Synthesis of the hexaphosphates of myo‐, scyllo‐, neo‐ and <scp>D</scp>‐inositol

Cosgrove, D. J.

doi:10.1002/jsfa.2740171206

Cited by 25 publications

(7 citation statements)

References 14 publications

(2 reference statements)

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“…The accumulation of scy/Zo-inositol hexakisphosphate compared to the myo isomer (that is, an increasing scyllo to myo ratio) in the early stages of soil development is consistent with the greater apparent recalcitrance of the scyllo structure (Cosgrove 1966), despite potentially larger inputs of myo-inositol hexakisphosphate from plant material (Raboy 2007).…”

Section: Discussionmentioning

confidence: 74%

Soil Organic Phosphorus Transformations During Pedogenesis

et al. 2007

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Long-term changes in soil phosphorus influence ecosystem development and lead to a decline in the productivity of forests in undisturbed landscapes. Much of the soil phosphorus occurs in a series of organic compounds that differ in their availability to organisms, but changes in the relative abundance of these compounds during pedogenesis remain unknown. We used alkaline extraction and solution phosphorus-31 nuclear magnetic resonance spectroscopy to assess the chemical nature of soil organic phosphorus along a 120,000-year postglacial chronosequence at Franz Josef, New Zealand. Inositol phosphates, DNA, phospholipids, and phosphonates accumulated rapidly during the first 500 years of soil development characterized by nitrogen limitation of biological productivity, but then declined slowly to low concentrations in older soils characterized by intense phosphorus limitation. However, the relative contribution of the various compounds to the total organic phosphorus varied along the sequence in dramatic and surprising ways. The proportion of inositol hexakisphosphate, conventionally considered to be relatively recalcitrant in the environment, declined markedly in older soils, apparently due to a corresponding decline in amorphous metal oxides, which weather to crystalline forms during pedogenesis. In contrast, the proportion of DNA, considered relatively bioavailable in soil, increased continually throughout the sequence, due apparently to incorporation within organic structures that provide protection from biological attack. The changes in soil organic phosphorus coincided with marked shifts in plant and microbial communities, suggesting that differences in the forms and bioavailability of soil organic phosphorus have ecological significance. Overall, the results strengthen our understanding of phosphorus transformations during pedogenesis and provide important insight into factors regulating the composition of soil organic phosphorus.

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Section: Discussionmentioning

confidence: 74%

Soil Organic Phosphorus Transformations During Pedogenesis

et al. 2007

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“…Without further purification, the crude material was dissolved in concentrated aqueous ammonia solution (30 mL), and the mixture was heated at 60 °C overnight in a Pyrex pressure tube. After evaporation of the solution under vacuum, the residue was purified by ion exchange chromatography to afford the pure triethyl ammonium salt of d - chiro -inositol 1,2,3,4,5,6-hexakisphosphate (1.06 g, 91% from d - chiro -inositol) as a hygroscopic white solid 25 (analytical information presented in the Supporting Information). …”

Section: Methodsmentioning

confidence: 99%

Determination of neo- and d-chiro-Inositol Hexakisphosphate in Soils by Solution ³¹P NMR Spectroscopy

Turner

Cheesman

Godage

et al. 2012

Environ. Sci. Technol.

130

102

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The inositol phosphates are an abundant but poorly understood group of organic phosphorus compounds found widely in the environment. Four stereoisomers of inositol hexakisphosphate (IP6) occur, although for three of these (scyllo, neo, and d-chiro) the origins, dynamics, and biological function remain unknown, due in large part to analytical limitations in their measurement in environmental samples. We synthesized authentic neo- and d-chiro-IP6 and used them to identify signals from these compounds in three soils from the Falkland Islands. Both compounds resisted hypobromite oxidation and gave quantifiable 31P NMR signals at δ = 6.67 ppm (equatorial phosphate groups of the 4-equatorial/2-axial conformer of neo-IP6) and δ = 6.48 ppm (equatorial phosphate groups of the 2-equatorial/4-axial conformer of d-chiro-IP6) in soil extracts. Inositol hexakisphosphate accounted for 46–54% of the soil organic phosphorus, of which the four stereoisomers constituted, on average, 55.9% (myo), 32.8% (scyllo), 6.1% (neo), and 5.2% (d-chiro). Reappraisal of the literature based on the new signal assignments revealed that neo- and d-chiro-IP6 occur widely in both terrestrial and aquatic ecosystems. These results confirm that the inositol phosphates can constitute a considerable fraction of the organic phosphorus in soils and reveal the prevalence of neo- and d-chiro-IP6 in the environment. The hypobromite oxidation and solution 31P NMR spectroscopy procedure allows the simultaneous quantification of all four IP6 stereoisomers in environmental samples and provides a platform for research into the origins and ecological significance of these enigmatic compounds.

