Ballistic Simulation Method for Lithium Ion Batteries (BASIMLIB) Using Thick Shell Composites (TSC) in LS-DYNA

DTIC Science & Technology

2016-08-04

BAllistic SImulation Method for Lithium Ion Batteries (BASIMLIB) using Thick Shell Composites (TSC) in LS-DYNA Venkatesh Babu, Dr. Matt Castanier, Dr...Objective • Objective and focus of this work is to develop a – Robust simulation methodology to model lithium - ion based batteries in its module and full...unlimited  Lithium Ion Phosphate (LiFePO4) battery cell, module and pack was modeled in LS-DYNA using both Thin Shell Layer (TSL) and Thick Shell

Multi-layer porous fiber-reinforced composites for implants: in vitro calcium phosphate formation in the presence of bioactive glass.

PubMed

Nganga, Sara; Zhang, Di; Moritz, Niko; Vallittu, Pekka K; Hupa, Leena

2012-11-01

Glass-fiber-reinforced composites (FRCs), based on bifunctional methacrylate resin, have recently shown their potential for use as durable cranioplasty, orthopedic and oral implants. In this study we suggest a multi-component sandwich implant structure with (i) outer layers out of porous FRC, which interface the cortical bone, and (ii) inner layers encompassing bioactive glass granules, which interface with the cancellous bone. The capability of Bioglass(®) 45S5 granules (100-250μm) to induce calcium phosphate formation on the surface of the FRC was explored by immersing the porous FRC-Bioglass laminates in simulated body fluid (SBF) for up to 28d. In both static (agitated) and dynamic conditions, bioactive glass granules induced precipitation of calcium phosphate at the laminate surfaces as confirmed by scanning electron microscopy. The proposed dynamic flow system is useful for the in vitro simulation of bone-like apatite formation on various new porous implant designs containing bioactive glass and implant material degradation. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Putty-like bone fillers based on CaP ceramics or Biosilicate® combined with carboxymethylcellulose: Characterization, optimization, and evaluation.

PubMed

Gabbai-Armelin, Paulo R; Renno, Ana Cm; Crovace, Murilo C; Magri, Angela Mp; Zanotto, Edgar D; Peitl, Oscar; Leeuwenburgh, Sander Cg; Jansen, John A; van den Beucken, Jeroen Jjp

2017-08-01

Calcium phosphates and bioactive glass ceramics have been considered promising biomaterials for use in surgeries. However, their moldability should be further enhanced. We here thereby report the handling, physicochemical features, and morphological characteristics of formulations consisting of carboxymethylcellulose-glycerol and hydroxyapatite-tricalcium phosphate or Biosilicate® particles. We hypothesized that combining either material with carboxymethylcellulose-glycerol would improve handling properties, retaining their bioactivity. In addition to scanning electron microscopy, cohesion, mineralization, pH, and viscoelastic properties of the novel formulations, cell culture experiments were performed to evaluate the cytotoxicity and cell proliferation. Putty-like formulations were obtained with improved cohesion and moldability. Remarkably, mineralization in simulated body fluid of hydroxyapatite-tricalcium phosphate/carboxymethylcellulose-glycerol formulations was enhanced compared to pure hydroxyapatite-tricalcium phosphate. Cell experiments showed that all formulations were noncytotoxic and that HA-TCP60 and BGC50 extracts led to an increased cell proliferation. We conclude that combining carboxymethylcellulose-glycerol with either hydroxyapatite-tricalcium phosphate or Biosilicate® allows for the generation of moldable putties, improves handling properties, and retains the ceramic bioactivity.

Bioactive calcium pyrophosphate glasses and glass-ceramics.

PubMed

Kasuga, Toshihiro

2005-01-01

Calcium phosphate glass-based materials in the pyrophosphate region are briefly reviewed. Calcium pyrophosphate glasses can be prepared by including a small amount of TiO(2) (

Multi-scale individual-based model of microbial and bioconversion dynamics in aerobic granular sludge.

PubMed

Xavier, Joao B; De Kreuk, Merle K; Picioreanu, Cristian; Van Loosdrecht, Mark C M

2007-09-15

Aerobic granular sludge is a novel compact biological wastewater treatment technology for integrated removal of COD (chemical oxygen demand), nitrogen, and phosphate charges. We present here a multiscale model of aerobic granular sludge sequencing batch reactors (GSBR) describing the complex dynamics of populations and nutrient removal. The macro scale describes bulk concentrations and effluent composition in six solutes (oxygen, acetate, ammonium, nitrite, nitrate, and phosphate). A finer scale, the scale of one granule (1.1 mm of diameter), describes the two-dimensional spatial arrangement of four bacterial groups--heterotrophs, ammonium oxidizers, nitrite oxidizers, and phosphate accumulating organisms (PAO)--using individual based modeling (IbM) with species-specific kinetic models. The model for PAO includes three internal storage compounds: polyhydroxyalkanoates (PHA), poly phosphate, and glycogen. Simulations of long-term reactor operation show how the microbial population and activity depends on the operating conditions. Short-term dynamics of solute bulk concentrations are also generated with results comparable to experimental data from lab scale reactors. Our results suggest that N-removal in GSBR occurs mostly via alternating nitrification/denitrification rather than simultaneous nitrification/denitrification, supporting an alternative strategy to improve N-removal in this promising wastewater treatment process.

ATP Hydrolysis Mechanism in a Maltose Transporter Explored by QM/MM Metadynamics Simulation.

