31P Nuclear Magnetic Resonance Spectroscopy Research Articles

Deciphering the Impact of ZnO Nanoparticles and a Sunscreen Product Containing ZnO on Phosphorus Dynamics and Release in Chlorella pyrenoidosa in Aquatic Systems.

Zinc oxide nanoparticles (ZnO NPs) expedite the conversion of organic phosphorus (OP) into PO4-P (Pi), facilitating phosphorus (P) absorption by algae. Our study explored the mechanisms of converting OP (2-aminoethylphosphonic acid (AEP) and β-glycerol phosphate (β-GP)) into Pi in Chlorella pyrenoidosa under P deficiency with sunscreen and ZnO NPs. Cell density followed the order of K2HPO4 > β-GP+ZnO > β-GP > AEP+ZnO > AEP > P-free. ZnO NPs promoted the conversion of β-GP, containing C-O-P bonds (0.028-0.041 mg/L), into Pi more efficiently than AEP, which possesses C-P bonds (0.022-0.037 mg/L). Transcriptomics revealed Pi transport/metabolism (phoB (3.99-12.01 fold), phoR (2.20-5.50 fold), ppa (4.49-10.40 fold), and ppk (2.50-5.40 fold)) and phospholipid metabolism (SQD1 (1.85-2.79 fold), SQD2 (2.60-6.53 fold), MGD (2.13-3.21 fold), and DGD (4.08-7.56 fold)) were up-regulated compared to K2HPO4. 31P nuclear magnetic resonance spectroscopy identified intracellular P as polyphosphate, orthophosphate, and pyrophosphate. Synchrotron radiation-based X-ray near-edge structure spectroscopy indicated that K2HPO4 and Zn3(PO4)2 in β-GP+ZnO were increased by 8.09% and 7.28% compared to AEP+ZnO, suggesting superior P storage in β-GP+ZnO. Overall, ZnO NPs improved photoinduced electron-hole pair separation and charge separation efficiency and amplified the ·OH and ·O2- levels, promoting OP photoconversion into Pi and algae growth.

Evolution and controls of organic phosphorus based on 31P nuclear magnetic resonance spectroscopy along a 2-million-year tropical soil chronosequence in northern Hainan Island, China

Evolution and controls of organic phosphorus based on 31P nuclear magnetic resonance spectroscopy along a 2-million-year tropical soil chronosequence in northern Hainan Island, China

Phospholipid analyses of rabbit ocular surface tissues

The tissues of the integument covering the ocular surface comprise a mucus membrane functioning as a protective physical barrier and has the ability to mount a defensive inflammatory response. Since lipid metabolism has a role in both of these functions, we studied normal membrane phospholipids (PL) of the cornea and bulbar conjunctiva to (1) determine baseline PL profiles of these tissues, (2) compare and contrast these individual PL metabolite profiles as well as groups of metabolites, and (3) describe pathway-specific metabolic interrelations among these tissues. Corneal and conjunctival tissue samples were isolated from rabbit eyes (n = 30) and extracted with chloroform-methanol using a modified Folch procedure. 31P nuclear magnetic resonance spectroscopy was used to qualitatively and quantitatively measure tissue PL profiles. The cornea and conjunctiva, respectively, have the following PL composition (mole % of total detected phospholipid): phosphatidylglycerol (PG) –, 0.4; lysophosphatidylethanolamine 1.2, –; phosphatidic acid –, 0.4; diPG (cardiolipin) 2.1, 3.5; unknown PL at the chemical shift of 0.13 δ 1.5, 0.9; ethanolamine plasmalogen 11.2, 13.0; phosphatidylethanolamine 11.5, 12.8; phosphatidylserine 8.9, 10.1; sphingomyelin 10.2, 10.7; lysophosphatidylcholine 0.9, 1.4; phosphatidylinositol 5.3, 5.3; phosphatidylcholine (PC) plasmalogen or alkylacylPC 2.2, 1.9; PC 45.1, 40.0. In addition, 28 PL metabolic indices were calculated from these data, which permitted pathway-specific lipid analyses. This study (1) establishes PL profiles of the two ocular tissues of the integument that cover the surface of the eye, (2) compares and contrasts indices comprised of ratios and combinations of PL, and (3) describes pathway-specific metabolic interrelations among these tissues to serve as baselines for studies involving the distribution of tissue phospholipids.

