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Slow-release fertilizers (SRFs) form the core of innovative strategies in sustainable agriculture. Layered Double Hydroxides (LDH), known for their high capacity to sequester plant nutrients, especially phosphate, are emerging as promising candidates for SRF synthesis. The phosphate release properties of MgAl LDH (with a targeted Mg/Al ratio of 2.0) intercalated with HPO42- anions were assessed in various aqueous environments. A comprehensive analysis, including in-depth chemical and structural characterizations (ICP-OES, XRD, PDF, 27Al NMR, 31P NMR, FTIR, SEM) of the as-prepared phase unveiled a more intricate composition than anticipated for a pure or ideal Mg2Al-HPO4 LDH, encompassing an excess of intercalated phosphate in conjunction with K+. Beyond the intercalated phosphate, solid state 31P NMR speciation identified multiple HxPO4(-3+x) environments, indicating a portion of the phosphate reacting with intralayer Mg2+ to form K-struvite. Additionally, some phosphates were adsorbed onto the surface of amorphous aluminum hydroxide, a side phase formed during MgAl coprecipitation. The phosphate release demonstrated rapid kinetics, occurring within 6 days. Moreover, the released phosphate increased significantly when reducing the Solid/Liquid (S/L) ratio (58%) and further increasing in the presence of carbonate ions (90%). The released phosphate varied from 12% to 90% under different release conditions, transitioning from water to a 3.33 mM NaHCO3 aqueous solution at a low S/L ratio (from 20 mg LDH per mL to 0.02 mg LDH per mL). The simultaneous release of K+, Mg2+, Al3+ indicated the complete dissolution of the K-struvite and partial dissolution of phosphate intercalated MgAl LDH. These results enhanced our understanding of the mechanism governing phosphate release from MgAl LDH, paving the way for potential phosphate recovery by LDH or for the development of LDH-based SRFs.
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In this study, cyanobacterial biochars (CBs) enriched/doped with non-metallic elements were prepared by pyrolysis of biomass amended with different N, S, and P containing compounds. Their catalytic reactivity was tested for persulfate oxidation of the antibiotic norfloxacin (NOR). N and S doping failed to improve CB catalytic reactivity, while P doping increased reactivity 5 times compared with un-doped biochar. Biochars produced with organic phosphorus dopants showed the highest reactivity. Post-acid-washing improved catalytic reactivity. In particular, 950 â acid-washed triphenyl-phosphate doped CB showed the largest degradation rate and reached 79% NOR mineralization in 2 h. Main attributes for P-doped CBs high reactivity were large specific surface areas (up to 655 m2/g), high adsorption, high C-P-O content, graphitic P and non-radical degradation pathway (electron transfer). This study demonstrates a new way to reuse waste biomass by producing efficient P-doped metal-free biochars and presents a basic framework for designing carbon-based catalysts for organic pollutant degradation.
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Antibacterianos , Cianobacterias , Norfloxacino , Fósforo , Carbón OrgánicoRESUMEN
Structural disorder and low crystallinity render it challenging to characterise the atomic-level structure of layered double hydroxides (LDH). We report a novel multi-step, first-principles computational workflow for the analysis of paramagnetic solid-state NMR of complex inorganic systems such as LDH, which are commonly used as catalysts and energy storage materials. A series of 13CO32--labelled Mg2-xNixAl-LDH, x ranging from 0 (Mg2Al-LDH) to 2 (Ni2Al-LDH), features three distinct eigenvalues δ11, δ22 and δ33 of the experimental 13C chemical shift tensor. The δii correlate directly with the concentration of the paramagnetic Ni2+ and span a range of |δ11 - δ33| ≈ 90 ppm at x = 0, increasing to 950 ppm at x = 2. In contrast, the isotropic shift, δiso(13C), only varies by -14 ppm in the series. Detailed insight is obtained by computing (1) the orbital shielding by periodic density-functional theory involving interlayer water, (2) the long-range pseudocontact contribution of the randomly distributed Ni2+ ions in the cation layers (characterised by an ab initio susceptibility tensor) by a lattice sum, and (3) the close-range hyperfine terms using a full first-principles shielding machinery. A pseudohydrogen-terminated two-layer cluster model is used to compute (3), particularly the contact terms. Due to negative spin density contribution at the 13C site arising from the close-by Ni2+ sites, this step is necessary to reach a semiquantitative agreement with experiment. These findings influence future NMR investigations of the formally closed-shell interlayer species within LDH, such as the anions or water. Furthermore, the workflow is applicable to a variety of complex materials.