PubMed

Hsu, Wei-Lin; Furuta, Tadaomi; Sakurai, Minoru

2016-11-03

Translocation of substrates across the cell membrane by adenosine 5'-triphosphate (ATP)-binding cassette (ABC) transporters depends on the energy provided by ATP hydrolysis within the nucleotide-binding domains (NBDs). However, the detailed mechanism remains unclear. In this study, we focused on maltose transporter NBDs (MalK 2 ) and performed a quantum mechanical/molecular mechanical (QM/MM) well-tempered metadynamics simulation to address this issue. We explored the free-energy profile along an assigned collective variable. As a result, it was determined that the activation free energy is approximately 10.5 kcal/mol, and the reaction released approximately 3.8 kcal/mol of free energy, indicating that the reaction of interest is a one-step exothermic reaction. The dissociation of the ATP γ-phosphate seems to be the rate-limiting step, which supports the so-called dissociative model. Moreover, Glu159, located in the Walker B motif, acts as a base to abstract the proton from the lytic water, but is not the catalytic base, which corresponds to an atypical general base catalysis model. We also observed two interesting proton transfers: transfer from the His192 ε-position nitrogen to the dissociated inorganic phosphate, Pi, and transfer from the Lys42 side chain to adenosine 5'-diphosphate β-phosphate. These proton transfers would stabilize the posthydrolysis state. Our study provides significant insight into the ATP hydrolysis mechanism in MalK 2 from a dynamical viewpoint, and this insight would be applicable to other ABC transporters.

Prediction of Metabolite Concentrations, Rate Constants and Post-Translational Regulation Using Maximum Entropy-Based Simulations with Application to Central Metabolism of Neurospora crassa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cannon, William; Zucker, Jeremy; Baxter, Douglas

We report the application of a recently proposed approach for modeling biological systems using a maximum entropy production rate principle in lieu of having in vivo rate constants. The method is applied in four steps: (1) a new ODE-based optimization approach based on Marcelin’s 1910 mass action equation is used to obtain the maximum entropy distribution, (2) the predicted metabolite concentrations are compared to those generally expected from experiment using a loss function from which post-translational regulation of enzymes is inferred, (3) the system is re-optimized with the inferred regulation from which rate constants are determined from the metabolite concentrationsmore » and reaction fluxes, and finally (4) a full ODE-based, mass action simulation with rate parameters and allosteric regulation is obtained. From the last step, the power characteristics and resistance of each reaction can be determined. The method is applied to the central metabolism of Neurospora crassa and the flow of material through the three competing pathways of upper glycolysis, the non-oxidative pentose phosphate pathway, and the oxidative pentose phosphate pathway are evaluated as a function of the NADP/NADPH ratio. It is predicted that regulation of phosphofructokinase (PFK) and flow through the pentose phosphate pathway are essential for preventing an extreme level of fructose 1, 6-bisphophate accumulation. Such an extreme level of fructose 1,6-bisphophate would otherwise result in a glassy cytoplasm with limited diffusion, dramatically decreasing the entropy and energy production rate and, consequently, biological competitiveness.« less

Secondary Waste Form Down Selection Data Package – Ceramicrete

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantrell, Kirk J.; Westsik, Joseph H.

2011-08-31

As part of high-level waste pretreatment and immobilized low activity waste processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed in the Integrated Disposal Facility. Currently, four waste forms are being considered for stabilization and solidification of the liquid secondary wastes. These waste forms are Cast Stone, Ceramicrete, DuraLith, and Fluidized Bed Steam Reformer. The preferred alternative will be down selected from these four waste forms. Pacific Northwest National Laboratorymore » is developing data packages to support the down selection process. The objective of the data packages is to identify, evaluate, and summarize the existing information on the four waste forms being considered for stabilization and solidification of the liquid secondary wastes. The information included will be based on information available in the open literature and from data obtained from testing currently underway. This data package is for the Ceramicrete waste form. Ceramicrete is a relatively new engineering material developed at Argonne National Laboratory to treat radioactive and hazardous waste streams (e.g., Wagh 2004; Wagh et al. 1999a, 2003; Singh et al. 2000). This cement-like waste form can be used to treat solids, liquids, and sludges by chemical immobilization, microencapsulation, and/or macroencapsulation. The Ceramicrete technology is based on chemical reaction between phosphate anions and metal cations to form a strong, dense, durable, low porosity matrix that immobilizes hazardous and radioactive contaminants as insoluble phosphates and microencapsulates insoluble radioactive components and other constituents that do not form phosphates. Ceramicrete is a type of phosphate-bonded ceramic, which are also known as chemically bonded phosphate ceramics. The Ceramicrete binder is formed through an acid-base reaction between calcined magnesium oxide (MgO; a base) and potassium hydrogen phosphate (KH{sub 2}PO{sub 4}; an acid) in aqueous solution. The reaction product sets at room temperature to form a highly crystalline material. During the reaction, the hazardous and radioactive contaminants also react with KH{sub 2}PO{sub 4} to form highly insoluble phosphates. In this data package, physical property and waste acceptance data for Ceramicrete waste forms fabricated with wastes having compositions that were similar to those expected for secondary waste effluents, as well as secondary waste effluent simulants from the Hanford Tank Waste Treatment and Immobilization Plant were reviewed. With the exception of one secondary waste form formulation (25FA+25 W+1B.A. fabricated with the mixed simulant did not meet the compressive strength requirement), all the Ceramicrete waste forms that were reviewed met or exceeded Integrated Disposal Facility waste acceptance criteria.« less

Mg2+ in the Major Groove Modulates B-DNA Structure and Dynamics

PubMed Central

Guéroult, Marc; Boittin, Olivier; Mauffret, Oliver; Etchebest, Catherine; Hartmann, Brigitte

2012-01-01

This study investigates the effect of Mg2+ bound to the DNA major groove on DNA structure and dynamics. The analysis of a comprehensive dataset of B-DNA crystallographic structures shows that divalent cations are preferentially located in the DNA major groove where they interact with successive bases of (A/G)pG and the phosphate group of 5′-CpA or TpG. Based on this knowledge, molecular dynamics simulations were carried out on a DNA oligomer without or with Mg2+ close to an ApG step. These simulations showed that the hydrated Mg2+ forms a stable intra-strand cross-link between the two purines in solution. ApG generates an electrostatic potential in the major groove that is particularly attractive for cations; its intrinsic conformation is well-adapted to the formation of water-mediated hydrogen bonds with Mg2+. The binding of Mg2+ modulates the behavior of the 5′-neighboring step by increasing the BII (ε-ζ>0°) population of its phosphate group. Additional electrostatic interactions between the 5′-phosphate group and Mg2+ strengthen both the DNA-cation binding and the BII character of the 5′-step. Cation binding in the major groove may therefore locally influence the DNA conformational landscape, suggesting a possible avenue for better understanding how strong DNA distortions can be stabilized in protein-DNA complexes. PMID:22844516