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“…The Nowra NaOH-EDTA soil extract (3.5 mL and 0.3 mL D 2 O) was consecutively spiked with 0.1-mL aqueous solutions of 4.1 g L −1 β-glycerophosphate (Sigma-Aldrich G26251, Sigma-Aldrich Pty., Sydney), 3.7 g L −1 of glycerol phosphate disodium salt (50% β-isomer and 50% rac-α-isomer; Sigma-Aldrich G6501), and 1.9 g L −1 ethanolamine phosphate (Sigma-Aldrich P0503). The Tocal extract was consecutively spiked with 0.1 mL of a 1.1 g L −1 aqueous phytate (Na salt from corn [Zea mays L.], Sigma-Aldrich P8810) solution, a small quantity (<2 mg) of scyllo-inositol hexakisphosphate (purifi ed and synthesized by the late Dr. D. Cosgrove [Cosgrove, 1963[Cosgrove, , 1966, formerly of CSIRO Plant Industry, Canberra, Australia; this was the same compound made available to Turner and Richardson [2004]), which was added directly into the redissolved NaOH-EDTA soil extract, and fi nally, a 0.1 mL aqueous solution of 0.5 g L −1 choline phosphate (Sigma-Aldrich 250457).…”

Section: Spikingmentioning

confidence: 99%

Spiking Improved Solution Phosphorus‐31 Nuclear Magnetic Resonance Identification of Soil Phosphorus Compounds

Doolette

Smernik

Dougherty

2009

Soil Science Soc of Amer J

191

250

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Chemical characterization of soil organic P using 31P nuclear magnetic resonance (NMR) spectroscopy relies on the correct assignment of resonances. We examined eight Australian soils and identified the main orthophosphate monoester peaks by spiking model organic P compounds (α‐ and β‐glycerophosphate, ethanolamine phosphate, phytate, scyllo‐inositol hexakisphosphate, and choline phosphate) into NaOH–ethylenediaminetetraacetic acid (EDTA) soil extracts. For five of the soils, the strongest monoester resonances were identified as being due to phytate, while for the other three soils, the strongest resonances were identified as being due to α‐ and β‐glycerophosphate. Importantly, the appearance of spectra dominated by phytate and those dominated by glycerophosphate were deceptively similar because the separation between the two strongest phytate resonances was very similar to the separation between the α‐ and β‐glycerophosphate resonances. We believe this may have resulted in the misidentification of these species in some previous studies. Identification of these species is hindered by the sensitivity of their chemical shifts to pH and electrolyte concentration. Our spiking methodology, in which we add only enough of the compound to approximately double the native concentration, overcomes this problem. We also investigated the alkaline hydrolysis of phospholipids as a likely source of α‐ and β‐glycerophosphate. We found that the rate of phospholipid hydrolysis was dependant on NaOH concentration and that the presence of glycerophosphate resonances in soil extracts probably results from the extraction and redissolution procedures rather than the presence of native glycerophosphate in the soils. We also identified an intermediate diester product that may have previously been misidentified as the phospholipid itself.

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Synthesis of the hexaphosphates of myo‐, scyllo‐, neo‐ and D‐inositol

Cited by 25 publications

References 14 publications

Soil Organic Phosphorus Transformations During Pedogenesis

Soil Organic Phosphorus Transformations During Pedogenesis

Determination of neo- and d-chiro-Inositol Hexakisphosphate in Soils by Solution ³¹P NMR Spectroscopy

Spiking Improved Solution Phosphorus‐31 Nuclear Magnetic Resonance Identification of Soil Phosphorus Compounds

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Synthesis of the hexaphosphates of myo‐, scyllo‐, neo‐ and D‐inositol

Cited by 25 publications

References 14 publications

Soil Organic Phosphorus Transformations During Pedogenesis

Soil Organic Phosphorus Transformations During Pedogenesis

Determination of neo- and d-chiro-Inositol Hexakisphosphate in Soils by Solution 31P NMR Spectroscopy

Spiking Improved Solution Phosphorus‐31 Nuclear Magnetic Resonance Identification of Soil Phosphorus Compounds

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Determination of neo- and d-chiro-Inositol Hexakisphosphate in Soils by Solution ³¹P NMR Spectroscopy