31P MAS NMR: a useful tool for the evaluation of VX natural weathering in various urban matrixes

The fate of chemical warfare agent VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) in various urban matrixes was monitored utilizing 31P MAS NMR. Chosen matrixes represent buildings, roads, pavement, and earth found in urban environments. In view of the high toxicity of VX, solid state NMR afforded a fairly safe experimental mode, omitting any chance for evaporation. Moreover, due to the nondestructive nature of these experiments, measurements could be repeated over and over using the same samples. Degradation rates of VX were obtained and compared to provide a list of relative reactivity toward VX: concrete > desert sand > beach sand > asphalt approximately to bitumen sheet. Chemical interactions between VX, its degradation products, and the matrixes were often expressed by widening of the peaks to the extent that mass balance could not be achieved. It is noteworthy that these experiments were usually carried out on crushed or milled specimens, allowing high reactivity and rapid reactions.     

Sequential extraction study of stability of adsorbed mercury in chemically modified activated carbons

Activated carbons chemically modified with sulfur and bromine are known for their greater effectiveness in capturing vapor Hg from coal combustion and other industrial flue gases. The stability of captured Hg in spent activated carbons determines the final fate of Hg and is critical to devising Hg control strategy. However, it remains a subject that is largely unknown, particularly for Br-treated activated carbons. Using a six-step sequential extraction procedure, this work evaluated the leaching potential of Hg captured with four activated carbons, one lignite-derived activated carbon, and three chemically treated with Br(2), KClO(3), and SO(2). The results demonstrated clearly the positive effect of Br- and SO(2)-treatment on the stability of captured Hg. The Hg captured with brominated activated carbon was very stable and likely in the form of mercurous bromide complex. Sulfur added at high temperature with SO(2) was able to stabilize a majority of Hg by forming sulfide and possibly sulfonate chelate. The presence of sulfate however made a small fraction of captured Hg (<10%) labile under mild conditions. Treating activated carbon with KClO(3) lowered the overall stability of captured Hg. A positive dependence of Hg stability on Hg loading temperature was observed for the first time.     

核磁共振磷谱法测定乳制品中的磷脂含量

为了测定乳制品中的磷脂含量,建立了基于核磁共振磷谱(³¹P NMR)的磷脂分析方法,并采用内标法对磷脂进行了定量。利用建立的方法对不同哺乳期母乳(初乳、过渡乳、成熟乳)、奶粉(全脂奶粉、婴幼儿配方奶粉)、富含乳磷脂的乳清蛋白粉、大豆磷脂及鸡蛋磷脂中的磷脂组成及含量进行了分析。结果表明：9种磷脂标准品的检出限范围为48.97～85.76μg/mL,定量限范围为97.94～171.52μg/mL,具有合理的加标回收率(83.40%～108.52%)和精密度(相对标准偏差小于15%)。母乳中总磷脂含量平均为19.27 mg/100 mL,随着哺乳期的延长总磷脂含量逐渐降低。不同来源的样品中磷脂的组成有较大差异,母乳中含量最高的磷脂类型为鞘磷脂,其他样品中的磷脂主要类型为磷脂酰胆碱。     

Use of perfused isolated muscle, as studied by (31)P NMR, to investigate metabolism and post-mortem changes

An experimental system was designed to study as independently as possible the effects of various in-vivo or post-mortem factors susceptible to influence muscle metabolism. This system was made up of an NMR probe, a physiological stimulator, a perfusion system and a force monitoring device. Rabbit muscles were isolated and perfused with bovine red cells, then put into the NMR probe to follow the evolution of pH and phosphorylated compounds. It was possible to keep muscle metabolism stable for 2 h. Death was simulated by stopping the perfusion which allowed post-mortem changes to be followed. The effects of adrenaline perfusion or of a 5 s tetanus on some traits of metabolism and on changes following muscle death were studied. Tetanus immediately before perfusion was stopped accelerated changes in pH and in phosphocreatine and ATP contents; adrenaline perfusion during 30 min before perfusion was stopped had little effect on these traits.     