Bent channel design in buried Er3+/Yb3+ codoped phosphate glass waveguide fabricated by field-assisted annealing

NASA Astrophysics Data System (ADS)

Zhao, Ruitu; Wang, Mu; Chen, Baojie; Liu, Ke; Pun, Edwin Yue-Bun; Lin, Hai

2011-04-01

Bent waveguide structures (S-, U-, and F-bend) based on buried Er3+/Yb3+ codoped phosphate glass waveguide channel fabricated by field-assisted annealing have been designed to achieve high-gain C-band integrated amplification. Using a simulated-bend method, the optimal radius for the curved structure is derived to be 0.90 cm with loss coefficient of 0.02 dB/cm, as the substrate size is schemed to be 4×3 cm2. In the wavelength range of 1520 to 1575 nm, obvious gain enhancement for the bent structure waveguides is anticipated, and for the F-bend waveguide, the internal gain at 1534-nm wavelength is derived to be 41.61 dB, which is much higher than the value of 26.22 and 13.81 dB in the U- and S-bend waveguides, respectively, and over three times higher than that of the straight one. The simulation results indicate that the bent structure design is beneficial in obtaining high signal gain in buried Er3+/Yb3+ codoped phosphate glass waveguides, which lays the foundation for further design and fabrication of integrated devices.

Lead-iron phosphate glass as a containment medium for the disposal of high-level nuclear wastes

DOEpatents

Boatner, L.A.; Sales, B.C.

1984-04-11

Disclosed are lead-iron phosphate glasses containing a high level of Fe/sub 2/O/sub 3/ for use as a storage medium for high-level radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste

Diffusion, Viscosity and Crystal Growth in Microgravity

NASA Technical Reports Server (NTRS)

Myerson, Allan S.

1996-01-01

The diffusivity of TriGlycine Sulfate (TGS), Potassium Dihydrogen Phosphate (KDP), Ammonium Dihydrogen Phosphate (ADF) and other compounds of interest to microgravity crystal growth, in supersaturated solutions as a function of solution concentration, 'age' and 'history was studied experimentally. The factors that affect the growth of crystals from water solutions in microgravity have been examined. Three non-linear optical materials have been studied, potassium dihydrogen phosphate (KDP), ammonium dihydrogen phosphate (ADP) and triglycine sulfate (TGC). The diffusion coefficient and viscosity of supersaturated water solutions were measured. Also theoretical model of diffusivity and viscosity in a metastable state, model of crystal growth from solution including non-linear time dependent diffusivity and viscosity effect and computer simulation of the crystal growth process which allows simulation of the microgravity crystal growth were developed.

Optomechanical design and analysis of a self-adaptive mounting method for optimizing phase matching of large potassium dihydrogen phosphate converter

NASA Astrophysics Data System (ADS)

Zhang, Zheng; Tian, Menjiya; Quan, Xusong; Pei, Guoqing; Wang, Hui; Liu, Tianye; Long, Kai; Xiong, Zhao; Rong, Yiming

2017-11-01

Surface control and phase matching of large laser conversion optics are urgent requirements and huge challenges in high-power solid-state laser facilities. A self-adaptive, nanocompensating mounting configuration of a large aperture potassium dihydrogen phosphate (KDP) frequency doubler is proposed based on a lever-type surface correction mechanism. A mechanical, numerical, and optical model is developed and employed to evaluate comprehensive performance of this mounting method. The results validate the method's advantages of surface adjustment and phase matching improvement. In addition, the optimal value of the modulation force is figured out through a series of simulations and calculations.

Effect of gold nanoparticle on stability of the DNA molecule: A study of molecular dynamics simulation.

PubMed

Izanloo, Cobra

2017-09-02

An understanding of the mechanism of DNA interactions with gold nanoparticles is useful in today medicine applications. We have performed a molecular dynamics simulation on a B-DNA duplex (CCTCAGGCCTCC) in the vicinity of a gold nanoparticle with a truncated octahedron structure composed of 201 gold atoms (diameter ∼1.8 nm) to investigate gold nanoparticle (GNP) effects on the stability of DNA. During simulation, the nanoparticle is closed to DNA and phosphate groups direct the particles into the major grooves of the DNA molecule. Because of peeling and untwisting states that are occur at end of DNA, the nucleotide base lies flat on the surface of GNP. The configuration entropy is estimated using the covariance matrix of atom-positional fluctuations for different bases. The results show that when a gold nanoparticle has interaction with DNA, entropy increases. The results of conformational energy and the hydrogen bond numbers for DNA indicated that DNA becomes unstable in the vicinity of a gold nanoparticle. The radial distribution function was calculated for water hydrogen-phosphate oxygen pairs. Almost for all nucleotide, the presence of a nanoparticle around DNA caused water molecules to be released from the DNA duplex and cations were close to the DNA.

Adverse Effects of Simulated Hyper- and Hypo-Phosphatemia on Endothelial Cell Function and Viability

PubMed Central

Zeng, Caihong; Rakheja, Dinesh; Zhu, Jiankun; Ye, Ting; Hutcheson, Jack; Vaziri, Nosratola D.; Liu, Zhihong; Mohan, Chandra; Zhou, Xin J.