Identification and quantification of phosphate turnover indicators after long-term compost application – long-term and single season effects

Abstract Background and aims Soil organic phosphorus (Porg) is of interest for plant nutrition because it can comprise between 20 and 80% of total soil phosphate (P). This study aims to examine the effect of compost application on soil phosphatases and microbial biomass, which influence the P turnover and, furthermore, to examine the speciation of Porg. Methods Soil from a long-term field experiment (since 1997) which compares compost application with inorganic fertilization was analyzed for calcium-acetate-lactate extractable P (CAL-P), Olsen-P, acid (Acid-Pase) and alkaline (Alk-Pase) phosphatase activity and microbial biomass P. Porg speciation was additionally analyzed with liquid-state 31P nuclear magnetic resonance spectroscopy (31P-NMR). Results We found a significant increasing long-term effect of high compost application (equivalent to 400 kg ha−1 N (400)) on Acid-Pase (45%) and Alk-Pase (58%). After compost application, Acid-Pase increased by 41% in treatment 400 (3 days after compost application (DAA)). The 31P-NMR analysis showed a significant increase of inorganic orthophosphate (55%) after high compost application. Furthermore, the total phosphomonoester region was significantly decreased in the treatment 400 (8%). Conclusions We demonstrated that long-term compost application increases phosphatase activity which plays a key role in the mineralization of soil Porg. In particular, the decrease of the concentration of Porg species in the phosphomonoester region in the treatment 400 with high compost application highlights that an increased turnover affects this soil P pool and may provide P to plants. This knowledge provides a better understanding of how the P cycle responds to long-term compost fertilization.

Phosphorus release and realignment in anaerobic digestion of thermal hydrolysis pretreatment sludge – Masking effects from high ammonium

Waste activated sludge (WAS) is a significant phosphorus (P) repository, and there is a growing interest in P recovery from WAS. Typically, the commercial technology for treating WAS involves thermal hydrolysis pretreatment (THP) coupled with anaerobic digestion (AD). However, there is ongoing debate regarding the transformation and distribution of P throughout this process. To address this, a long-term THP-AD process was operated in this study to comprehensively investigate P transformation and distribution. The results revealed that a substantial biodegradation of dissolved organic nitrogen (DON) raised the pH of the digestate to 8.3 during the AD process. This increased pH facilitated the dissolution of Al, leading to a reduction of 6.92 mg/L of NaOH-P. Simultaneously, sulfate reduction contributed to a decrease of 11.04 mg/L of Bipy-P in the solid. However, the reduction of Bipy-P and NaOH-P in the solid did not result in an improved P release to the supernatant. Conversely, a decrease of 23.60 mg/L P in the aqueous phase was observed after anaerobic digestion. The disappeared P was primarily precipitated with Mg and Ca, driven by the increased pH, and it contributed to the increase of HCl-P in the solid from 107.80 to 144.52 mg/L. These findings were further confirmed by results obtained from scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and solid-state 31P nuclear magnetic resonance (NMR) spectroscopy. This study provides valuable insights into the mechanisms of P transformation during THP-AD process that is nearly opposite from conventional AD system.

From Pulp to Aromatic Products-Reaction Pathways of Lignin Depolymerization.

This study investigated the depolymerization of lignin into aromatic monomer compounds under hydrothermal conditions. A reaction scheme highlighting secondary alkylation reactions as well as the molecular weight shift was developed based on the experimental data. Lignin is produced in large quantities in paper production and dissolved in what is known as black liquor (BL). To avoid lignin recovery as an additional process step, BL is used directly as feedstock in the hydrothermal liquefaction (HTL) in this work. We performed various batch experiments in micro autoclaves with BL and model substances at different reaction temperatures (TR = 250-400 °C) and a holdingtime of tR = 20 min, as well as continuous experiments (TR = 325-375 °C, tR = 20 min). We were able to show that different derivatives of catechols are the main products among the monomers in our process. With the help of the model substance experiments, we were able to work out three main reactions: demethoxylation, demethylation, and alkylation. This behavior could be observed in the case of BL from hardwood as well as from softwood. 31P nuclear magnetic resonance (NMR) spectroscopy analysis has shown that these reactions take place on aromatic monomers as well as on larger aromatic oligomer structures. At higher temperatures, a large fraction of the carbon ends up in the solid product, while the yields of the monomers decrease sharply. 13C NMR spectroscopy of the solid material shows that the monomers are probably incorporated into the solid phase by repolymerization. We were also able to see this effect using size exclusion chromatography analysis based on the relative molecular weight. From all of the analytical results of the products, a reaction scheme was developed that describes the reaction pathways of the lignin during HTL. Based on this, a reaction kinetic model can be developed in the next step.

