpy)8(μ-CN)4][PF6]4,. are given here. These units may be used in several ways to construct polynuclear compounds. One approach involves a hexacyanometalate core decorated with peripheral metal centers, e.g., [{Cu(tpa)(CN)}6Fe][ClO4]8. or [Cr{CNNi(tetren)}6][ClO4]9. An octacyanometalate unit can lead to higher nuclearity condensed compounds, as in [Co{Co(MeOH)3}8(μ-CN)30{Mo(CN)3}6]. Alternatively, a cluster core may be substituted with cyano complexes as ligands, as in [PPh4]2[Fe4S4{NCW(CO)5}4]. If there are two cis cyano ligands on the building block, then quadrilateral or square structures often result, as in {CpFe(CO(μ-CN)2Cu(PCy3)}2 and [Fe2Cu2(bpy)6(μ-CN)4][PF6]4 However, if there are three adjacent cyano ligands, then cubic cages may be constructed as in [(CpCo)4(Cp*Rh)4(μ-CN)12][PF6]4.

DETERMINANTS OF THE SELECTIVE PHAGOCYTOSIS OF CARCINOGENIC PARTICULATE NICKEL COMPOUNDS

Certain inorganic nickel compounds such as crystalline NiS and Ni(,3)S(,2) are potent inducers of carcinogenesis and in vitro cell transformation, while several closely-related compounds such as amorphous NiS are essentially devoid of genotoxic activity. The phenomenon of selectivity of phagocytosis among such particulate nickel compounds has been hypothesized to account for their widely varying toxicological potency, yet the determinants of this selectivity have not been well characterized. Extracellular medium composition, particle dissolution, and particle surface charge were examined as potential determinants of selective phagocytosis for the carcinogenic crystalline and noncarcinogenic amorphous modifications of NiS. Selectivity and avidity of uptake of crystalline NiS by CHO cells was not dependent upon serum: phagocytosis of crystalline, but not amorphous NiS proceeded readily in a minimal salts/glucose medium at 37(DEGREES)C. The evolution of phagocytosis-inhibiting Ni(II) from the surface of amorphous NiS particles did not demonstrably contribute to the lower uptake of these noncarcinogenic particles despite their somewhat greater dissolution rate than the readily phagocytosed crystalline NiS particles. Significant differences in surface charge were noted between crystalline and amorphous NiS, the former being more negative in charge in distilled water suspension. Exposure of amorphous NiS particles to the vigorously reducing environment of a LiAlH(,4) solution under an inert atmosphere resulted in the particles' acquisition of a more negative surface charge. Amorphous NiS particles thus treated were phagocytosed by CHO cells to an extent similar to that of untreated crystalline NiS particles and likewise were shown to induce morphological transformation of primary Syrian hamster embryo cells with a similar potency. The potentiation of uptake characteristic of LiAlH(,4)-treated amorphous NiS was lost gradually upon storage of particles in ambient oxygenated atmosphere and was lost rapidly by apparent particle surface oxidation in aerated distilled water suspensions aged for up to 7 days. Concomitant with this loss of uptake there occurred a loss of negative surface charge. These results suggest the predominant role of particle surface charge rather than adsorbed serum components or particle dissolution as a determinant of selective phagocytosis among particulate nickel compounds. ^

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2006)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2006 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2006 in spring. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA Autoanalyzer [Bran&Luebbe, Norderstedt, Germany]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.04 mg P l-1 (Autoanalyzer, Bran&Luebbe).

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2004)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2004 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2004 in spring, fall, and winter. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (for samples collected until spring 2004: CFA SAN++, Skalar [Breda, The Netherlands]; for samples collected later: CFA Autoanalyzer [Bran&Luebbe, Norderstedt, Germany]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar) and 0.04 mg P l-1 (Autoanalyzer, Bran&Luebbe).