Sediment depth attenuation of biogenic phosphorus compounds measured by 31P NMR

Being a major cause of eutrophication and subsequent loss of water quality, the turnover of phosphorus (P) in lake sediments is in need of deeper understanding. A major part of the flux of P to eutrophic lake sediments is organically bound or of biogenic origin. This P is incorporated in a poorly described mixture of autochthonous and allochthonous sediment and forms the primary storage of P available for recycling to the water column, thus regulating lake trophic status. To identify and quantify biogenic sediment P and assess its lability, we analyzed sediment cores from Lake Erken, Sweden, using traditional P fractionation, and in parallel, NaOH extracts were analyzed using 31P NMR. The surface sediments contain orthophosphates (ortho-P) and pyrophosphates (pyro-P), as well as phosphate mono- and diesters. The first group of compounds to disappear with increased sediment depth is pyrophosphate, followed by a steady decline of the different ester compounds. Estimated half-life times of these compound groups are about 10 yr for pyrophosphate and 2 decades for mono- and diesters. Probably, these compounds will be mineralized to ortho-P and is thus potentially available for recycling to the water column, supporting further growth of phytoplankton. In conclusion, 31P NMR is a useful tool to asses the bioavailability of certain P compound groups, and the combination with traditional fractionation techniques makes quantification possible.     

Adsorption of methyl mercaptan on activated carbons

Activated carbons of different origins were studied as methyl mercaptan adsorbents in wet, dry, and oxidizing conditions. The materials were characterized using adsorption of nitrogen, Boehm titration, and thermal analysis. Investigation was focused on the feasibility of the removal of methyl mercaptan on activated carbons and on the role of surface chemistry and porosity in the adsorption/oxidation processes. The results showed relatively high capacities of carbons for removal of CH3SH. The amount adsorbed depends on the surface features. Methyl mercaptan, in general, is oxidized to disulfides, which, depending on the chemistry of the carbon surface, can be converted to sulfonic acid due to the presence of water and active radicals.     

Investigation of commercial lecithin by 31P NMR in a ternary CUBO solvent

Many different ways have been devised over the years for analysing phospholipids in solution by ³¹P NMR. One promising method entails the use of the so‐called CUBO solvent, a ternary mixture of dimethylformamide, triethylamine and guanidinium hydrochloride. As this interesting system seems to have been overlooked in the literature, we present here a study on the quantification of phospholipids and lysophospholipids contained in 10 samples of commercial lecithin using the CUBO/³¹P NMR method. Cluster analysis and principal component analysis of the NMR data showed clear differences among the samples according to the actual lecithin producer. Multivariate analysis of the chemical and physical parameters of the samples confirmed these differences. Copyright © 2004 Society of Chemical Industry     

Determination of the Posphorylation of Starch from Native Potato Varieties by 31P NMR

³¹P NMR technique was used to determine variations between potato varieties in the degree of phosphorylalion on the C-3 and C-6 sites of the glucosidyl units of the amylopectin molecules. The C-3 phosphorylation was independent of the potato variety, while a substantial variation in the C-6 phosphorylation was observed.     

Determination of neo- and D-chiro-inositol hexakisphosphate in soils by solution 31P NMR spectroscopy

The inositol phosphates are an abundant but poorly understood group of organic phosphorus compounds found widely in the environment. Four stereoisomers of inositol hexakisphosphate (IP(6)) 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-IP(6) and used them to identify signals from these compounds in three soils from the Falkland Islands. Both compounds resisted hypobromite oxidation and gave quantifiable (31)P NMR signals at δ = 6.67 ppm (equatorial phosphate groups of the 4-equatorial/2-axial conformer of neo-IP(6)) and δ = 6.48 ppm (equatorial phosphate groups of the 2-equatorial/4-axial conformer of D-chiro-IP(6)) 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-IP(6) 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-IP(6) in the environment. The hypobromite oxidation and solution (31)P NMR spectroscopy procedure allows the simultaneous quantification of all four IP(6) stereoisomers in environmental samples and provides a platform for research into the origins and ecological significance of these enigmatic compounds.     