The Effects of Nitrogen‐Containing Monomers on the Thermal Degradation and Combustion Attributes of Polystyrenes Chemically Modified With Phosphonate Groups

AbstractIn the present study, polystyrene (PS) is chemically modified with diethyl(acryloyloxymethyl)phosphonate (DEAMP) and an N‐containing monomer, selected from different classes of compounds, via a ter‐polymerization route; thus, exploring possible P–N synergistic effects on fire retardance of the base polymer. The successful incorporation of P and N monomeric units is confirmed by Fourier Transform Infrared (FT‐IR), 1H and 31P Nuclear Magnetic Resonance (NMR) spectroscopies. The thermal degradation and combustion attributes of modified polymeric materials are measured using standard techniques, including Thermo‐Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), “bomb” calorimetry, and Pyrolysis Combustion Flow Calorimetry (PCFC). The thermal and combustion studies demonstrate that the thermal stability and combustion characteristics of styrenic polymers are significantly altered by the presence of even nominal amounts of P‐ and N‐containing groups, and in certain cases, synergistic interactions of these groups are also evident. For instance, as revealed by TGA, the extent of char formation, under the oxidative atmosphere, in the prepared ter‐polymers, is enhanced by 16–44%, when compared to the unmodified PS. The heat release rates and heat release capacities of ter‐polymers, measured using the PCFC technique, are reduced by 18–50%, in comparison to the same parameters obtained for the unmodified counterpart.

Internal phosphorus loading in a chain of eutrophic hardwater lakes in Saskatchewan, Canada

Sediments can act as a source or sink of phosphorus (P) for the water column of lakes. In iron (Fe)-rich softwater lakes, redox processes are important contributors to sediment P flux. However, the contribution of redox processes to P flux in hardwater lakes, with high pH and high concentrations of redox-insensitive calcium (Ca) is unknown. Intact sediment cores, collected in different seasons (summer or fall) from a chain of eutrophic hardwater lakes in southeastern Saskatchewan, Canada, were used to quantify sediment P fluxes in laboratory incubations under hypoxic or oxic conditions at temperatures consistent with the season of sample collection. Geochemical analyses determined concentrations of sediment total (TP) and organic P (TPo), organic matter (OM), total Ca and magnesium, and total and extractable manganese, Fe and aluminum. Sediment P pools were determined using sequential fractionation and solution 31P nuclear magnetic resonance spectroscopy. Sediment P fluxes were significantly higher in sediment cores incubated under hypoxic conditions (−24.4 to 28.5 mg P m−2 d−1) than oxic conditions (−60.3 to 14.2 mg P m−2 d−1). There were significant seasonal and lake differences for TP, TPo and cation concentrations, with Ca the dominant cation in all but one lake. Phosphate bound in the redox-sensitive pool was the only sediment P fraction that significantly differed among the lakes (0.10 to 0.18 mg P g−1 d.w.; 9 to 16 % of TP), with an inverse relationship to sediment P flux. Principal component analysis suggests that high concentrations of internally-generated TPo forms and OM in surface sediments play a key role in internal P loading in these lakes. However, sediment Ca appears to have an overriding effect on sediment P, partially masking the impact of redox control on internal P loading in these hardwater prairie lakes.

Quantitative lipid composition characterization of intact liposomes via 31P nuclear magnetic resonance spectroscopy.

Drug delivery systems (DDS) are important methods to maximize drug efficacy by enabling in vivo accumulation at the target site. Liposomes, which are nanoscale vesicles consisting of lipid bilayers, are widely used for clinical DDS. The lipid composition of an intact liposome is a significant factor that directly affects its characteristics and functions. Thus, it is important to develop quantitative or qualitative analytical methods to characterize the lipid composition. Nuclear magnetic resonance (NMR) of phosphorus (31P) is a particularly sensitive and non-destructive approach because phospholipid components have one 31P nucleus per molecule. Here, we demonstrate quantitative observations of individual phospholipids in intact liposomes via solution 31P-NMR. In addition, the 31P linewidths became narrower if the liposomes contained > 10mol% of polyethylene glycol-(PEGylated) phospholipids, which also contributed to liposome down-sizing. Down-sizing and PEGylation are important strategies for efficient drug delivery. Hence, 31P-NMR can be used to analyze phospholipids in liposomes and related pharmaceutical preparations for quality control.

