Oscar Urrutia

Design, Synthesis, and Biological Evaluation of Phosphoramide Derivatives as Urease Inhibitors

The design, synthesis, and biological evaluation of phosphoramide derivatives as urease inhibitors to reduce the loss of ammonia has been carried out. Forty phosphorus derivatives were synthesized and their inhibitory activities evaluated against that of jack bean urease. In addition, in vivo assays have been carried out. All of the compounds were characterized by IR, (1)H NMR, MS, and elemental microanalysis. In some cases, detailed molecular modeling studies were carried out, and these highlighted the interaction between the enzyme active center and the compounds and also the characteristics related to their activity as urease inhibitors. According to the IC(50) values for in vitro inhibitory activity, 12 compounds showed values below 1 microM and 8 of them represent improvements of activity in comparison to the commercial urease inhibitor N-n-butylthiophosphorictriamide (NBPT) (100 nM) (AGROTAIN). On the basis of the activity results and the conclusions of the molecular modeling study, a structural model for new potential inhibitors has been defined.

Efficiency of urease and nitrification inhibitors in reducing ammonia volatilization from diverse nitrogen fertilizers applied to different soil types and wheat straw mulching.

BACKGROUND Some authors suggest that the absence of tillage in agricultural soils might have an influence on the efficiency of nitrogen applied in the soil surface. In this study we investigate the influence of no-tillage and soil characteristics on the efficiency of a urease inhibitor (N-(n-butyl)thiophosphoric triamide, NBPT) and a nitrification inhibitor (diciandiamide, DCD) in decreasing ammonia volatilization from urea and ammonium nitrate (AN), respectively. RESULTS The results indicate that ammonia volatilization in soils amended with urea was significantly higher than in those fertilized with AN. Likewise, the main soil factors affecting ammonia volatilization from urea are clay and sand soil contents. While clay impedes ammonia volatilization, sand favours it. The presence of organic residues on soil surface (no-tillage) tends to increase ammonia volatilization from urea, although this fact depended on soil type. The presence of NBPT in urea fertilizer significantly reduced soil ammonia volatilization. This action of NBPT was negatively affected by acid soil pH and favoured by soil clay content. CONCLUSION The presence of organic residues on soil surface amended with urea increased ammonia volatilization, and was particularly high in sandy compared with clay soils. Application of NBPT reduced ammonia volatilization although its efficiency is reduced in acid soils. Concerning AN fertilization, there were no differences in ammonia volatilization with or without DCD in no-tillage soils.

Structural Characteristics of Phosphoramide Derivatives as Urease Inhibitors. Requirements for Activity

Taking as a reference the structural characteristics of a set of compounds that act as jack bean ( Canavalia ensiformis) urease inhibitors, namely, phenylphosphorodiamidate (PPD), N- n-butylthiophosphorictriamide (NBPT), and N- n-butylphosphorictriamide (NBPTO), we have studied the structure-activity relationships of a series of phosphoramide derivatives for which the activity as urease inhibitors in both in vitro and in vivo assays is known. Molecular modeling studies were carried out, and the results highlighted the relevance of characteristics such as the presence of intramolecular hydrogen bonds, the volume of the fragment involved in the enzyme interaction, and the degree of conformational freedom as well as the HOMO orbital and atomic orbital contributions to the HOMO orbital, electron density, and PEM distributions on the activity of these compounds as urease inhibitors. These data, along with the preliminary docking study carried out, allow us to propose a union mode to the active site of the enzyme for these compounds.

Theoretical chemical characterization of phosphate‐metal–humic complexes and relationships with their effects on both phosphorus soil fixation and phosphorus availability for plants

BACKGROUND Previous studies showed that phosphate can be complexed by humic acids (HA) through stable metal (M) bridges (PMHA). We studied the thermodynamic properties of PMHA and their relationships with the ability of PMHA to both decrease soil P fixation and increase P availability for plants. With this aim, we studied the theoretical stability of PFeHA, PAlHA and PCaHA by molecular modelling methods in relation to the degree and intensity of P absorption in soils and the ability of plants to take up complexed P. RESULTS A density functional theory (DFT) quantum chemical study enabled us to obtain stable structures for the three PMHA complexes in water solution. The theoretical stabilities (ΔG⁰) were consistent with that for apparent stability obtained by Scatchard method, PFeHA ≥ PAlHA > PCaHA, though the differences were clearer by the DFT method. Also the reduction of soil P fixation and the release of P from PMHA in the presence of an anionic resin confirmed the stability order of the different PMHA. Plant studies confirmed the ability of diverse plant species to take up both P and metal complexed in PMHA. CONCLUSION The results indicated the potential efficiency of PMHA-based fertilizers to optimize P fertilization for crops cultivated in soils with high P fixation ability.