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P-glycoprotein (P-gp) inhibitors, like zosuquidar, partly increase oral bioavailability of P-gp substrates, such as etoposide. Here, it was hypothesised that co-release of etoposide and zosuquidar from amorphous solid dispersions (ASDs) may further increase oral etoposide bioavailability. This was envisioned through simultaneous co-release and subsequent spatiotemporal association of etoposide and zosuquidar in the small intestinal lumen. To further achieve this, ASDs of etoposide and zosuquidar in polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC) 5, and HPMC 4 k were prepared by freeze-drying. From these ASDs, etoposide release was fastest from PVP, then HPMC 5 and slowest from HPMC 4. Release from PVP and HPMC5 resulted in stable supersaturations of etoposide. In transcellular permeability studies across MDCKII-MDR1 cell monolayers, the accumulated amount of etoposide increased 3.7-4.9-fold from amorphous etoposide or when incorporated into PVP- or HPMC 5-based ASDs, compared to crystalline etoposide. In vivo, the oral bioavailability in Sprague Dawley rats increased from 1.0 to 2.4-3.4 %, when etoposide was administered as amorphous drug or in ASDs. However, when etoposide and zosuquidar were co-administered, the oral bioavailability increased further to 8.2-18 %. Interestingly, a distinct increase in oral etoposide bioavailability to 26 % was observed when etoposide and zosuquidar were co-administration in HPMC5-based ASDs. The supersaturation of etoposide as well as the simultaneous co-release of etoposide and zosuquidar in the small intestinal lumen may explain the observed bioavailability increase. Overall, this study suggested that simultaneous co-release of an amorphous P-gp substrate and inhibitor may be a novel and viable formulation strategy to increase the bioavailability P-gp substrates.
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Povidona , Ratas , Animales , Etopósido , Disponibilidad Biológica , Solubilidad , Ratas Sprague-Dawley , Preparaciones Farmacéuticas/química , Povidona/química , Derivados de la Hipromelosa/químicaRESUMEN
P-glycoprotein (P-gp) limits the oral absorption of drug substances. Potent small molecule P-gp inhibitors (e.g., zosuquidar) and nonionic surfactants (e.g., polysorbate 20) inhibit P-gp by proposedly different mechanisms. Therefore, it was hypothesised that a combination of zosuquidar and polysorbate 20 may potentiate inhibition of P-gp-mediated efflux. P-gp inhibition by zosuquidar and polysorbate 20 in combination was assessed in a calcein-AM assay and in a transcellular etoposide permeability study in MDCKII-MDR1 and Caco-2 cells. Furthermore, solutions of etoposide, zosuquidar, and polysorbate 20 were orally administered to Sprague Dawley rats. Zosuquidar elicited a high level of nonspecific adsorption to various labware, which significantly affected the outcomes of the in vitro studies. Still, at certain zosuquidar and polysorbate 20 concentrations, additive P-gp inhibition was observed in vitro. In vivo, however, oral etoposide bioavailability decreased by coadministration of both zosuquidar and polysorbate 20 when compared to coadministration of etoposide with zosuquidar alone. For future formulation development, the present study provided important and novel knowledge about nonspecific zosuquidar adsorption, as well as insights into combinational P-gp inhibition by a third-generation P-gp inhibitor and a P-gp-inhibiting nonionic surfactant.