The Fundamental Disorder Unit in (Si, P)-(O, N) Networks.

This study presents the synthesis and characterization of oxonitridosilicate phosphates Sr3SiP3O2N7, Sr5Si2P4ON12, and Sr16Si9P9O7N33 as the first of their kind. These compounds were synthesized under high-temperature (1400 °C) and high-pressure (3 GPa) conditions. A unique structural feature is their common fundamental building unit, a vierer single chain of (Si, P)(O, N)4 tetrahedra. All tetrahedra comprise substitutional disorder which is why we refer to it as the fundamental disorder unit (FDU). We classified four different FDU motifs, revealing systematic bonding patterns. Including literature known Sr5Si2P6N16, three of the four patterns were found in the presented compounds. Common techniques like single-crystal X-ray diffraction (SCXRD), elemental analyses, and 31P nuclear magnetic resonance (NMR) spectroscopy were utilized for structural analysis. Additionally, low-cost crystallographic calculations (LCC) provided insights into the structure of Sr16Si9P9O7N33 where NMR data were unavailable due to the lack of bulk samples. The optical properties of these compounds, when doped with Eu2+, were investigated using photoluminescence excitation (PLE), photoluminescence (PL) measurements, and density functional theory (DFT) calculations. Factors influencing the emission properties, including thermal quenching mechanisms, were discussed. This research reveals the new class of oxonitridosilicate phosphates with unique systematic structural features that offer potential for theoretical studies of luminescence and band gap tuning in insulators.

The Fundamental Disorder Unit in (Si, P)−(O, N) Networks

AbstractThis study presents the synthesis and characterization of oxonitridosilicate phosphates Sr3SiP3O2N7, Sr5Si2P4ON12, and Sr16Si9P9O7N33 as the first of their kind. These compounds were synthesized under high‐temperature (1400 °C) and high‐pressure (3 GPa) conditions. A unique structural feature is their common fundamental building unit, a vierer single chain of (Si, P)(O, N)4 tetrahedra. All tetrahedra comprise substitutional disorder which is why we refer to it as the fundamental disorder unit (FDU). We classified four different FDU motifs, revealing systematic bonding patterns. Including literature known Sr5Si2P6N16, three of the four patterns were found in the presented compounds. Common techniques like single‐crystal X‐ray diffraction (SCXRD), elemental analyses, and 31P nuclear magnetic resonance (NMR) spectroscopy were utilized for structural analysis. Additionally, low‐cost crystallographic calculations (LCC) provided insights into the structure of Sr16Si9P9O7N33 where NMR data were unavailable due to the lack of bulk samples. The optical properties of these compounds, when doped with Eu2+, were investigated using photoluminescence excitation (PLE), photoluminescence (PL) measurements, and density functional theory (DFT) calculations. Factors influencing the emission properties, including thermal quenching mechanisms, were discussed. This research reveals the new class of oxonitridosilicate phosphates with unique systematic structural features that offer potential for theoretical studies of luminescence and band gap tuning in insulators.

Chemical kinetics of silver diammine fluoride in demineralization and remineralization solutions-an in vitro study.