2011-01-01

Background Dysregulaiton of phosphate homeostasis as occurs in chronic kidney disease is associated with cardiovascular complications. It has been suggested that both hyperphosphatemia and hypophosphatemia can cause cardiovascular disease. The molecular mechanisms by which high or low serum phosphate levels adversely affect cardiovascular function are poorly understood. The purpose of this study was to explore the mechanisms of endothelial dysfunction in the presence of non-physiologic phosphate levels. Methodology/Principal Findings We studied the effects of simulated hyper- and hypophosphatemia in human umbilical vein endothelial cells in vitro. We found both simulated hyperphosphatemia and hypophosphatemia decrease eNOS expression and NO production. This was associated with reduced intracellular calcium, increased protein kinase C β2 (PKCβ2), reduced cell viability, and increased apoptosis. While simulated hyperphosphatemia was associated with decreased Akt/p-Akt, Bcl-xl/Bax ratios, NFkB-p65 and p-Erk abundance, simulated hypophosphatemia was associated with increased Akt/p-Akt and Bcl-xl/Bax ratios and p-Mek, p38, and p-p38 abundance. Conclusions/Significance This is the first demonstration of endothelial dysfunction with hypophosphatemia. Our data suggests that both hyperphosphatemia and hypophosphatemia decrease eNOS activity via reduced intracellular calcium and increased PKCβ2. Hyperphosphatemia also appears to reduce eNOS transcription via reduced signaling through PI3K/Akt/NF-kB and MAPK/NF-kB pathways. On the other hand, hypophosphatemia appears to activate these pathways. Our data provides the basis for further studies to elucidate the relationship between altered phosphate homeostasis and cardiovascular disease. As a corollary, our data suggests that the level of phosphate in the culture media, if not in the physiologic range, may inadvertently affect experimental results. PMID:21858050

Evidence for a hydroxide ion bridging two magnesium ions at the active site of the hammerhead ribozyme.

PubMed Central

Hermann, T; Auffinger, P; Scott, W G; Westhof, E

1997-01-01

In the presence of magnesium ions, cleavage by the hammerhead ribozyme RNA at a specific residue leads to 2'3'-cyclic phosphate and 5'-OH extremities. In the cleavage reaction an activated ribose 2'-hydroxyl group attacks its attached 3'-phosphate. Molecular dynamics simulations of the crystal structure of the hammerhead ribozyme, obtained after flash-freezing of crystals under conditions where the ribozyme is active, provide evidence that a mu-bridging OH-ion is located between two Mg2+ions close to the cleavable phosphate. Constrained simulations show further that a flip from the C3'- endo to the C2'- endo conformation of the ribose at the cleavable phosphate brings the 2'-hydroxyl in proximity to both the attacked phosphorous atom and the mu-bridging OH-ion. Thus, the simulations lead to a detailed new insight into the mechanism of hammerhead ribozyme cleavage where a mu-hydroxo bridged magnesium cluster, located on the deep groove side, provides an OH-ion that is able to activate the 2'-hydroxyl nucleophile after a minor and localized conformational change in the RNA. PMID:9254698

Comparable stability of Hoogsteen and Watson-Crick base pairs in ionic liquid choline dihydrogen phosphate.

PubMed

Tateishi-Karimata, Hisae; Nakano, Miki; Sugimoto, Naoki

2014-01-08

The instability of Hoogsteen base pairs relative to Watson-Crick base pairs has limited biological applications of triplex-forming oligonucleotides. Hydrated ionic liquids (ILs) provide favourable environments for a wide range of chemical reactions and are known to impact the stabilities of Watson-Crick base pairs. We found that DNA triplex formation was significantly stabilized in hydrated choline dihydrogen phosphate as compared with an aqueous buffer at neutral pH. Interestingly, the stability of Hoogsteen base pairs was found to be comparable with that of Watson-Crick base pairs in the hydrated IL. Molecular dynamics simulations of a DNA triplex in the presence of choline ions revealed that the DNA triplex was stabilized because of the binding of choline ion around the third strand in the grooves. Our finding will facilitate the development of new DNA materials. Our data also indicate that triplex formation may be stabilized inside cells where choline ions and their derivatives are abundant in vivo.

Comparable Stability of Hoogsteen and Watson–Crick Base Pairs in Ionic Liquid Choline Dihydrogen Phosphate

PubMed Central

Tateishi-Karimata, Hisae; Nakano, Miki; Sugimoto, Naoki

2014-01-01

The instability of Hoogsteen base pairs relative to Watson–Crick base pairs has limited biological applications of triplex-forming oligonucleotides. Hydrated ionic liquids (ILs) provide favourable environments for a wide range of chemical reactions and are known to impact the stabilities of Watson–Crick base pairs. We found that DNA triplex formation was significantly stabilized in hydrated choline dihydrogen phosphate as compared with an aqueous buffer at neutral pH. Interestingly, the stability of Hoogsteen base pairs was found to be comparable with that of Watson–Crick base pairs in the hydrated IL. Molecular dynamics simulations of a DNA triplex in the presence of choline ions revealed that the DNA triplex was stabilized because of the binding of choline ion around the third strand in the grooves. Our finding will facilitate the development of new DNA materials. Our data also indicate that triplex formation may be stabilized inside cells where choline ions and their derivatives are abundant in vivo. PMID:24399194

Laboratory-Scale Bismuth Phosphate Extraction Process Simulation To Track Fate of Fission Products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serne, R. JEFFREY; Lindberg, Michael J.; Jones, Thomas E.

2007-02-28

Recent field investigation that collected and characterized vadose zone sediments from beneath inactive liquid disposal facilities at the Hanford 200 Areas show lower than expected concentrations of a long-term risk driver, Tc-99. Therefore laboratory studies were performed to re-create one of the three processes that were used to separate the plutonium from spent fuel and that created most of the wastes disposed or currently stored in tanks at Hanford. The laboratory simulations were used to compare with current estimates based mainly on flow sheet estimates and spotty historical data. Three simulations of the bismuth phosphate precipitation process show that lessmore » that 1% of the Tc-99, Cs-135/137, Sr-90, I-129 carry down with the Pu product and thus these isotopes should have remained within the metals waste streams that after neutralization were sent to single shell tanks. Conversely, these isotopes should not be expected to be found in the first and subsequent cycle waste streams that went to cribs. Measurable quantities (~20 to 30%) of the lanthanides, yttrium, and trivalent actinides (Am and Cm) do precipitate with the Pu product, which is higher than the 10% estimate made for current inventory projections. Surprisingly, Se (added as selenate form) also shows about 10% association with the Pu/bismuth phosphate solids. We speculate that the incorporation of some Se into the bismuth phosphate precipitate is caused by selenate substitution into crystal lattice sites for the phosphate. The bulk of the U daughter product Th-234 and Np-237 daughter product Pa-233 also associate with the solids. We suspect that the Pa daughter products of U (Pa-234 and Pa-231) would also co-precipitate with the bismuth phosphate induced solids. No more than 1 % of the Sr-90 and Sb-125 should carry down with the Pu product that ultimately was purified. Thus the current scheme used to estimate where fission products end up being disposed overestimates by one order of magnitude the partitioning Sr-90, Cs-137, and Sb-125 and by at least two orders of magnitude the portioning of Tc-99 to the first and subsequent cycle waste streams that went to cribs. Conversely, the current scheme underestimates the lanthanide and yttrium fission product quantities that went to cribs by a factor of about 3.« less

Assessing the influence of media composition and ionic strength on drug release from commercial immediate-release and enteric-coated aspirin tablets.

