Phosphoryl Triamide Research Articles

Insight in the 3D morphology of silica-based nanotubes using electron microscopy

Amorphous silica-based nanotubes (SBNTs) were synthesized from phosphoryl triamide, OP(NH2)3, thiophosphoryl triamide, SP(NH2)3, and silicon tetrachloride, SiCl4, at different temperatures and with varying amount of the starting material SiCl4 using a recently developed template-free synthesis approach. Diameter and length of the SBNTs are tunable by varying the synthesis parameters. The 3D mesocrystals of the SBNTs were analyzed with focused ion beam sectioning and electron tomography in the transmission electron microscope showing the hollow tubular structure of the SBNTs. The reconstruction of a small SBNT assembly was achieved from a high-angle annular-dark field scanning transmission electron microscopy tilt series containing only thirteen images allowing analyzing beam sensitive material without altering the structure. The reconstruction revealed that the individual nanotubes are forming an interconnected array with an open channel structure.

Ba6P12N17O9Br3 – A Column‐Type Phosphate Structure Solved from Single‐Nanocrystal Data Obtained by Automated Electron Diffraction Tomography

AbstractOxonitridophosphate Ba6P12N17O9Br3 was synthesized by heating a multicomponent mixture of BaBr2, BaS, phosphoryl triamide and thiophosphoryl triamide in an evacuated and sealed silica‐glass ampoule to 750 °C. Ba6P12N17O9Br3 was obtained as the main product as a nanocrystalline powder. The crystal structure was determined ab initio on the basis of electron diffraction data acquired from a single needle‐shaped nanocrystal by automated diffraction tomography. Ba6P12N17O9Br3 crystallizes in the hexagonal space group P63/m (no. 176) with unit cell parameters a = 14.654(19), c = 8.255(9) Å and Z = 2. Its structure includes triangular, column‐shaped anions of ∞1{(P12N17O9)9–}, which are built from vertex‐sharing P(O,N)4 tetrahedra with 3‐rings and three‐coordinate nitrogen atoms. The 1D anions are separated by Ba2+ and Br– ions, which are arranged in channels parallel to the phosphate anions along [001]. The Ba2+ ions are eight‐ and nine‐coordinated by Br– and O/N atoms, respectively.

SrP3N5O: A Highly Condensed Layer Phosphate Structure Solved from a Nanocrystal by Automated Electron Diffraction Tomography

The oxonitridophosphate SrP(3)N(5)O has been synthesized by heating a multicomponent reactant mixture that consisted of phosphoryl triamide OP(NH(2))(3), thiophosphoryl triamide SP(NH(2))(3), SrS, and NH(4)Cl enclosed in evacuated and sealed silica-glass ampoules up to 750 °C. The compound was obtained as nanocrystalline powder with needle-shaped crystallites. The crystal structure was solved ab initio on the basis of electron diffraction data by means of automated electron diffraction tomography (ADT) and verified by Rietveld refinement with X-ray powder diffraction data. SrP(3)N(5)O crystallizes in the orthorhombic space group Pnma (no. 62) with unit-cell data of a=18.331(2), b=8.086(1), c=13.851(1) Å and Z=16. The compound is a highly condensed layer phosphate with a degree of condensation κ=½. The corrugated layers (∞)(2){(P(3)N(5)O)(2-)} consist of linked, triangular columns built up from P(O,N)(4) tetrahedra with 3-rings and triply binding nitrogen atoms. The Sr(2+) ions are located between the layers and exhibit six-, eight-, and ninefold coordination. FTIR and solid-state NMR spectra of SrP(3)N(5)O are discussed as well.

Unprecedented Zeolite-Like Framework Topology Constructed from Cages with 3-Rings in a Barium Oxonitridophosphate