Silver Diammine Fluoride (SDF) is a clinical minimal intervention to manage dentin caries. Its chemistry in demineralization conditions has been investigated widely, but far less in remineralization conditions. The aim was to investigate and compare the chemical reactions when SDF is added to remineralization and demineralization solutions. 0.01 ml SDF (Riva Star) was added to deionized water (DW); demineralization (DS = pH4) and remineralization (RS = pH7.0) solutions. The time sequence of concentrations of NH4+, F-, and Ag+ were measured using ion selective electrodes (ISEs) every 2 min. The pH was also measured. Precipitates were characterized using x-ray Diffraction (XRD) and, 31P and 19F nuclear magnetic resonance spectroscopy (NMR). The concentrations of NH4+ and Ag+ showed decreasing trends in DW (-0.12 and -0.08 mM/h respectively), and in DS (-1.06 and -0.5 mM/h respectively); with corresponding increase in F- concentration (0.04 and 0.7 mM/h respectively). However, in RS, NH4+ concentration showed little change (0.001 mM/h), and Ag+ and F- concentrations were negligible. XRD results showed that precipitates (in RS only) contained AgCl, and metallic Ag. NMR showed that fluorapatite/carbonated fluorapatite (FAP/CFAP) were formed. The pH increased after SDF addition in all three solutions. SDF dissolved to release NH4+, F- and Ag + . In DW and DS, NH4+ combined with Ag+ to form diamminesilver, causing an increase of F- and pH. In RS, F- reacted with Ca2+ and (PO)43- to form FAP/CFAP, and Ag+ reacted with Cl- to form AgCl/Ag. These suggests why SDF is effective in managing dentin caries.

Preparation of waterborne intumescent flame-retardant coatings using adenosine-based phosphonates for wood surfaces

Here, organic solvent-free adenosine-based waterborne flame retardant curing agents were synthesized and introduction into a melamine urea-formaldehyde resin (MUF) to construct flame-retardant coatings for wood surfaces. Adenosine-based phosphonate (APU), composed of adenosine, urea, formaldehyde, and phosphorous acid, was synthesized by the Mannich reaction. The chemical structure of APU was investigated by Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and 31P nuclear magnetic resonance (NMR) spectroscopy. In contrast to MAW0, the coatings containing APU exhibited similar physical characteristics. MAW4 achieved a vertical combustion (UL-94) V-0 rating and an impressive limiting oxygen index (LOI) of 54.5 %. Cone calorimetry indicated that the time to ignition (TTI) of MAW4 was 89 s, an increase of 790 % compared with MAW0, which may significantly prolong the escape time from a fire. Scanning electron microscopy (SEM), thermal infrared imaging, and Raman spectroscopy all confirmed that continuous and dense char layers reduced the transport of heat, ignitable gases, and smoke. This limited the further pyrolysis and combustion of wood, showing that the waterborne intumescent flame-retardant coatings proposed in this research endowed wood with excellent flame retardancy.

Investigation of the lithiation mechanism of tin phosphite SnHPO3 as anode for Lithium-ion batteries

Phosphite-based anodes are attracting increasing attention in energy storage, especially for lithium-ion technology, due to their distinctive structures and their good electrochemical performances. Herein, the lithiation mechanism of tin phosphite SnHPO3 as lithium anode was examined for the first time. SnHPO3 has been synthesized through a soft hydrothermal route. Its structure was characterized by X-ray diffraction, Fourier Transform Infrared spectroscopy and 31P Nuclear Magnetic Resonance spectroscopy techniques. The reaction mechanisms of lithiation-delithiation of SnHPO3 anode was conducted using operando X-ray diffraction, ex-situ X-ray and ex-situ Fourier Transform Infrared spectroscopy techniques at room temperature. Both in-situ and ex-situ measurements show that SnHPO3 undergoes a conversion mechanism. The lithiation-delithiation of tin phosphite took place in a complex redox reaction sequence, and the reversible electrochemical phenomenon exclusively occurs through the alloying of tin at a low potential. The lithiation of tin phosphite begins by partial degradation of its structure, signifying the start of the conversion process. Then, the phosphite matrix becomes amorphous. The reversible capacity of the system is governed by the lithium‑tin alloying de-alloying process, produced at low potential.

Arrangement of lipid vesicles and bicelle-like structures formed in the presence of Aβ(25–35) peptide

Our complementary experimental data and molecular dynamics (MD) simulations results reveal the structure of previously observed lipid bicelle-like structures (BLSs) formed in the presence of amyloid-beta peptide Aβ(25–35) below the main phase transition temperature (Tm) of saturated phosphatidylcholine lipids and small unilamellar vesicles (SUVs) above this temperature. First, we show by using solid-state 31P nuclear magnetic resonance (NMR) spectroscopy that our BLSs being in the lipid gel phase demonstrate magnetic alignment along the magnetic field of NMR spectrometer and undergo a transition to SUVs in the lipid fluid phase when heated through the Tm. Secondly, thanks to the BLS alignment we present their lipid structure. Lipids are found located not only in the flat bilayered part but also around its perimeter, which is corroborated by the results of coarse-grained (CG) MD simulations. Finally, peptides appear to mix randomly with lipids in SUVs while assuming predominantly unordered secondary structures revealed by circular dichroism (CD), Raman spectroscopy, and all-atom MD simulations. Importantly, the former is changing little when the system undergoes morphological transitions between BLSs and SUVs. Our structural results then offer a platform for studying and understanding mechanisms of morphological transformations caused by the disruptive effect of amyloid-beta peptides on the lipid bilayer.

