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Esterification of inorganic phosphate accompanies the oxidation of succinic acid by cell-free extracts of E. coli. Inorganic phosphate appears to be an essential requirement for the dehydrogenation of the C(4)-dicarboxylic acid.
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The 1:1 reactions of [((i)()Pr(2)N)BP(H)B(N(i)()Pr(2))PLi.DME] (1) and [(tmp)BP(H)B(tmp)PLi.DME] (2; tmp = 2,2,6,6-tetramethylpiperidino) with organylhalostannanes have been examined, and stannyl-substituted diphosphadiboretanes, (R(2)N)BP(H)B(NR(2))PSn(Cl)R'(2) (R(2)N = (i)()Pr(2)N, tmp; R' = Me, (t)()Bu) have been isolated and characterized. Dehydrohalogenation of these compounds with (t)()BuLi produced bicyclic cage compounds P(2)(R(2)NB)(2)SnR'(2) (R(2)N = (i)()Pr(2)N (9), tmp (8); R' = (t)()Bu) or an oligomer [-P(R(2)NB)(2)PSn(R'(2))-] (R(2)N = tmp; R' = Me). The 2:1 reactions of R'(2)SnCl(2) with 1 and 2 have been studied, and with a small R' group (Me) a disubstitution product, [HP(tmpB)(2)P](2)SnMe(2) (11), is obtained. With a larger R' group ((t)()Bu), cage products P(2)(tmpB)(2)Sn(t)()Bu(2) and P(2)((i)()Pr(2)NB)(2)Sn(t)()Bu(2) are isolated. The molecular structures of 8 and 9 have been determined by single crystal X-ray diffraction techniques, and these structures and their spectroscopic features are discussed in relation to other boron-phosphorus cage compounds.
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Phytase, an enzyme that degrades the phosphorus storage compound phytate, has the potential to enhance phosphorus availability in animal diets when engineered into soybean (Glycine max) seeds. The phytase gene from Aspergillus niger was inserted into soybean transformation plasmids under control of constitutive and seed-specific promoters, with and without a plant signal sequence. Suspension cultures were used to confirm phytase expression in soybean cells. Phytase mRNA was observed in cultures containing constitutively expressed constructs. Phytase activity was detected in the culture medium from transformants that received constructs containing the plant signal sequence, confirming expectations that the protein would follow the default secretory pathway. Secretion also facilitated characterization of the biochemical properties of recombinant phytase. Soybean-synthesized phytase had a lower molecular mass than did the fungal enzyme. However, deglycosylation of the recombinant and fungal phytase yielded polypeptides of identical molecular mass (49 kD). Temperature and pH optima of the recombinant phytase were indistinguishable from the commercially available fungal phytase. Thermal inactivation studies of the recombinant phytase suggested that the additional protein stability would be required to withstand the elevated temperatures involved in soybean processing.
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Phosphorus nitride (PN) has been detected in the interstellar medium. The J = 2-1, 3-2, 5-4, and 6-5 rotational lines of this species have been observed toward Orion-KL, and the J = 2-1 transition in Sgr B2 and W51. The PN line profiles in Orion indicate that the molecule's emission arises from the "plateau" or "doughnut" region associated with the outflow from IRc2. The species is thus primarily present in hot, dense gas. Column densities derived for PN toward Orion-KL are 3-4 X 10(13) cm-2, but may be as high as 10(14) cm-2, if the species is located in a 10" region. These column densities imply a fractional abundance for PN in the Orion "plateau" of approximately 1-4 X 10(-10). Such a large abundance for phosphorus nitride is not predicted by quiescent cloud ion-molecule chemistry and suggests that high-temperature processes are responsible for the synthesis of PN in the KL outflow.