Some Structural and Electronic Features of the Interaction of Phosphate with Metal−Humic Complexes

Previous studies demonstrated the formation of stable phosphate-metal-humic complexes in solution. These studies, however, indicated that the proportion of complexed metal that intervenes in phosphate fixation is rather low. In this study we investigate the possible structural and electronic features of the binding site involved in phosphate fixation in metal-humic complexes that could explain this fact. To this end, we have studied phosphate-metal-humic complexes involving Fe(III), Al(III), and Zn(II) using three complementary techniques: infrared spectroscopy (FTIR), fluorescence, and molecular modeling. The FTIR study indicated that, in the case of those complexes involving Fe and Zn phosphate, fixation is associated with a stabilization of the metal-carboxylate bond. In the case of Al this effect is less clear. This effect of phosphate fixation on the characteristics of the metal-humic binding site was also supported by the results obtained in the Fluorescence study, which showed significant changes in the quenching effect normally associated with metal complexation in humic substances upon phosphate fixation. Finally, the molecular modeling study revealed that the stability of phosphate-metal-humic complexes is inversely related to the stability of the metal-humic interaction. This result could explain why only a relatively low proportion of humic complexed metal is involved in phosphate fixation.

Organic Complexed Superphosphates (CSP): Physicochemical Characterization and Agronomical Properties

A new type of superphosphate (organic complexed superphosphate (CSP)) has been developed by the introduction of organic chelating agents, preferably a humic acid (HA), into the chemical reaction of single superphosphate (SSP) production. This modification yielded a product containing monocalcium phosphate complexed by the chelating organic agent through Ca bridges. Theoretically, the presence of these monocalcium-phosphate-humic complexes (MPHC) inhibits phosphate fixation in soil, thus increasing P fertilizer efficiency. This study investigateed the structural and functional features of CSP fertilizers produced employing diverse HA with different structural features. To this end were used complementary analytical techniques: solid-phase ³¹P NMR, ¹³C NMR, laser-confocal microscopy, X-ray diffraction, and molecular modeling. Finally, the agronomical efficiency of four CSP have been compared with that of SSP as P sources for wheat plants grown in both alkaline and acidic soils in greenhouse pot trials under controlled conditions. The results obtained from the diverse analytical studies showed the formation of MPHC in CSP. Plant-soil studies showed that CSP products were more efficient than SSP in providing available phosphate for wheat plants cultivated in various soils with different physicochemical features. This fact is probably associated with the ability of CSP complexes to inhibit phosphate fixation in soil.

Structural Characterization of Anion–Calcium–Humate Complexes in Phosphate‐based Fertilizers

Fertilizers based on phosphate-metal-humate complexes are a new family of compounds that represents a more sustainable and bioavailable phosphorus source. The characterization of this type of complex by using solid (31)P NMR in several fertilizers, based on single superphosphate (SSP) and triple superphosphate (TSP) matrices, yielded surprising and unexpected trends in the intensity and fine structure of the (31)P NMR peaks. Computational chemistry methods allowed the characterization of phosphate-calcium-humate complexes in both SSP and TSP matrices, but also predicted the formation of a stable sulfate-calcium-humate complex in the SSP fertilizers, which has not been described previously. The stability of this complex has been confirmed by using ultrafiltration techniques. Preference towards the humic substance for the sulfate-metal phase in SSP allowed the explanation of the opposing trends that were observed in the experimental (31)P NMR spectra of SSP and TSP samples. Additionally, computational chemistry has provided an assignment of the (31)P NMR signals to different phosphate ligands as well as valuable information about the relative strength of the phosphate-calcium interactions within the crystals.

Incorporation of humic-derived active molecules into compound NPK granulated fertilizers: main technical difficulties and potential solutions

Numerous studies carried out both in open field and laboratory scale have provided experimental evidence for a beneficial action of humic substances (HS) on plant growth and mineral nutrition. In fact, many products containing diverse concentrations of humic substances, mainly humic and fulvic acids, are marketed as plant growth enhancers all over the world. However, the incorporation of molecules containing humic substances into the granules of compound NPK fertilizers is not a common practice mainly due to technical difficulties and problems associated with the manufacture process of these mineral fertilizers. These problems are normally linked to the potential deleterious effects of granulation conditions (principally, heat and pH) on the structure and properties of molecules containing humic substances. In this review, we discuss several strategies for the incorporation of active molecules containing humic substances into granules of NPK compound fertilizers as well as the main constraints that have to be considered in this process, which normally depend on the agronomical results intended with the preparation of special humic-containing NPK compound fertilizers. We also discuss why, in our opinion, the beneficial action of HS in NPK compound fertilizers is more related to the “so called” indirect effects of HS on plant growth than to the “so called” direct effects.Graphical abstractLocalization of humic-calcium-phosphate based NPK fertilizer granule into the rhizosphere of maize plants cultivated in a calcareous soil

New Amphiphilic Composite for Preparing Efficient Coated Potassium-Fertilizers for Top-Dressing Fertilization of Annual Crops

This study describes the efficiency of a new coating material for preparing granulated potassium-fertilizers with a potassium release to the soil solution sensitive to rainfall intensity. The composite is prepared by reaction of an alkyd-resin with cement in the absence of water. The complementary use of diverse analytical techniques showed that the presence of the cement fraction induced alkyd resin reticulation and gradual cement-resin hardening. Scanning electron microscopy revealed the formation of micro and nanopores within cement-clusters, whose water permeability is affected by the resin reticulation and amphiphilic character. Potassium release was evaluated in water, soil-columns, and in soil-plant trials in pots and open-field. Agronomic results were consistent with potassium release rates obtained in water solution and soil columns. The composite-coated potassium fertilizer was more efficient than the noncoated one in providing plant available potassium, with this effect being dependent on water presence in soil.