PubMed

Karkossa, Frank; Klein, Sandra

2017-10-01

The objective of this test series was to elucidate the importance of selecting the right media composition for a biopredictive in-vitro dissolution screening of enteric-coated dosage forms. Drug release from immediate-release (IR) and enteric-coated (EC) aspirin formulations was assessed in phosphate-based and bicarbonate-based media with different pH, electrolyte composition and ionic strength. Drug release from aspirin IR tablets was unaffected by media composition. In contrast, drug release from EC aspirin formulations was affected by buffer species and ionic strength. In all media, drug release increased with increasing ionic strength, but in bicarbonate-based buffers was delayed when compared with that in phosphate-based buffers. Interestingly, the cation species in the dissolution medium had also a clear impact on drug release. Drug release profiles obtained in Blank CarbSIF, a new medium simulating pH and average ionic composition of small intestinal fluid, were different from those obtained in all other buffer compositions studied. Results from this study in which the impact of various media parameters on drug release of EC aspirin formulations was systematically screened clearly show that when developing predictive dissolution tests, it is important to simulate the ionic composition of intraluminal fluids as closely as possible. © 2017 Royal Pharmaceutical Society.

Simulating transport of nitrogen and phosphorus in a Cambisol after natural and simulated intense rainfall.

PubMed

Kaufmann, Vander; Pinheiro, Adilson; Castro, Nilza Maria dos Reis

2014-05-01

Intense rainfall adversely affects agricultural areas, causing transport of pollutants. Physically-based hydrological models to simulate flows of water and chemical substances can be used to help decision-makers adopt measures which reduce such problems. The purpose of this paper is to evaluate the performance of SWAP and ANIMO models for simulating transport of water, nitrate and phosphorus nutrients, during intense rainfall events generated by a simulator, and during natural rainfall, on a volumetric drainage lysimeter. The models were calibrated and verified using daily time series and simulated rainfall measured at 10-minute intervals. For daily time-intervals, the Nash-Sutcliffe coefficient was 0.865 for the calibration period and 0.805 for verification. Under simulated rainfall, these coefficients were greater than 0.56. The pattern of both nitrate and phosphate concentrations in daily drainage flow under simulated rainfall was acceptably reproduced by the ANIMO model. In the simulated rainfall, loads of nitrate transported in surface runoff varied between 0.08 and 8.46 kg ha(-1), and in drainage form the lysimeter, between 2.44 and 112.57 kg ha(-1). In the case of phosphate, the loads transported in surface runoff varied between 0.002 and 0.504 kg ha(-1), and in drainage, between 0.005 and 1.107 kg ha(-1). The use of the two models SWAP and ANIMO shows the magnitudes of nitrogen and phosphorus fluxes transported by natural and simulated intense rainfall in an agricultural area with different soil management procedures, as required by decision makers. Copyright © 2014 Elsevier B.V. All rights reserved.

A Binary-Encounter-Bethe Approach to Simulate DNA Damage by the Direct Effect

NASA Technical Reports Server (NTRS)

Plante, Ianik; Cucinotta, Francis A.

2013-01-01

The DNA damage is of crucial importance in the understanding of the effects of ionizing radiation. The main mechanisms of DNA damage are by the direct effect of radiation (e.g. direct ionization) and by indirect effect (e.g. damage by.OH radicals created by the radiolysis of water). Despite years of research in this area, many questions on the formation of DNA damage remains. To refine existing DNA damage models, an approach based on the Binary-Encounter-Bethe (BEB) model was developed[1]. This model calculates differential cross sections for ionization of the molecular orbitals of the DNA bases, sugars and phosphates using the electron binding energy, the mean kinetic energy and the occupancy number of the orbital. This cross section has an analytic form which is quite convenient to use and allows the sampling of the energy loss occurring during an ionization event. To simulate the radiation track structure, the code RITRACKS developed at the NASA Johnson Space Center is used[2]. This code calculates all the energy deposition events and the formation of the radiolytic species by the ion and the secondary electrons as well. We have also developed a technique to use the integrated BEB cross section for the bases, sugar and phosphates in the radiation transport code RITRACKS. These techniques should allow the simulation of DNA damage by ionizing radiation, and understanding of the formation of double-strand breaks caused by clustered damage in different conditions.

Hydrothermal synthesis of porous triphasic hydroxyapatite/(alpha and beta) tricalcium phosphate.

PubMed

Vani, R; Girija, E K; Elayaraja, K; Prakash Parthiban, S; Kesavamoorthy, R; Narayana Kalkura, S

2009-12-01

A novel, porous triphasic calcium phosphate composed of nonresorbable hydroxyapatite (HAp) and resorbable tricalcium phosphate (alpha- and beta-TCP) has been synthesized hydrothermally at a relatively low temperature. The calcium phosphate precursor for hydrothermal treatment was prepared by gel method in the presence of ascorbic acid. XRD, FT-IR, Raman analyses confirmed the presence of HAp/TCP. The surface area and average pore size of the samples were found to be 28 m2/g and 20 nm, respectively. The samples were found to be bioactive in simulated body fluid (SBF).

Long range molecular dynamics study of interactions of the eukaryotic glucosamine-6-phosphate synthase with fructose-6-phosphate and UDP-GlcNAc.