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The magnetic properties of the nickelalumite-type layered double hydroxides (LDH), MAl4(OH)12(SO4)·3H2O (MAl4-LDH) with M = Co2+ (S = 3/2), Ni2+ (S = 1), or Cu2+ (S = 1/2) were determined by a combined experimental and computational approach. They represent three new inorganic, low-dimensional magnetic systems with a defect-free, structurally ordered magnetic lattice. They exhibit no sign of magnetic ordering down to 2 K in contrast to conventional hydrotalcite LDH. Detailed insight into the complex interplay between the choice of magnetic ion (M2+) and magnetic properties was obtained by a combination of magnetic susceptibility, heat capacity, neutron scattering, solid-state NMR spectroscopy, and first-principles calculations. The NiAl4- and especially CoAl4-LDH have pronounced zero-field splitting (ZFS, easy-axis and easy-plane, respectively) and weak ferromagnetic nearest-neighbour interactions. Thus, they are rare examples of predominantly zero-dimensional spin systems in dense, inorganic matrices. In contrast, CuAl4-LDH (S = 1/2) consists of weakly ferromagnetic S = 1/2 spin chains. For all three MAl4-LDH, good agreement is found between the experimental magnetic parameters (J, D, g) and first-principles quantum chemical calculations, which also predict that the interchain couplings are extremely weak (< 0.1 cm-1). Thus, our approach will be valuable for evaluation and prediction of magnetic properties in other inorganic materials.
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The variation in phosphorus (P) speciation of sewage sludge throughout three wastewater treatment plants (WWTPs) was obtained by combining sequential P extraction with optical and scanning electron microscopy (SEM), chemical analyses, powder X-ray diffraction (PXRD), and 27Al and 31P nuclear magnetic resonance (NMR) spectroscopy. The WWTPs combine chemical P removal (CPR) and enhanced biological P removal (EBPR) and were compared to understand the effect of iron (Fe) dosing with and without codosing of aluminum (Al) and thermal hydrolysis on the P speciation. 31P NMR showed comparable inorganic orthophosphate (ortho-P, 53-60% of total P) and organophosphate (organic-P, 37-45%) in primary sludge, whereas polyphosphate (poly-P, 23-44%) from poly-P accumulating organisms (PAOs) was mainly observed in the secondary sludge. Inorganic ortho-P (90-98%) dominated after anaerobic digestion, which degraded poly-P and most organic-P. The inorganic ortho-P was mainly Fe bound P (Fe-P), especially after anaerobic digestion (71%). Codosing of Fe and Al led to two comparable fractions: Fe-P (38%) and P sorbed on amorphous Al (hydr)oxides (38%). Vivianite was identified in all samples by microscopy and chemical extraction but was PXRD amorphous in 12 out of 17 samples. Thus, vivianite may be more common in sewage sludge than previously known.
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Aguas del Alcantarillado , Purificación del Agua , Aluminio , Espectroscopía de Resonancia Magnética , Microscopía , Fósforo/química , Polifosfatos , Polvos , Aguas del Alcantarillado/química , Eliminación de Residuos Líquidos , Difracción de Rayos XRESUMEN
Phosphorus (P) is present in activated sludge from wastewater treatment plants in the form of metal salt precipitates, extracellular polymeric substances, or bound into the biomass, for example, as intracellular polyphosphate (poly-P). Several methods for a reliable quantification of the different P-fractions have recently been developed, and this study combines them to obtain a comprehensive P mass-balance of activated sludge from four enhanced biological phosphate removal (EBPR) plants. Chemical characterization by ICP-OES and sequential P fractionation showed that chemically bound P constituted 38-69% of total P, most likely in the form of Fe, Mg, or Al minerals. Raman microspectroscopy, solution state 31P NMR, and 31P MAS NMR spectroscopy applied before and after anaerobic P-release experiments, were used to quantify poly-P, which constituted 22-54% of total P and was found in approximately 25% of all bacterial cells. Raman microspectroscopy in combination with fluorescence in situ hybridization was used to quantify poly-P in known polyphosphate-accumulating organisms (PAO) (Tetrasphaera, Candidatus Accumulibacter, and Dechloromonas) and other microorganisms known to possess high level of poly-P, such as the filamentous Ca. Microthrix. Interestingly, only 1-13% of total P was stored by unidentified PAO, highlighting that most PAOs in the full-scale EBPR plants investigated are known.