31P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium-Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal-Phosphorus Bond Order.

We report the use of solution and solid-state 31P Nuclear Magnetic Resonance (NMR) spectroscopy combined with Density Functional Theory calculations to benchmark the covalency of actinide-phosphorus bonds, thus introducing 31P NMR spectroscopy to the investigation of molecular f-element chemical bond covalency. The 31P NMR data for [Th(PH2)(TrenTIPS)] (1, TrenTIPS = {N(CH2CH2NSiPri3)3}3-), [Th(PH)(TrenTIPS)][Na(12C4)2] (2, 12C4 = 12-crown-4 ether), [{Th(TrenTIPS)}2(μ-PH)] (3), and [{Th(TrenTIPS)}2(μ-P)][Na(12C4)2] (4) demonstrate a chemical shift anisotropy (CSA) ordering of (μ-P)3- > (═PH)2- > (μ-PH)2- > (-PH2)1- and for 4 the largest CSA for any bridging phosphido unit. The B3LYP functional with 50% Hartree-Fock mixing produced spin-orbit δiso values that closely match the experimental data, providing experimentally benchmarked quantification of the nature and extent of covalency in the Th-P linkages in 1-4 via Natural Bond Orbital and Natural Localized Molecular Orbital analyses. Shielding analysis revealed that the 31P δiso values are essentially only due to the nature of the Th-P bonds in 1-4, with largely invariant diamagnetic but variable paramagnetic and spin-orbit shieldings that reflect the Th-P bond multiplicities and s-orbital mediated transmission of spin-orbit effects from Th to P. This study has permitted correlation of Th-P δiso values to Mayer bond orders, revealing qualitative correlations generally, but which should be examined with respect to specific ancillary ligand families rather than generally to be quantitative, reflecting that 31P δiso values are a very sensitive reporter due to phosphorus being a soft donor that responds to the rest of the ligand field much more than stronger, harder donors like nitrogen.

On the structure of Ag-containing sol-gel bioactive glasses: A surface crystal growth of metallic silver removes its network modifier role in the glass structure

Ag-containing bioactive glasses (Ag-BG) have been extensively studied as a bactericidal biomaterial, produced mainly by the sol-gel method over the last decades. According to the literature, sol-gel-derived Ag-BG may show metallic or ionic silver species in the glass structure. However, most of these works lack detailed information about how the addition of silver affects the glass network. In this study, we systematically produced sol-gel derived 58S glasses containing different quantities of Ag2O (1, 5, and 10 wt%), yielding glasses with different proportions of silver species (Ag0 or Ag+1). Results from X-ray diffraction and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) evidenced the progressive formation of silver crystals due to the addition of silver in the glass structure. 29Si and 31P nuclear magnetic resonance and photoelectronic X-ray spectroscopies evidenced a glass depolymerization caused by Ag1+ addition in the glass structure. On the other hand, the presence of silver crystals (Ag0) removes the network modifier role of silver, yielding glasses with higher network connectivity. A possible mechanism to explain the formation of silver crystals was proposed based on surface nucleation and growth. Finally, we suggest understanding Ag1+ or Ag0 formation as a solution to design glasses with tuned bactericidal properties.