PubMed

Miszkiel, Aleksandra; Wojciechowski, Marek

2017-11-01

Glucosamine-6-phosphate synthase (EC 2.6.1.16) is responsible for catalysis of the first and practically irreversible step in hexosamine metabolism. The final product of this pathway, uridine 5' diphospho N-acetyl-d-glucosamine (UDP-GlcNAc), is an essential substrate for assembly of bacterial and fungal cell walls. Moreover, the enzyme is involved in phenomenon of hexosamine induced insulin resistance in type II diabetes, which makes of it a potential target for anti-fungal, anti-bacterial and anti-diabetic therapy. The crystal structure of isomerase domain from human pathogenic fungus Candida albicans has been solved recently but it doesn't reveal the molecular mechanism details of inhibition taking place under UDP-GlcNAc influence, the unique feature of eukaryotic enzyme. The following study is a continuation of the previous research based on comparative molecular dynamics simulations of the structures with and without the enzyme's physiological inhibitor (UDP-GlcNAc) bound. The models used for this study included fructose-6-phosphate, one of the enzyme's substrates in its binding pocket. The simulation results studies demonstrated differences in mobility of the compared structures. Some amino acid residues were determined, for which flexibility is evidently different between the models. Importantly, it has been confirmed that the most fixed residues are related to the inhibitor binding process and to the catalysis reaction. The obtained results constitute an important step towards understanding of the inhibition that GlcN-6-P synthase is subjected by UDP-GlcNAc molecule. Copyright © 2017 Elsevier Inc. All rights reserved.

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

PubMed

Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2016-10-04

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

Ultra-Small-Angle X-ray Scattering – X-ray Photon Correlation Spectroscopy Studies of Incipient Structural Changes in Amorphous Calcium Phosphate Based Dental Composites

PubMed Central

Zhang, F.; Allen, A.J.; Levine, L.E.; Espinal, L.; Antonucci, J.M.; Skrtic, D.; O’Donnell, J.N.R.; Ilavsky, J.

2012-01-01

The local structural changes in amorphous calcium phosphate (ACP) based dental composites were studied under isothermal conditions using both static, bulk measurement techniques and a recently developed methodology based on combined ultra-small angle X-ray scattering – X-ray photon correlation spectroscopy (USAXS-XPCS), which permits a dynamic approach. While results from conventional bulk measurements do not show clear signs of structural change, USAXS-XPCS results reveal unambiguous evidence for local structural variations on a similar time scale to that of water loss in the ACP fillers. A thermal-expansion based simulation indicates that thermal behavior alone does not account for the observed dynamics. Together, these results suggest that changes in the water content of ACP affect the composite morphology due to changes in ACP structure that occur without an amorphous-to-crystalline conversion. It is also noted that biomedical materials research could benefit greatly from USAXS-XPCS, a dynamic approach. PMID:22374649

Multiscale QM/MM molecular dynamics study on the first steps of guanine damage by free hydroxyl radicals in solution.

PubMed

Abolfath, Ramin M; Biswas, P K; Rajnarayanam, R; Brabec, Thomas; Kodym, Reinhard; Papiez, Lech

2012-04-19

Understanding the damage of DNA bases from hydrogen abstraction by free OH radicals is of particular importance to understanding the indirect effect of ionizing radiation. Previous studies address the problem with truncated DNA bases as ab initio quantum simulations required to study such electronic-spin-dependent processes are computationally expensive. Here, for the first time, we employ a multiscale and hybrid quantum mechanical-molecular mechanical simulation to study the interaction of OH radicals with a guanine-deoxyribose-phosphate DNA molecular unit in the presence of water, where all of the water molecules and the deoxyribose-phosphate fragment are treated with the simplistic classical molecular mechanical scheme. Our result illustrates that the presence of water strongly alters the hydrogen-abstraction reaction as the hydrogen bonding of OH radicals with water restricts the relative orientation of the OH radicals with respect to the DNA base (here, guanine). This results in an angular anisotropy in the chemical pathway and a lower efficiency in the hydrogen-abstraction mechanisms than previously anticipated for identical systems in vacuum. The method can easily be extended to single- and double-stranded DNA without any appreciable computational cost as these molecular units can be treated in the classical subsystem, as has been demonstrated here. © 2012 American Chemical Society

FTIR spectra and properties of iron borophosphate glasses containing simulated nuclear wastes

NASA Astrophysics Data System (ADS)

Liao, Qilong; Wang, Fu; Chen, Kuiru; Pan, Sheqi; Zhu, Hanzhen; Lu, Mingwei; Qin, Jianfa

2015-07-01

30 wt.% simulated nuclear wastes were successfully immobilized by B2O3-doped iron phosphate base glasses. The structure and thermal stability of the prepared wasteforms were characterized by Fourier transform infrared spectroscopy and differential thermal analysis, respectively. The subtle structural variations attributed to different B2O3 doping modes have been discussed in detail. The results show that the thermal stability and glass forming tendency of the iron borophosphate glass wasteforms are faintly affected by different B2O3 doping modes. The main structural networks of iron borophosphate glass wasteforms are PO43-, P2O74-, [BO4] groups. Furthermore, for the wasteform prepared by using 10B2O3-36Fe2O3-54P2O5 as base glass, the distributions of Fe-O-P bonds, [BO4], PO43- and P2O74- groups are optimal. In general, the dissolution rate (DR) values of the studied iron borophosphate wasteforms are about 10-8 g cm-2 min-1. The obtained conclusions can offer some useful information for the disposal of high-level radioactive wastes using boron contained phosphate glasses.

New Insights into Active Site Conformation Dynamics of E. coli PNP Revealed by Combined H/D Exchange Approach and Molecular Dynamics Simulations.

PubMed

Kazazić, Saša; Bertoša, Branimir; Luić, Marija; Mikleušević, Goran; Tarnowski, Krzysztof; Dadlez, Michal; Narczyk, Marta; Bzowska, Agnieszka

2016-01-01

The biologically active form of purine nucleoside phosphorylase (PNP) from Escherichia coli (EC 2.4.2.1) is a homohexamer unit, assembled as a trimer of dimers. Upon binding of phosphate, neighboring monomers adopt different active site conformations, described as open and closed. To get insight into the functions of the two distinctive active site conformations, virtually inactive Arg24Ala mutant is complexed with phosphate; all active sites are found to be in the open conformation. To understand how the sites of neighboring monomers communicate with each other, we have combined H/D exchange (H/DX) experiments with molecular dynamics (MD) simulations. Both methods point to the mobility of the enzyme, associated with a few flexible regions situated at the surface and within the dimer interface. Although H/DX provides an average extent of deuterium uptake for all six hexamer active sites, it was able to indicate the dynamic mechanism of cross-talk between monomers, allostery. Using this technique, it was found that phosphate binding to the wild type (WT) causes arrest of the molecular motion in backbone fragments that are flexible in a ligand-free state. This was not the case for the Arg24Ala mutant. Upon nucleoside substrate/inhibitor binding, some release of the phosphate-induced arrest is observed for the WT, whereas the opposite effects occur for the Arg24Ala mutant. MD simulations confirmed that phosphate is bound tightly in the closed active sites of the WT; conversely, in the open conformation of the active site of the WT phosphate is bound loosely moving towards the exit of the active site. In Arg24Ala mutant binary complex Pi is bound loosely, too.