A novel oxonitridophosphate, Ba(19)P(36)O(6+x)N(66-x)Cl(8+x) (x ≈ 4.54), has been synthesized by heating a multicomponent reactant mixture consisting of phosphoryl triamide OP(NH(2))(3), thiophosphoryl triamide SP(NH(2))(3), BaS, and NH(4)Cl enclosed in an evacuated and sealed silica glass ampule up to 750 °C. Despite the presence of side phases, the crystal structure was elucidated ab initio from high-resolution synchrotron powder diffraction data (λ = 39.998 pm) applying the charge flipping algorithm supported by independent symmetry information derived from electron diffraction (ED) and scanning transmission electron microscopy (STEM). The compound crystallizes in the cubic space group Fm ̅3c (no. 226) with a = 2685.41(3) pm and Z = 8. As confirmed by Rietveld refinement, the structure comprises all-side vertex sharing P(O,N)(4) tetrahedra forming slightly distorted 3(8)4(6)8(12) cages representing a novel composite building unit (CBU). Interlinked through their 4-rings and additional 3-rings, the cages build up a 3D network with a framework density FD = 14.87 T/1000 Å(3) and a 3D 8-ring channel system. Ba(2+) and Cl(-) as extra-framework ions are located within the cages and channels of the framework. The structural model is corroborated by (31)P double-quantum (DQ) /single-quantum (SQ) and triple-quantum (TQ) /single-quantum (SQ) 2D correlation MAS NMR spectroscopy. According to (31)P{(1)H} C-REDOR NMR measurements, the H content is less than one H atom per unit cell.

Phosphoryl Triamide Polymers Revisited: Identification of Structural Units with ESI-MS/MS and Solid State NMR

The thermal condensation of phosphoryl triamide was reinvestigated and analyzed with ESI-MS as well as 31P- and 1H-NMR spectroscopy in the solid state and in solution. Our results indicate that strongly crosslinked polymers are formed even at temperatures lower than 300 °C; and, furthermore, evidence for facile partial hydrolysis of oligomeric condensation products on contact with water has been established using ESI-MS/MS.

Comparison of The Efficiencies of Urea Nitrogen and Phosphoryl Triamide Nitrogen forLolium Multiflorumand Their Influence on the Soil Nitrogen Reserve

Abstract 15N-Labelled phosphoryl triamide (PTA) was synthesized. Experiments with Lolium multiflorum plants in vegetation pots have shown that there are important differences between urea and PTA treatments. At high N rates, uptake of N by plants increased in both treatments and N uptake from the soil reserve decreased. The coefficient of N utilization by plants was higher in the urea than in the PTA treatments. However, at the highest N rate, the coefficient of N utilization by plants was higher in the PTA than in the urea treatment. A strong negative correlation was found between the rates applied and the decrease of N content in the soil reserve.

Inhibition of jack bean urease by phosphoric-and thiophosphorictriamides

Three phosphorictriamides and two thiophosphorictriamides were tested for their urease inhibitory activities by using jack bean urease in an enzyme assay. The phosphorictriamides were N-(n-butyl)phosphorictriamide (NBPTO), cyclohexylphosphorictriamide (CHPT) and phosphoryltriamide (PT), and the thiophosphorictriamides were N-(n-butyl)thiophosphorictriamide (NBPT) and thiophosphoryltriamide. The assay technique used provided a relatively quick assessment of the effectiveness of the compounds tested to inhibit jack bean urease. NBPTO was a more effective inhibitor of jack bean urease than CHPT and PT. The concentrations of NBPTO, CHPT and PT required for 50% inhibition under the conditions of the experiment were 0.2, 6 and 23 μ m, respectively. Evaluation of these compounds at various concentration ranges showed NBPTO and CHPT to be promising urease inhibitors.

Inhibition of urease activity in flooded soils: Effect of thiophosphorictriamides and phosphorictriamides

The effectiveness of two thiophosphorictriamides, [N-(n-butyl)thiophosphorictriamide (NBPT) and thiophosphoryltriamide (TPT)], and three phosphorictriamides, [N-(n-butyl)phosphorictriamide (NBPTO), phosphoryltriamide (PT) and cyclohexylphosphorictriamide (CHPT)], to inhibit urease activity in flooded soils in the presence or absence of photosynthetic algae was evaluated in laboratory experiments. Both TPT and its oxygen analogue PT were poor inhibitors of urease activity in these flooded soils in the presence or absence of algae. In the absence of photosynthetic algae, the rate of urea hydrolysis was retarded slightly by the addition of NBPT. However, in the presence of algae the capacity of NBPT to inhibit urease activity was enhanced considerably. It appears that the oxygen produced by the photosynthetic algae resulted in more rapid conversion of the pro inhibitor NBPT to NBPTO, which is the effective urease inhibitor. The phosphorictriamides CHPT and NBPTO were significantly better than the other compounds for retarding urease activity, and CHPT ranked above NBPTO as a urease inhibitor. In the presence of photosynthetic algae the effectiveness of these inhibitors appears to be reduced, and this seems to be related to algal uptake of nitrogen and more rapid volatilization of ammonia and nitrification. The results suggest that the phosphorictriamides CHPT and NBPTO in conjunction with an algicide, to control the growth of floodwater algae, have the potential to considerably reduce ammonia loss from flooded rice soils.