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Fósforo , Aguas del Alcantarillado , Reactores Biológicos/microbiología , Hibridación Fluorescente in Situ , Polifosfatos , Aguas del Alcantarillado/microbiologíaRESUMEN
BACKGROUND AND PURPOSE: With the introduction of hybrid magnetic resonance linacs (MR-linac), improved imaging has enabled daily treatment adaptation. However, the use of gadolinium based contrast agents (GBCAs) is desired to further improve MR image contrast. GBCAs are in the form of a non-toxic metalorganic gadolinium complex, but toxic un-chelated aqueous gadolinium(III), Gd3+(aq), can be released in patients if the organic ligand is degraded by the radiation. In this study, T1 relaxation measurements were performed to study the effect of radiation on three GBCAs. MATERIALS AND METHODS: GBCAs, gadoteric acid, gadobutrol and gadoxectic acid were investigated in a concentration range of 10-100 mM. Measurements were performed on a 500 MHz nuclear MR (NMR) spectrometer with a high-resolution inversion recovery sequence to determine T1. Samples were irradiated with 7 MV photons on an MR-linac to a total dose of 100 Gy. The lower detection limit of Gd3+(aq) was established by estimating the overall measurement uncertainty and comparing to corresponding changes in R1 when replacing chelated Gd3+ with gadolinium nitrate at predefined percentages. RESULTS: The overall measurement uncertainty was estimated to ±0.0053 ms-1, corresponding to Gd3+(aq) detection levels 1%-1.5% or 1-4.5 micro molar at clinical GBCA dosage. No detectable differences in R1 were observed between irradiated and non-irradiated samples for any GBCA. CONCLUSIONS: This study did not find any measurable degradation of GBCAs due to irradiation with high-energy X-rays, however, in-vivo investigations are needed to provide the clinical basis for safe use of contrast agents in a radiotherapy workflow.
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The synthesis and thermal degradation of MAl4(OH)12SO4·3H2O layered double hydroxides with M = Co2+, Ni2+, Cu2+, and Zn2+ ("MAl4-LDH") were investigated by inductively coupled plasma-optical emission spectroscopy, thermogravimetric analysis, powder X-ray diffraction, Rietveld refinement, scanning electron microscopy, scanning tunnel electron microscopy, energy-dispersive X-ray spectroscopy, and solid-state 1H and 27Al NMR spectroscopy. Following extensive synthesis optimization, phase pure CoAl4- and NiAl4-LDH were obtained, whereas 10-12% unreacted bayerite (Al(OH)3) remained for the CuAl4-LDH. The optimum synthesis conditions are hydrothermal treatment at 120 °C for 14 days (NiAl4-LDH only 9 days) with MSO4(aq) concentrations of 1.4-2.8, 0.7-0.8, and 0.08 M for the CoAl4-, NiAl4-, and CuAl4-LDH, respectively. A pH ≈ 2 for the metal sulfate solutions is required to prevent the formation of byproducts, which were Ni(OH)2 and Cu3(SO4)(OH)4 for NiAl4- and CuAl4-LDH, respectively. The thermal degradation of the three MAl4-LDH and ZnAl4-LDH in a nitrogen atmosphere proceeds in three steps: (i) dehydration and dehydroxylation between 200 and 600 °C, (ii) loss of sulfate between 600 and 900 °C, and (iii) formation of the end products at 900-1200 °C. For CoAl4-LDH (ZnAl4-LDH), these are α-Al2O3 and CoAl2O4 (ZnAl2O4) spinel. For NiAl4-LDH, a spinel-like NiAl4O7 phase forms, whereas CuAl4-LDH degrades by a redox reaction yielding a diamagnetic CuAlO2 (delafossite structure) and α-Al2O3.