Hydrophobicity, transparency, mechanically excellent and fire safety multifunctional epoxy resin based on a novel DOPO derivative with cyano group

A novel derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) bearing cyano groups, referred to as PDPO, was successfully synthesized and applied as an additive for epoxy resin (E-44, with epoxide equivalent weights ranging from 201 to 240 g/epoxide), along with the curing agent 4,4′-diaminodiphenylmethane (DDM). Comprehensive characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, 1H and 31P nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis (EA), were employed to confirm the chemical structure of PDPO. Thermogravimetric analysis (TGA) revealed remarkable thermal stability for PDPO, with a substantial char residue of 43.1 wt% at 800 °C. Introducing 5 wt% PDPO into the EP formulation resulted in a notable enhancement of fire retardancy, as evident from the increased Limiting Oxygen Index (LOI) value of 32.2 % and the attainment of UL-94 V-0 rating for the EP/PDPO-5. The efficacy of fire retardancy was further underscored by cone calorimeter (CC) testing, which showcased a reduction in heat release rate and smoke production. An in-depth analysis of pyrolysis behavior and char formation demonstrated that PDPO exhibited multifaceted roles in both the gas and condensed phases, contributing to the fire retardant properties of the material. Additionally, the incorporation of PDPO at a concentration of 1 wt% led to notable enhancements in the tensile and flexural strength of EP/PDPO-1 by 15.2 % and 10.4 %, respectively, compared to neat EP. Remarkably, the transparency of EP/PDPO-1 was preserved at 95.6 %, while the water contact angle was elevated to 115.5°, indicating improved hydrophobicity. These results collectively highlight the potential of PDPO as a fire-retardant additive, demonstrating its ability to simultaneously stay transparency and enhance mechanical properties and hydrophobic characteristics in the EP/PDPO systems.

Organic/inorganic phosphorus partition and transformation in long-term paddy cultivation in the Pearl River Delta, China

Identification and quantification of different soil phosphorus (P) fractions level are important for improving agricultural productivity and developing sustainable management practices in these agricultural soils under long-term cultivation. However, few studies have been conducted to investigate P fractions level and their transformation in these soils. This study was conducted to characterize P fractions as affected by different paddy cultivation ages (200, 400-yr and 900-yr) among soils of the Pearl River Delta Plain in China. A sequential chemical fractionation scheme and 31P nuclear magnetic resonance spectroscopy (31P NMR) were employed to quantify various P fractions and speciation. Results showed soil easily-labile P, moderately-labile P and non-labile P had a positive relationship with total P (TP) and available P (AP). Analysis with 31P NMR spectroscopy revealed that inorganic P including orthophosphate (Ortho-P) and pyrophosphate (Pyro-P) increased with cultivation age, while organic species monoester phosphate (Mono-P) and diester phosphate (Diester-P) decreased. Moreover, acid phosphatase (AcP), neutral phosphatase (NeP), exchangeable Ca and sand contents are the main factors that affected the transformation of soil P composition, and non-labile P (Dil.HCl-Pi) and Pyro-P had significant contribution to soil P availability by affecting P activation coefficient. Therefore, long-term paddy cultivation, influenced by these soil parameters including NeP, AcP, exchangeable Ca and sand, accelerated the transformation of soil organic P/non-labile P to inorganic P.

Design and Synthesis of Amphiphilic Graft Polyphosphazene Micelles for Docetaxel Delivery.

The structural versatility of polydichlorophosphazene derived from the inestimable possibilities to functionalize the two halogens, attached to each phosphazene main chain unit, attracted increasing attention in the last decade. This uncountable chemical derivatization is doubled by the amphiphilic roleplay demonstrated by polyphosphazenes containing twofold side-chained hydrophilic and hydrophobic moieties. Thus, it is able to encapsulate specific bioactive molecules for various targeted nanomedicine applications. A new amphiphilic graft, polyphosphazenes (PPP/PEG-NH/Hys/MAB), was synthesized via the thermal ring-opening polymerization of hexachlorocyclotriphosphazene, followed by a subsequent two-step substitution reaction of chlorine atoms with hydrophilic methoxypolyethylene glycol amine/histamine dihydrochloride adduct (PEG-NH2)/(Hys) and hydrophobic methyl-p-aminobenzoate (MAB), respectively. Fourier transform infrared spectroscopy (FTIR) and 1H and 31P-nuclear magnetic resonance spectroscopy (NMR) have been used to validate the expected architectural assembly of the copolymer. Docetaxel loaded micelles based on synthesized PPP/PEG-NH/Hys/MAB were designed by dialysis method. The micelles size was evaluated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The drug release profiles from the PPP/PEG-NH/Hys/MAB micelles were established. In vitro cytotoxicity tests of PPP/PEG-NH/Hys/MAB micelles loaded with Docetaxel revealed that designed polymeric micelles exhibited an increased cytotoxic effect on MCF-7 cells.