多聚磷酸盐在鸡腿肉中水解的~(31)P核磁共振研究

利用31P核磁共振(NMR)对添加到鸡腿肉中的焦磷酸四钠(TSPP)和三聚磷酸钠(STPP)所发生的水解进行了研究。三组新鲜鸡腿肉样品,按照200ml腌制液/kg的比例分别注入新配制的腌制液5%NaCl、5%NaCl+6%TSPP、5%NaCl+6%STPP。结果表明,TSPP和STPP在肉中均发生水解。TSPP水解成正磷酸钠,STPP水解成焦磷酸钠和正磷酸钠,生成的焦磷酸钠随即水解成正磷酸钠。STPP水解速率大于TSPP。     

(31)P NMR study of post mortem changes in pig muscle

The rate and the extent of post mortem pH changes in pig muscle largely determine pork quality. Fast pH fall combined with low ultimate pH leads to pale soft exudative (PSE) meat; high ultimate pH leads to dark firm dry (DFD) meat. Post mortem metabolism was studied in pig muscle using(31)P NMR. Fifteen pigs, i.e. 7 Large White pigs and 8 Pietrain pigs, were used. Five pigs of each breed were slaughtered, taking care to minimize preslaughter stress. The other pigs (3 Large Whites and 2 Pietrains) were injected with 0·1 mg adrenaline per kg liveweight before slaughter, in order to increase meat ultimate pH. All the animals were killed by electronarcosis and exsanguination. Three of the adrenaline-treated pigs (1 Large White and 2 Pietrains) gave meat with ultimate pH above 6 (DFD meat). The pigs with normal muscle ultimate pH, i.e. 6 Large Whites and 6 Pietrains, had very variable rates of post mortem muscle metabolism (pH at 30 min after slaughter: 6·17-6·85 in Large Whites; 6·04-6·23 in Pietrains). The relationships between pH and ATP changes were similar in all pigs showing normal muscle ultimate pH, whereas ATP disappeared at a high pH value (on average pH 6·4) in pigs with high ultimate pH. The course of post mortem biochemical changes in a given animal could be predicted rather well by examination of a single(31)P NMR spectrum obtained around 30 min after death. At this time, muscle with a low rate of metabolism simultaneously showed medium to high pH, high ATP content (4-6·8 μmol/g) and rather low Pi content (6-14 μmol/g); muscle with a fast rate of metabolism (PSE-prone muscle) had low pH, low to medium ATP content (1·1-4 μmol/g) and generally high phosphomonoester (PME) content (9-23 μmol/g); muscle with high ultimate pH (DFD-prone muscle) had high pH, low PME content (4-8 μmol/g) and high Pi content (22-27 μmol/g).     

Monitoring the effect of three humic acids on a model membrane system using 31P NMR

The sorption of three humic acids to 1,2-dipalmitoyl-sn-glycero-3-phosphocholine multilamellar vesicle model membrane systems was studied by phosphorus nuclear magnetic resonance (31P NMR). The effects of temperature and pH were investigated. The gel --> bilayer transition did not appear to be affected by any of the humic acids at pH 7; however, all three humic acids induced a perturbation to this transition and to the bilayer structure at pH 4. On the basis of the findings from this and other work, a conceptual adsorption/absorption model for the sorption of humic acid (HA) to biomembranes has been put forward. The model requires an initial adsorption step initiated at an acidic pH by hydrogen bridging and electrostatic interactions between the functional groups of the HAs and the head groups of the phospholipids. Once the HA material is adsorbed, its hydrophobic domains can further seek a more thermodynamically favorable environment within the bilayer using hydrophobic interactions. These interactions lead to the HA being absorbed into the membrane, which subsequently induces the observed perturbation by disturbing the ordered packing of the phospholipid tail groups. This model is also related to other humic substances/biomembrane observations in the literature.     