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Vivianite (Fe3(PO4)2â 8H2O) is a potential phosphorus (P) recovery product from wastewater treatment plants (WWTPs). However, routine methods for quantification of vivianite bound P (vivianite-P) are needed to establish the link between vivianite formation and operating conditions, as current approaches require specialized instrumentation (Mössbauer or synchrotron). This study modified a conventional sequential P extraction protocol by insertion of an extraction step (0.2% 2,2'-bipyridine + 0.1 M KCl) targeting vivianite-P (Gu et al., Water Research, 2016, 103, 352-361). This protocol was tested on digested and dewatered sludge from two WWTPs, in which vivianite (molar Fe:P ratios of 1.0-1.6) was unambiguously identified by optical microscopy, powder X-ray diffraction, and scanning electron microscopy with energy dispersive X-ray spectroscopy. The results showed that vivianite-P was separated from iron(III)-bound P (Fe(III)-P) in the sludge. Vivianite-P constituted about half of the total P (TP) in the sludge from a Fe dosing chemical P removal (CPR) WWTP, but only 16-26% of TP in the sludge from a WWTP using a combination of Fe dosing CPR and enhanced biological P removal (EBPR). The modified protocol revealed that Fe-bound P (Fe-P, i.e., vivianite-P + Fe(III)-P) was the dominant P fraction, in agreement with quantitative 31P nuclear magnetic resonance (NMR) experiments. Moreover, it was shown that the conventional P extraction protocol underestimated the Fe-P content by 6-35%. The established protocol represents a reliable in-house analytical method that can distinguish and quantify vivianite-P and Fe(III)-P in sludge, i.e. facilitate optimized vivianite production at WWTPs.
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Compuestos Férricos , Aguas del Alcantarillado , Compuestos Ferrosos , Espectroscopía de Resonancia Magnética , Fosfatos , Fósforo , Eliminación de Residuos LíquidosRESUMEN
Calcium controls important processes in fungal metabolism, such as hyphae growth, cell wall synthesis, and stress tolerance. Recently, it was reported that calcium affects polyphosphate and lipid accumulation in fungi. The purpose of this study was to assess the effect of calcium on the accumulation of lipids and polyphosphate for six oleaginous Mucoromycota fungi grown under different phosphorus/pH conditions. A Duetz microtiter plate system (Duetz MTPS) was used for the cultivation. The compositional profile of the microbial biomass was recorded using Fourier-transform infrared spectroscopy, the high throughput screening extension (FTIR-HTS). Lipid content and fatty acid profiles were determined using gas chromatography (GC). Cellular phosphorus was determined using assay-based UV-Vis spectroscopy, and accumulated phosphates were characterized using solid-state 31P nuclear magnetic resonance spectroscopy. Glucose consumption was estimated by FTIR-attenuated total reflection (FTIR-ATR). Overall, the data indicated that calcium availability enhances polyphosphate accumulation in Mucoromycota fungi, while calcium deficiency increases lipid production, especially under acidic conditions (pH 2-3) caused by the phosphorus limitation. In addition, it was observed that under acidic conditions, calcium deficiency leads to increase in carotenoid production. It can be concluded that calcium availability can be used as an optimization parameter in fungal fermentation processes to enhance the production of lipids or polyphosphates.