Contencentrations of reduced inorganic sulfur forms in Mediterranean Sea waters

The first data on content of inorganic reduced sulfur compounds [H2S, S°, S2O3(2-), SO3(2-)] were obtained at two stations in the northeastern Levant Sea (Mediterranean Basin). With lower detection limit for the mentioned sulfur forms of 30 nM, sulfide forms were not found, while thiosulfate concentration varied from 178 to 890 nM (from 24 to 78 % of total reduced S), and S° varied from 156 to 1090 nM. Vertical distribution of these compounds showed irregular character; correlation between total reduced S maxima, fluorescence, and increase of nutrient element content near the lower pycnocline boundary was observed. The maximum total sulfur concentration in the surface layer was likely due an anthropogenic influence. The ''starting'' mechanism that controls appearance and distribution of sulfur compounds in oxygen-containing water is the process of bacterial sulfate reduction in micropatches of fresh organic detritus. Reduced sulfur forms participate further in a series of chemical and biochemical processes. Contribution of hydrolysis of organic sulfur-containing compounds is insignificant for the region in study.

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2003)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2003 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2003 in spring, fall, and winter. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA SAN++, Skalar [Breda, The Netherlands]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar).

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2005)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2005 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2005 in spring, and winter. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA Autoanalyzer [Bran&Luebbe, Norderstedt, Germany]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.04 mg P l-1 (Autoanalyzer, Bran&Luebbe).

(Table 1) Reduced compounds of sulfur in waters of the Baltic Sea

Concentrations of sulfide, S°, and thiosulfate were determined in waters of the Baltic Sea. Microquantities of these compounds were observed in oxic waters. Concentration levels of reduced sulfur compounds in Baltic oxic waters were very close to levels of the Black Sea oxic zone. Thiosulfate and S° were predominate compounds in oxic water whereas sulfide was a predominant compound of Baltic waters high in hydrogen sulfide. Conclusion was made that during sedimentation in oxic waters anaerobic microorganisms along with aerobic bacteria take part in mineralization of organic matter. They exist on surfaces and in microniches of particles of organic detritus.

Ocean acidification increases the accumulation of toxic phenolic compounds across trophic levels

Increasing atmospheric CO2 concentrations are causing ocean acidification (OA), altering carbonate chemistry with consequences for marine organisms. Here we show that OA increases by 46-212% the production of phenolic compounds in phytoplankton grown under the elevated CO2 concentrations projected for the end of this century, compared with the ambient CO2 level. At the same time, mitochondrial respiration rate is enhanced under elevated CO2 concentrations by 130-160% in a single species or mixed phytoplankton assemblage. When fed with phytoplankton cells grown under OA, zooplankton assemblages have significantly higher phenolic compound content, by about 28-48%. The functional consequences of the increased accumulation of toxic phenolic compounds in primary and secondary producers have the potential to have profound consequences for marine ecosystem and seafood quality, with the possibility that fishery industries could be influenced as a result of progressive ocean changes.

Response of Nodularia spumigena to pCO2 - Part 3: Turnover of phosphorus compounds

Diazotrophic cyanobacteria often form extensive summer blooms in the Baltic Sea driving their environment into phosphate limitation. One of the main species is the heterocystous cyanobacterium Nodularia spumigena. N. spumigena exhibits accelerated uptake of phosphate through the release of the exoenzyme alkaline phosphatase that also serves as an indicator of the hydrolysis of dissolved organic phosphorus (DOP). The present study investigated the utilization of DOP and its compounds (e.g. ATP) by N. spumigena during growth under varying CO2 concentrations, in order to estimate potential consequences of ocean acidification on the cell's supply with phosphorus. Cell growth, phosphorus pool fractions, and four DOP-compounds (ATP, DNA, RNA, and phospholipids) were determined in three set-ups with different CO2 concentrations (341, 399, and 508 µatm) during a 15-day batch experiment. The results showed rapid depletion of dissolved inorganic phosphorus (DIP) in all pCO2 treatments while DOP utilization increased with elevated pCO2, in parallel with the growth stimulation of N. spumigena. During the growth phase, DOP uptake was enhanced by a factor of 1.32 at 399 µatm and of 2.25 at 508 µatm compared to the lowest pCO2 concentration. Among the measured DOP compounds, none was found to accumulate preferentially during the incubation or in response to a specific pCO2 treatment. However, at the beginning 61.9 ± 4.3% of the DOP were not characterized but comprised the most highly utilized fraction. This is demonstrated by the decrement of this fraction to 27.4 ± 9.9% of total DOP during the growth phase, especially in response to the medium and high pCO2 treatment. Our results indicate a stimulated growth of diazotrophic cyanobacteria at increasing CO2 concentrations that is accompanied by increasing utilization of DOP as an alternative P source.