Soil urease inhibition by thermal polymers of thioposphoryl triamide and phosphoryl triamide

Ammonia volatilization losses from urea applications are particularly high when urea is not mixed well into soils. These losses have been shown to be reduced by use of urease inhibitors, but as yet there has been no commercial development of these materials. The effectiveness of urease inhibitors formed by the thermal polymerization of phosphoryl triamide (PTA) and thiophosphoryl triamide (TPTA) was investigated under carefully controlled experimental conditions. The PTA-derived thermal polymers showed less apparent urease inhibitory activity than phenyl phosphorodiamidate (PPDA) but were nearly equal or slightly better than PTA itself. The TPTA-derived polymers were significantly better urease inhibitors than their PTA-derived counterparts. Several of the PTA-derived products had greater persistence than PPDA. The urease inhibition in soils indicated that the optimum chain length for these polymeric inhibitors may be from two to four.

Shrink-Proof Finish of Cellulosics by Phosphoryl Amides Part 1. Preparation of Phosphoryl Amides in Methanol Saturated with Ammonia.

A comparative study was carried out on the reaction products of phosphoryl chloride and ammonia (phosphoryl amides) in a conventional solvent, ethyl ether, and in methanol saturated with ammonia. In ethyl ether, amide-substituted products were practically insoluble in the solvent, thus the reaction mixture became slurry in the course of the reaction and the complete substitution of amide for chlorine was difficult, while in the ammonia-saturated solution, the reaction products were almost soluble in the solvent and more than 90% of reaction products was phosphoryl triamide. While phosphoryl triamide and ammonium chloride (a by-product of the reaction) have low solubility in both solvents, methanol and liquid ammonia, the ammonia-saturated methanol was a good solvent for both phosphoryl triamide and ammonium chloride. Although the reaction of methanol with phosphoryl chloride proceeded vigorously even at lower temperatures, only a very small amount of methoxy-substituted products were detected in the reaction mixture by use of the ammonia-saturated solution. Therefore, the ammonia-satu-rated methanol was very suitable for the preparation of phosphoryl triamide for shrink-proof finish of rayon and silk.

Formation of phosphoryl triamide by decomposition of thiophosphoryl triamide in soil

Thiophosphoryl triamide inhibits soil urease activity when added to soil and is under consideration as a fertilizer amendment for retarding hydrolysis of urea fertilizer by soil urease. Work reported showed that this compound is a poor inhibitor of jackbean urease and that its ability to retard soil urease activity is due to its decomposition in soil with formation of phosphoryl triamide, which is a potent inhibitor of urease activity. This conclusion was supported by studies showing a close relationship between the peak area of the 31P-nuclear magnetic resonance (NMR) signal from phosphoryl triamide in thiophosphoryl triamide solutions that had been incubated with soil for various times and the ability of these solutions to inhibit jackbean urease activity.

Phosphorus-nitrogen compounds electrical conductivity of phosphoryl triamide polymer

The polycondensation at 180°C of phosphoryl triamide, PO(NH 2) 3, gave the linear polymer; at higher temperatures up to 300°C the product was the network polymer. The temperature dependence was measured under various conditions. The activation energy for conduction of both polymers was 1.2 eV. Broad line 1H-NMR spectroscopy was used in confirmation of the electrical conductivity, and the temperature dependence of line-width was also measured. Comparison of the electrical conductivities of ▪ indicates that the proton in the amido group may play an important part in the conductivity.

Foliar Application of P. I. Screening of Various Inorganic and Organic P Compounds1

AbstractThe suitability of 32 different P compounds for foliar application was tested by using a new technique in which predetermined quantities of P were applied to a fixed leaf area. This made it possible to obtain quantitative data on absorption of added P and on translocation of absorbed P out of the treated area. Presently foliar applications of P are used less than N, one reason being that no P compound is available which can be sprayed on plants in large enough quantities without damaging the leaves. Several representatives of the condensed phosphates and some compounds containing P‐N bonds or P‐N‐P linkages proved promising. Both group of compounds hydrolyze spontaneously to release orthophosphate, and all share the quality of delayed action. These P sources could be applied at 2.5 to 3 times the quantity of P that could be applied as orthophosphate in a greenhouse experiment without causing leaf damage. The most successful compound for corn (Zea mays L.) was ammonium tripolyphosphate, which could be applied at 370 µg of P/cm2 without causing leaf damage; 66% of the applied P was absorbed within 10 days, and 87% of the absorbed P was translocated out of the area of application in the same period. Other successful compounds for corn were ammonium tetrapolyphosphate and phosphoryl triamide. Soybeans (Glycine max L. Merr.) proved more sensitive than corn and could, in general, tolerate only two‐thirds to three‐fourths of the quantity of the various compounds that could be applied to corn, with the exception of phosphonitrilic hexaamide, which could be applied at 340 µg of P/cm2. Ammonium tri‐ and tetrapolyphosphate could be applied at 220 µg of P/cm2 to soybeans. Rapid intake is suspected to be an important reason for the damage observed with orthophosphate. Several organic P compounds were tested, but none of them was superior to the condensed P sources.