Linking phosphorus sequestration to carbon humification in wetland soils by 31P and 13C NMR spectroscopy

Phosphorus sequestration in wetland soils is a prerequisite for long-term maintenance of water quality in downstream aquatic systems, but can be compromised if phosphorus is released following changes in nutrient status or hydrological regimen. The association of phosphorus with relatively refractory natural organic matter (e.g., humic substances) might protect soil phosphorus from such changes. Here we used hydrofluoric acid (HF) pretreatment to remove phosphorus associated with metals or anionic sorption sites, allowing us to isolate a pool of phosphorus associated with the soil organic fraction. Solution (31)P and solid state (13)C NMR spectra for wetland soils were acquired before and after hydrofluoric acid pretreatment to assess quantitatively and qualitatively the changes in phosphorus and carbon functional groups. Organic phosphorus was largely unaffected by HF treatment in soils dominated by refractory alkyl and aromatic carbon groups, indicating association of organic phosphorus with stable, humified soil organic matter. Conversely, a considerable decrease in organic phosphorus following HF pretreatment was detected in soils where O-alkyl groups represented the major fraction of the soil carbon. These correlations suggest that HF treatment can be used as a method to distinguish phosphorus fractions that are bound to the inorganic soil components from those fractions that are stabilized by incorporation into soil organic matter.     

Liquid droplet-like behaviour of whole casein aggregates adsorbed on graphite studied by nanoindentation with AFM

AFM measurements in the force volume mode were performed over the total penetration depth for different positions on casein aggregates adsorbed to a graphite surface in a liquid cell. The stiffness of the force curves was correlated to indentation depths, layer depth and lateral position within the aggregates with the aim of arriving at a credible explanation for the shapes of the force curves. The commonly used Hertz-based models did not fit the experimental data.The ratio between the height and diameter of the adsorbed casein aggregates was found to be linear, suggesting surface energy dominated liquid droplet behaviour. To investigate the possibility, numerical simulations were performed using the Surface Evolver, an interactive finite element program for the study of surfaces shaped by surface tension and other energies. Simulated force curves were in good agreement with experimental findings, both with respect to slope as a function of indentation as well as describing the variation with indentation position on the aggregate due to interfacial and geometric effects.By comparing the simulated force curves to the measurement data it was found that there would have been an interfacial energy equivalent to 10 mJ/m².     

Studies of polyphosphate composition and their interaction with dairy matrices by ion chromatography and 31P NMR spectroscopy

The use of ion-exchange chromatography and ³¹P nuclear magnetic resonance (³¹P NMR) to analyse the composition and the chain length of phosphate emulsifying salts were studied, as well as the impact of these salts in dairy products. Ion chromatography was more appropriate than ³¹P NMR to study polyphosphate composition in complex environments, whereas interactions between phosphate species and dairy components were elucidated by ³¹P NMR. Phosphate species interacting with calcium, as well as the percentage of chelated calcium, were identified using ³¹P NMR. Thus, ion chromatography and solid-sate ³¹P NMR could be used as complementary methods to study compositions of polyphosphate blends and their interactions with dairy matrices.     

Phosphorus composition of sheep feces and changes in the field determined by 31P NMR spectroscopy and XRPD

Information on the P species in sheep feces is lacking. Such information is required to understand P-cycling in grazed ecosystems. The P composition of feces from sheep grazing grass in Scotland was assessed on freeze-dried samples by 31P MAS (magic angle spinning) NMR (nuclear magnetic resonance) spectroscopy and XRPD (X-ray powder diffraction). The 31P MAS NMR spectrum showed resonances and sidebands consistent with dicalcium phosphate dihydrate (brushite) and ammonium magnesium phosphate hexahydrate (struvite). XRPD confirmed the result and allowed quantification of these minerals, which accounted for 63% of the P. To determine transformations in the field, sheep feces were collected and reapplied to sheep-free pasture in synthetic patches during late summer. The dry weight decreased with time and the feces disappeared between 84 and 112 days following heavy rainfall. The concentration of P in the feces recovered at intervals up to 84 days changed little with time but the contribution from brushite and struvite decreased and within 1 week <50% remained indicating conversion into other forms. Solution-phase 31P NMR spectra of NaOH/EDTA extracts of the feces were dominated by the inorganic orthophosphate with minor amounts of organic P that were attributed to phosphate esters and polyphosphates.     