The effect of CPP-ACP-propolis chewing gum on calcium and phosphate ion release on caries-active subjects’ saliva and the formation of Streptococcus mutans biofilm

NASA Astrophysics Data System (ADS)

Hasnamudhia, F.; Bachtiar, E. W.; Sahlan, M.; Soekanto, S. A.

2017-08-01

The aim of this study was to analyze the effect of CPP-APP and propolis wax if they are combined in a chewing gum formulation, observed from the calcium and phosphate ion level released by CPP-ACP and the emphasis of Streptococcus mutans mass in the biofilm by propolis wax on caries-active subjects’ saliva. Chewing gum simulation was done in vitro on 25 caries-active subjects’ saliva using five concentrations of chewing gum (0% propolis + 0% CPP-ACP, 0% propolis + CPP-ACP, 2% propolis + CPP-ACP, 4% propolis + CPP-ACP, and 6% propolis + CPP-ACP) and was then tested using an atomic absorption spectrophotometer to analyze calcium ion levels, an ultraviolet-visible spectrophotometer to analyze phosphate ion levels, and a biofilm assay using crystal violet to analyze the decline in biofilm mass. After the chewing simulation, calcium ion levels on saliva+gum eluent increased significantly compared to the saliva control, with the highest calcium level released by CPP-ACP + 2% propolis chewing gum. There was an insignificant phosphate level change between the saliva control and saliva+gum eluent. There was also a significant decline of S. mutans biofilm mass in the saliva+gum eluent, mostly by the CPP-ACP chewing gum and CPP-ACP + 6% propolis. The CPP-ACP-propolis chewing gum simulation generated the largest increase in calcium and phosphate ion level and the largest decline in S. mutans biofilm mass.

Covalent attachment of a bioactive hyperbranched polymeric layer to titanium surface for the biomimetic growth of calcium phosphates

PubMed Central

Tsiourvas, D.; Arkas, M.; Diplas, S.; Mastrogianni, E.

2010-01-01

This work is investigating the chemical grafting on Ti surface of a polymer/calcium phosphate coating of improved adhesion for enhanced bioactivity. For this purpose, a whole new methodology was developed based on covalently attaching a hyperbranched poly(ethylene imine) layer on Ti surface able to promote calcium phosphate formation in a next deposition stage. This was achieved through an intermediate surface silanization step. The research included optimization both of the reaction conditions for covalently grafting the intermediate organosilicon and the subsequent hyperbranched poly(ethylene imine) layers, as well as of the conditions for the mechanical and chemical pretreatment of Ti surface before coating. The reaction steps were monitored employing FTIR and XPS analyses, whereas the surface morphology and structure of the successive coating layers were studied by SEM combined with EDS. The analysis confirmed the successful grafting of the hybrid layer which demonstrated very good ability for hydroxyapatite growth in simulated body fluid. PMID:21069559

Covalent attachment of a bioactive hyperbranched polymeric layer to titanium surface for the biomimetic growth of calcium phosphates.

PubMed

Tsiourvas, D; Tsetsekou, A; Arkas, M; Diplas, S; Mastrogianni, E

2011-01-01

This work is investigating the chemical grafting on Ti surface of a polymer/calcium phosphate coating of improved adhesion for enhanced bioactivity. For this purpose, a whole new methodology was developed based on covalently attaching a hyperbranched poly(ethylene imine) layer on Ti surface able to promote calcium phosphate formation in a next deposition stage. This was achieved through an intermediate surface silanization step. The research included optimization both of the reaction conditions for covalently grafting the intermediate organosilicon and the subsequent hyperbranched poly(ethylene imine) layers, as well as of the conditions for the mechanical and chemical pretreatment of Ti surface before coating. The reaction steps were monitored employing FTIR and XPS analyses, whereas the surface morphology and structure of the successive coating layers were studied by SEM combined with EDS. The analysis confirmed the successful grafting of the hybrid layer which demonstrated very good ability for hydroxyapatite growth in simulated body fluid.

The 3D structures of G-quadruplexes of HIV-1 integrase inhibitors: molecular dynamics simulations in aqueous solution and in the gas phase.

PubMed

Li, Ming-Hui; Zhou, Yi-Han; Luo, Quan; Li, Ze-Sheng

2010-04-01

The unimolecular G-quadruplex structures of d(GGGTGGGTGGGTGGGT) (G1) and d(GTGGTGGGTGGGTGGGT) (G2) are known as the potent nanomolar HIV-1 integrase inhibitors, thus investigating the 3D structures of the two sequences is significant for structure-based rational anti-HIV drug design. In this research, based on the experimental data of circular dichroism (CD) spectropolarimetry and electrospray ionization mass spectrometry (ESI-MS), the initial models of G1 and G2 were constructed by molecular modeling method. The modeling structures of G1 and G2 are intramolecular parallel-stranded quadruplex conformation with three guanine tetrads. Particularly, the structure of G2 possesses a T loop residue between the first and the second G residues that are the component of two adjacent same-stranded G-tetrad planes. This structure proposed by us has a very novel geometry and is different from all reported G-quadruplexes. The extended (35 ns) molecular dynamic (MD) simulations for the models indicate that the G-quadruplexes maintain their structures very well in aqueous solution whether the existence of K(+) or NH (4) (+) in the central channel. Furthermore, we perform 500 ns MD simulations for the models in the gas phase. The results show that all the ion-G-quadruplex complexes are maintained during the whole simulations, despite the large magnitude of phosphate-phosphate repulsions. The gas phase MD simulations provide a good explanation to ESI-MS experiments. Our 3D structures for G1 and G2 will assist in understanding geometric formalism of G-quadruplex folding and may be helpful as a platform for rational anti-HIV drug design.