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P-glycoprotein inhibitors, like zosuquidar, have widely been used to study the role of P-glycoprotein in oral absorption. Still, systematic studies on the inhibitor dose-response relationship on intestinal drug permeation are lacking. In the present study, we investigated the effect of 0.79 nM-2.5 µM zosuquidar on etoposide permeability across Caco-2 cell monolayers. We also investigated etoposide pharmacokinetics after oral or IV administration to Sprague Dawley rats with co-administration of 0.063-63 mg/kg zosuquidar, as well as the pharmacokinetics of zosuquidar itself. Oral zosuquidar bioavailability was 2.6-4.2%, while oral etoposide bioavailability was 5.5 ± 0.9%, which increased with increasing zosuquidar doses to 35 ± 5%. The intestinal zosuquidar concentration required to induce a half-maximal increase in bioavailability was estimated to 180 µM. In contrast, the IC50 of zosuquidar on etoposide permeability in vitro was only 5-10 nM, and a substantial in vitro-in vivo discrepancy of at least four orders of magnitude was thereby identified. Overall, the present study provides valuable insights for future formulation development that applies fixed dose combinations of P-glycoprotein inhibitors to increase the absorption of poorly permeable P-glycoprotein substrate drugs.
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Environmental science is an interdisciplinary field, which integrates chemical, physical, and biological sciences to study environmental problems and human impact on the environment. This article highlights the use of solid-state NMR spectroscopy (SSNMR) in studies of environmental processes and remediation with examples from both laboratory studies and samples collected in the field. The contemporary topics presented include soil chemistry, environmental remediation (e.g., heavy metals and radionuclides removal, carbon dioxide mineralization), and phosphorus recovery. SSNMR is a powerful technique, which provides atomic-level information about speciation in complex environmental samples as well as the interactions between pollutants and minerals/organic matter on different environmental interfaces. The challenges in the application of SSNMR in environmental science (e.g., measurement of paramagnetic nuclei and low-gamma nuclei) are also discussed, and perspectives are provided for the future research efforts.
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Potassium chromium jarosite, KCr3(OH)6(SO4)2 (Cr-jarosite), is considered a promising candidate to display spin liquid behavior due to the strong magnetic frustration imposed by the crystal structure. However, the ground state magnetic properties have been debated, since Cr-jarosite is notoriously non-stoichiometric. Our study reports the magnetic properties for deuterated KCr3(OD)6(SO4)2 on chemically well-defined samples, which have been characteried by a combination of powder X-ray diffraction, neutron diffraction, solid state NMR spectroscopy, and scanning electron microscopy with energy dispersive spectroscopy. Eight polycrystalline samples, which all contained only 1-3% Cr vacancies were obtained. However, significant substitution (2-27%) of potassium with H2O and/or H3O+ was observed and resulted in pronounced stacking disorder along the c-axis. A clear second-order transition to an antiferromagnetically ordered phase at TN = 3.8(1) K with a small net moment of 0.03 µB per Cr3+-ion was obtained from vibrating sample magnetometry and temperature dependent neutron diffraction. The moment is attributed to spin canting caused by the Dzyaloshinskii-Moriya interaction. Thus, our experimental results imply that even ideal potassium chromium jarosite will exhibit magnetic order below 4 K and therefore it does not qualify as a true spin liquid material.
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Layered double hydroxides (LDH) and their magnetic composites have been intensively investigated as recyclable high-capacity phosphate sorbents but with little attention to their stability as function of pH and phosphate concentration. The stability of a Fe3O4@SiO2-Mg3Fe LDH P sorbent as function of pH (5-11) and orthophosphate (Pi) concentration (1-300 mg P/L) was investigated. The composite has high adsorption capacity (approx. 80 mg P/g) at pH 5 but with fast dissolution of the LDH component resulting in formation of ferrihydrite as evidenced by Mössbauer spectroscopy. At pH 7 more than 60% of the LDH dissolves within 60 min, while at alkaline pH, the LDH is more stable but with less than 40% adsorption capacity as compared to pH 5. The high Pi sorption at acid to neutral pH is attributed to Pi bonding to the residual ferrihydrite. Under alkaline conditions Pi is sorbed to LDH at low Pi concentration while magnesium phosphates form at higher Pi concentration evidenced by solid-state 31P MAS NMR, powder X-ray diffraction and chemical analyses. Sorption as function of pH and Pi concentration has been fitted by a Rational 2D function allowing for estimation of Pi sorption and precipitation. In conclusion, the instability of the LDH component limits its application in wastewater treatment from acid to alkaline pH. Future use of magnetic LDH composites requires substantial stabilisation of the LDH component.