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The processes that affect removal and retention of nitrogen during wastewater treatment in constructed wetlands (CWs) are manifold and include NH(3) volatilization, nitrification, denitrification, nitrogen fixation, plant and microbial uptake, mineralization (ammonification), nitrate reduction to ammonium (nitrate-ammonification), anaerobic ammonia oxidation (ANAMMOX), fragmentation, sorption, desorption, burial, and leaching. However, only few processes ultimately remove total nitrogen from the wastewater while most processes just convert nitrogen to its various forms. Removal of total nitrogen in studied types of constructed wetlands varied between 40 and 55% with removed load ranging between 250 and 630 g N m(-2) yr(-1) depending on CWs type and inflow loading. However, the processes responsible for the removal differ in magnitude among systems. Single-stage constructed wetlands cannot achieve high removal of total nitrogen due to their inability to provide both aerobic and anaerobic conditions at the same time. Vertical flow constructed wetlands remove successfully ammonia-N but very limited denitrification takes place in these systems. On the other hand, horizontal-flow constructed wetlands provide good conditions for denitrification but the ability of these system to nitrify ammonia is very limited. Therefore, various types of constructed wetlands may be combined with each other in order to exploit the specific advantages of the individual systems. The soil phosphorus cycle is fundamentally different from the N cycle. There are no valency changes during biotic assimilation of inorganic P or during decomposition of organic P by microorganisms. Phosphorus transformations during wastewater treatment in CWs include adsorption, desorption, precipitation, dissolution, plant and microbial uptake, fragmentation, leaching, mineralization, sedimentation (peat accretion) and burial. The major phosphorus removal processes are sorption, precipitation, plant uptake (with subsequent harvest) and peat/soil accretion. However, the first three processes are saturable and soil accretion occurs only in FWS CWs. Removal of phosphorus in all types of constructed wetlands is low unless special substrates with high sorption capacity are used. Removal of total phosphorus varied between 40 and 60% in all types of constructed wetlands with removed load ranging between 45 and 75 g N m(-2) yr(-1) depending on CWs type and inflow loading. Removal of both nitrogen and phosphorus via harvesting of aboveground biomass of emergent vegetation is low but it could be substantial for lightly loaded systems (cca 100-200 g N m(-2) yr(-1) and 10-20 g P m(-2) yr(-1)). Systems with free-floating plants may achieve higher removal of nitrogen via harvesting due to multiple harvesting schedule.
This article explores a new, convenient route to beta-phosphorus nitroxides. Specifically, the reaction sequence involves the novel 1,3-addition of trimethylsilyl phosphites (e.g. diethyl) or trimethylsilyl phosphines (e.g. diphenyl) to aldo-nitrones [e.g. alpha-phenyl-N-tert-butylnitrone (PBN) or 5,5-dimethyl-l-pyrroline-N-oxide (DMPO)] or keto-nitrones [e.g. 2-ethyl-5,5-dimethyl-1 pyrroline-N-oxide (2-Et-DMPO) or 2-phenyl-5,5-dimethyl-l-pyrroline-N-oxide (2-Ph-DMPO)] to form alpha-phosphityl- or alpha-phosphinyl-O-silylhydroxylamines. Acidic hydrolysis provides the corresponding hydroxylamines that are easily oxidized to the title beta-phosphorus-nitroxides. ESR spectroscopic analysis revealed some very large beta-phosphorus hyperfine splittings (i.e. in excess of 5 mT). For this reason and their remarkable stability (persistence) some of these nitroxides show promise as integral components in new, improved weak-field dynamic nuclear polarization (DNP) magnetometers.
In this article solid-state NMR methods for the determination of internuclear dipole-dipole couplings between homonuclear spin-1/2 nuclei are presented. They are suitable for relatively dense dipolar networks which are still dominated by 2-spin interactions. C-/R-symmetry theory is applied to create a double-quantum average Hamiltonian using phase-modulated radio-frequency irradiation and magic-angle sample-rotation. Symmetry derived pulse sequences with improved compensation against chemical shift anisotropies were found assuming a small isotropic chemical shift difference and using numerical calculations of the spin dynamics. Moreover it is shown that a constant time procedure can be used to acquire reliable double-quantum build-up curves even in systems in which damping obscures oscillations in their symmetric build-up curve. This technique is demonstrated on four crystalline model compounds with 31P and 13C spin systems typical for inorganic and biological applications. Comparison to crystal structure data indicates that the distances derived this way from 31P and 13C double-quantum NMR carry only small systematic errors caused for example by anisotropic J-coupling, dipolar contributions from adjacent spins and relaxation.
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