Direct speciation of phosphorus in alum-amended poultry litter: solid-state 31P NMR investigation

Amending poultry litter (PL) with aluminum sulfate (alum) has proven to be effective in reducing water-soluble phosphorus (P) in the litter and in runoff from fields that have received PL applications; it has therefore been suggested as a best management practice. Although its effectiveness has been demonstrated on a macroscopic scale in the field, little is known about P speciation in either alum-amended or unamended litter. This knowledge is important forthe evaluation of the long-term stability and bioavailability of P, which is a necessary prerequisite forthe assessment of the sustainability of intensive poultry operations. Both solid-state MAS and CP-MAS 31P NMR as well as 31P[27Al]-TRAPDOR were used to investigate P speciation in alum-amended and unamended PL. The results indicate the presence of a complex mixture of organic and inorganic orthophosphate phases. A calcium phosphate phase, probably a surface precipitate on calcium carbonate, could be identified in both unamended and alum-amended PL, as well as physically bound HPO4(2-). Phosphate associated with Al was found in the alum-amended PL, most probably a mixture of a poorly ordered wavellite and phosphate surface complexes on aluminum hydroxide that had been formed by the hydrolysis of alum. However, a complex mixture of organic and inorganic phosphate species could not be resolved. Phosphate associated with Al comprised on average 40 +/- 14% of the total P in alum-amended PL, whereas calcium phosphate phases comprised on average 7 +/- 4% in the alum-amended PL and 14 +/- 5% in the unamended PL.     

Influence of surface properties on the mechanism of H2S removal by alkaline activated carbons

Alkaline activated carbons are widely used as adsorbents of hydrogen sulfide (H2S), one of the major odorous compounds arising from sewage treatment facilities. Although a number of studies have explored the effects of various parameters, mechanisms of H2S adsorption by alkaline carbons are not yet fully understood. The major difficulty seems to lie in the fact that little is known with certainty about the predominant reactions occurring on the carbon surface. In this study, the surface properties of alkaline activated carbons were systematically investigated to further exploit and better understand the mechanisms of H2S adsorption by alkaline activated carbons. Two commercially available alkaline activated carbons and their representative exhausted samples (8 samples collected at different height of the column after H2S breakthrough tests) were studied. The 8 portions of the exhausted carbon were used to represent the H2S/carbon reaction process. The surface properties of both the original and the exhausted carbons were characterized using the sorption of nitrogen (BET test), surface pH, Boehm titration, thermal and FTIR analysis. Porosity and surface area provide detailed information about the pore structure of the exhausted carbons with respect to the reaction extent facilitating the understanding of potential pore blockages. Results of Boehm titration and FTIR both demonstrate the significant effects of surface functional groups, and identification of oxidation products confirmed the different mechanisms involved with the two carbons. From the DTG curves of thermal analysis, two well-defined peaks representing two products of surface reactions (i.e., sulfur and sulfuric acid) were observed from the 8 exhausted portions with gradually changing patterns coinciding with the extent of the reaction. Surface pH values of the exhausted carbons show a clear trend of pH drop along the reaction extent, while pH around 2 was observed for the bottom of the bed indicating sulfuric acid as the predominant products. Although both carbons are coal-based and of KOH impregnated type, performances of different carbons differ significantly. A correlation is well established to link the reaction extent with various surface properties. In summary, not only the homogeneous alkali impregnation and physical porosity but also the carbon surface chemistry are significant factors influencing the performances of alkaline activated carbons as H2S adsorbents.     

Colloidal calcium phosphates in casein micelles studied by slow-speed-spinning 31P magic angle spinning solid-state nuclear magnetic resonance.

The composition of bovine casein micelles was analyzed by 31P magic angle spinning solid-state nuclear magnetic resonance spectroscopy. By looking at isotropic and anisotropic 31P chemical shift parameters, resonance line shapes, the combination of single-pulse and 1H to 31P cross-polarization spectra, and comparison with spectra for various model compounds combined with multiple-component simulation and iterative fitting procedures, we were able to identify and quantify a variety of inorganic and organic phosphates in the micelles. These include phosphates from mobile and immobile inorganic hydroxyapatite-type phosphates as well as phosphates from kappa-casein and the Ca2+-binding phosphoserines from alphas1-, alphas2-, and beta-casein. This information is discussed in relation to previous knowledge and various models for the colloid formation.