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13C solid-state MAS NMR spectra of a series of paramagnetic metal acetylacetonate complexes; [VO(acac)2] (d1, S = ½), [V(acac)3] (d2, S = 1), [Ni(acac)2(H2O)2] (d8, S = 1), and [Cu(acac)2] (d9, S = ½), were assigned using modern NMR shielding calculations. This provided a reliable assignment of the chemical shifts and a qualitative insight into the hyperfine couplings. Our results show a reversal of the isotropic 13C shifts, δiso(13C), for CH3 and CO between the d1 and d2versus the d8 and d9 acetylacetonate complexes. The CH3 shifts change from about -150 ppm (d1,2) to roughly 1000 ppm (d8,9), whereas the CO shifts decrease from 800 ppm to about 150 ppm for d1,2 and d8,9, respectively. This was rationalized by comparison of total spin-density plots and computed contact couplings to those corresponding to singly occupied molecular orbitals (SOMOs). This revealed the interplay between spin delocalization of the SOMOs and spin polarization of the lower-energy MOs, influenced by both the molecular symmetry and the d-electron configuration. A large positive chemical shift results from spin delocalization and spin polarization acting in the same direction, whereas their cancellation corresponds to a small shift. The SOMO(s) for the d8 and d9 complexes are σ-like, implying spin-delocalization on the CH3 and CO groups of the acac ligand, cancelled only for CO by spin polarization. In contrast, the SOMOs of the d1 and d2 systems are π-like and a large CO-shift results from spin polarization, which accounts for the reversed assignment of δiso(13C) for CH3 and CO.
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In the small intestine, P-glycoprotein (P-gp) may limit the permeability of its substrates, which lead to reduced oral absorption. To circumvent the effect of P-gp, a nanocomposite material termed montmorillonite-surfactant hybrid particles was developed. The particles consisted of montmorillonite, the P-gp-inhibiting, nonionic surfactant, polysorbate 20, and the P-gp substrate, digoxin. The present study aimed to investigate if montmorillonite-surfactant hybrid particles could modulate the absorption of digoxin in vivo. Montmorillonite-surfactant hybrid particles were prepared by lyophilising an aqueous suspension of the constituents. Scanning electron microscopy, thermogravimetric analysis, and powder X-ray diffraction revealed an altered surface morphology, decreased water content, and intercalation of polysorbate 20 between montmorillonite layers. The particles were administered orally to Sprague Dawley rats, and digoxin was quantified by liquid chromatography-tandem mass spectrometry. Control digoxin-containing montmorillonite decreased the exposure of digoxin. In contrast, montmorillonite-surfactant hybrid particles increased AUC and Cmax by 31 and 91%, respectively, compared to digoxin in solution. It was hypothesised that montmorillonite-surfactant hybrid particles increased digoxin exposure by forming mucosa-localised elevated concentrations of polysorbate 20 and digoxin, which enhanced the inhibitory effect of polysorbate 20 on P-gp.