Foliar Application of P. II. Yield Responses of Corn and Soybeans Sprayed with Various Condensed Phosphates and P‐N Compounds in Greenhouse and Field Experiments1

AbstractGreenhouse and field experiments were conducted with corn (Zea mays L.) and soybeans (Glycine max L. Merr.) to evaluate the growth response of foliar sprays with several condensed phosphates and P‐N compounds. The maximum concentration of P tolerated in solutions of tri‐ and tetrapolyphosphates applied as sprays in the greenhouse was 1.3% with corn and 1.1% with soybeans. The maximum concentration of P tolerated as orthophosphate was 0.5% with corn and 0.4% with soybeans. With soybeans, the yields of plants sprayed with various condensed P compounds significantly exceeded the yields of the unsprayed control, which would not be classed as P‐deficient on the basis of the P content of the leaves. Spraying the plants, however, increased the P concentration in the leaves. Phosphoryl triamide produced the highest yields of above‐ground dry matter of corn plants in an experiment in which several P‐N compounds and condensed phosphates were brushed on the leaves. Several different condensed phosphates were sprayed on corn and soybeans in a field experiment on a fine loamy, mixed, mesic typic haplaquoll (Webster silt loam). An increase in yield of corn that was statistically significant at the 5% level was obtained from spraying. The yields with tri‐ and tetrapolyphosphate were, respectively, 760 and 754 kg/ha above the control yield of 10,234 kg/ha. With soybeans, the increase in yield due to treatment was significant at the 18% level, and the increase was equivalent to 256 kg/ha above the control yield of 3747 kg/ha.

Reaction Products between Phosphoryl Triamide and Some Transition Metal Chlorides in Aqueous Solution

The reactions between phosphoryl triamide and MCl2 {M = Mn(II), Co(II), Cu(II) (as trace nutrient)} in aqueous solutions were studied, and the products were examined by chemical analysis, ion-exchange chromatography, paper chromatography, X-ray powder diffraction method, IR spectroscopy, etc.M {PO(NH2)3}2Cl2(M = Mn(II), Co(II)) complexes that contained a small amount of diamidophosphate (6-11%) were obtained by adding acetone to the mixture of MCl2(M = Mn, Co) and PO(NH2)3 (P/M atomic ratio 1.5-2.0) at room temperature. On the other hand, PO(NH2)3 was hydrolyzed rapidly in the initial stage of its reaction with Cu(II), resulting in a precipitation of Cu(II) phosphates. Further, when a solid mixture of PO(NH2)3 and MCl2(M = Mn(II), Co(II)) with a molar ratio of 2:1 was dried in a vacuum desiccator after it had been wetted with a small amount of water and mixed thoroughly, it also yielded M{PO(NH2)3}2Cl2 complexes as major constituent.In the reaction of PO(NH2)3 with MCl2(M = Mn(II), Co(II), Cu(II), though it was hydrolyzed as the reaction time became longer (-72hr) and at higher temperature (-60°C), metal salts were precipitated that consisted of mainly amidophosphate, orthophosphate and diphosphate. The percentage of diphosphate in the hydrolysis products were 27%, 33% and 25% for Mn(II), Co(II) and Cu(II), respectively.The hydrolysis process of PO(NH2)3 in the reaction with MCl2 is discussed.

ボスホリルトリアミドとホルムアルデヒドとの反応及び反応生成物の添加によるポリビニルアルコールの難燃化

ボスホリルトリアミドとホルムアルデヒドとの反応及び反応生成物の添加によるポリビニルアルコールの難燃化

Enthalpy of formation of phosphoryl triamide

Enthalpy of formation of phosphoryl triamide

Low-temperature heat capacity and entropy of phosphoryl triamide

Low-temperature heat capacity and entropy of phosphoryl triamide