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Miembro 1 de la Subfamilia B de Casetes de Unión a ATP/antagonistas & inhibidores , Digoxina/farmacocinética , Portadores de Fármacos/farmacología , Polisorbatos/farmacología , Tensoactivos/administración & dosificación , Miembro 1 de la Subfamilia B de Casetes de Unión a ATP/metabolismo , Administración Oral , Animales , Área Bajo la Curva , Bentonita/química , Digoxina/administración & dosificación , Portadores de Fármacos/química , Composición de Medicamentos/métodos , Absorción Intestinal/efectos de los fármacos , Mucosa Intestinal/efectos de los fármacos , Mucosa Intestinal/metabolismo , Intestino Delgado/efectos de los fármacos , Intestino Delgado/metabolismo , Masculino , Modelos Animales , Permeabilidad , Polisorbatos/química , Ratas Sprague-DawleyRESUMEN
Polyphosphate (poly-P) is a major constituent in activated sludge from wastewater treatment plants with enhanced biological phosphorus removal due to poly-P synthesis by poly-P accumulating organisms where it plays an important role for recovery of phosphorus from waste water. Our aim was to develop a reliable protocol for poly-P quantification by 31P NMR spectroscopy. This has so far been complicated by the risks of inefficient extraction and poly-P hydrolysis in the extracts. A protocol for complete extraction, identification and quantification of poly-P in activated sludge from a waste water treatment plant was identified based on test and evaluation of existing extraction protocols in combination with poly-P determination and quantification by solution and solid state 31P NMR spectroscopy. The total poly-P middle group content was quantified by solid state NMR for comparison with the poly-P middle groups quantified by solution NMR, which is novel. Three different extraction protocols previously used in literature were compared: 1) a single 0.25â¯M NaOH-0.05â¯M EDTA extraction, 2) a 0.05â¯M EDTA pre-extraction followed by a 0.25â¯M NaOH main extraction and 3) a 0.05â¯M EDTA pre-extraction followed by a 0.25â¯M NaOH-0.05â¯M EDTA main extraction. The results showed that the extraction protocol 2 was optimal for fresh activated sludge, extracting 10.8⯱â¯0.4 to 11.4⯱â¯1.2 mgP/gDW poly-P. Extraction protocols 1 and 3 extracted less than 9.4⯱â¯0.5 mgP/gDW poly-P. A comparison of the quantification of poly-P by 31P solution NMR and by 31P solid state NMR spectroscopy of lyophilised activated sludge showed 86⯱â¯9% extraction efficiency of poly-P, which confirms that the extraction protocol recovered most of the poly-P from the samples without pronounced poly-P degradation.
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Aguas del Alcantarillado , Purificación del Agua , Espectroscopía de Resonancia Magnética , Fósforo , Polifosfatos , Aguas Residuales , AguaRESUMEN
The phase purity of a series of ZnAl4(OH)12SO4· nH2O layered double hydroxides (ZnAl4-LDH) obtained from a reaction of bayerite (Al(OH)3) with an excess of zinc(II) sulfate under hydrothermal conditions was investigated as a function of the reaction temperature, the duration of the hydrothermal treatment, and the zinc(II) concentration. The product quality, i.e., crystalline impurities, Al impurities, and bulk Zn:Al ratio, were assessed by powder X-ray diffraction (PXRD), 27Al MAS NMR, and elemental analysis. Structural characterization of a stoichiometric ZnAl4-LDH (120 °C, 9 days, and 2.8 M Zn(II)) showed a well-defined structure of the metal ion layer as evidenced by a single, well-defined Zn environment: i.e., no Zn substitution on the Al sites according to Zn k-edge EXAFS and PXRD. Furthermore, nearly all of the 12 different 1H atoms in the -OH groups and 4 27Al resonances could be assigned using 1H,27Al NMR correlation experiments recorded with ultrafast MAS. The interlayer water content is variable on the basis of thermogravimetric analysis and changes in the 1H MAS NMR spectra with temperature. A composition of ZnAl4(OH)12(SO4)·2.6H2O was obtained from a combination of these techniques and confirmed that ZnAl4-LDH is isostructural with the mineral nickelalumite (NiAl4(OH)12SO4·3H2O).