Iron Phosphate Glass-Containing Hanford Waste Simulant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sevigny, Gary J.; Kimura, Marcia L.; Fischer, Christopher M.

2012-01-18

Resolution of the nation's high-level tank waste legacy requires the design, construction, and operation of large and technically complex one-of-a-kind processing waste treatment and vitrification facilities. While the ultimate limits for waste loading and melter efficiency have yet to be defined or realized, significant reductions in glass volumes for disposal and mission life may be possible with advancements in melter technologies and/or glass formulations. This test report describes the experimental results from a small-scale test using the research-scale melter (RSM) at Pacific Northwest National Laboratory (PNNL) to demonstrate the viability of iron-phosphate-based glass with a selected waste composition that ismore » high in sulfate (4.37 wt% SO3). The primary objective of the test was to develop data to support a cost-benefit analysis related to the implementation of phosphate-based glasses for Hanford low-activity waste (LAW) and/or other high-level waste streams within the U.S. Department of Energy complex. The testing was performed by PNNL and supported by Idaho National Laboratory, Savannah River National Laboratory, Missouri University of Science and Technology, and Mo-Sci Corporation.« less

Evaluation of amorphous magnesium phosphate (AMP) based non-exothermic orthopedic cements.

PubMed

Babaie, Elham; Lin, Boren; Goel, Vijay K; Bhaduri, Sarit B

2016-10-07

This paper reports for the first time the development of a biodegradable, non-exothermic, self-setting orthopedic cement composition based on amorphous magnesium phosphate (AMP). The occurrence of undesirable exothermic reactions was avoided through using AMP as the solid precursor. The phenomenon of self-setting with optimum rheology is achieved by incorporating a water soluble biocompatible/biodegradable polymer, polyvinyl alcohol (PVA). Additionally, PVA enables a controlled growth of the final phase via a biomimetic process. The AMP powder was synthesized using a precipitation method. The powder, when in contact with the aqueous PVA solution, forms a putty resulting in a nanocrystalline magnesium phosphate phase of cattiite. The as-prepared cement compositions were evaluated for setting times, exothermicity, compressive strength, biodegradation, and microstructural features before and after soaking in SBF, and in vitro cytocompatibility. Since cattiite is relatively unexplored in the literature, a first time evaluation reveals that it is cytocompatible, just like the other phases in the MgO-P 2 O 5 (Mg-P) system. The cement composition prepared with 15% PVA in an aqueous medium achieved clinically relevant setting times, mechanical properties, and biodegradation. Simulated body fluid (SBF) soaking resulted in coating of bobierrite onto the cement particle surfaces.

Discovery of Selective Inhibitors of Imidazoleglycerol-Phosphate Dehydratase from Mycobacterium tuberculosis by Virtual Screening

NASA Astrophysics Data System (ADS)

Podshivalov, D.; Mandzhieva, Yu. B.; Sidorov-Biryukov, D. D.; Timofeev, V. I.; Kuranova, I. P.

2018-01-01

Bacterial imidazoleglycerol-phosphate dehydratase from Mycobacterium tuberculosis (HisB- Mt) is a convenient target for the discovery of selective inhibitors as potential antituberculosis drugs. The virtual screening was performed to find compounds suitable for the design of selective inhibitors of HisB- Mt. The positions of four ligands, which were selected based on the docking scoring function and docked to the activesite region of the enzyme, were refined by molecular dynamics simulation. The nearest environment of the ligands was determined. These compounds selectively bind to functionally essential active-site residues, thus blocking access of substrates to the active site of the enzyme, and can be used as lead compounds for the design of selective inhibitors of HisB- M.

Multi-Functions of Carbonated Calcium Deficient Hydroxyapatite (CDHA)

NASA Astrophysics Data System (ADS)

Zhou, Huan

Natural bone is a complex composite mainly constituted of inorganic minerals and organic collagen molecules. Calcium phosphate (CaP) based materials have been proposed as the predominant bone substitute for bone tissue engineering applications due to their chemical similarity to bone mineral. Amorphous carbonated calcium deficient hydroxyapatite (CDHA) is an important compound among CaP materials because of the amorphous crystallite structure. The presence of extra ions in its lattice structure not only influences cell attachment and proliferation of osteoblasts, but also helps in bone metabolism. Biomimetic coating approach is the most widely used approach to produce CDHA coatings to implant. It is a process using simulated body fluid (SBF) to deposit bone-like CDHA coating to various material surfaces. The CDHA formation mechanism, SBF compositions and reacting conditions of biomimetic coating have already been sufficiently studied and compared in the past 20 years. It is an attempt in this thesis to explore new applications of SBF in biomedical research, focusing on different biomaterial applications: 1) based on the low temperature reaction condition of SBF, bisphosphonate incorporated CDHA coatings were deposited onto Ti6Al4V surface for the treatment of osteoporosis; 2) amorphous calcium phosphate nanospheres with extra elements in the lattice structure were prepared by a novel microwave assisted approach, providing a new potential of CaP materials production; 3) CDHA particles formed in SBF can be used as great fillers with biopolymers for preparing biocomposites for biomedical applications; 4) based on the high activity of CDHA amorphous structure and the stabilization ability of ethanol, yttrium and europium doped calcium phosphates were prepared using CDHA as a sacrificing template. In the end, future work based on these observations in the thesis is addressed, including areas of drug delivery, biocomposite fabrication and preparation of functionalized calcium phosphate materials.

Prebiotic Evolution of Nitrogen Compounds

NASA Technical Reports Server (NTRS)

Arrhenius, G.

1999-01-01

Support from this four year grant has funded our research on two general problems. One involves attempts to model the abiotic formation of simple source compounds for functional biomolecules, their concentration from dilute state in the hydrosphere and, in several cases, surface induced reactions to form precursor monomers for bioactive end products (refs. 1-5). Because of the pervasiveness and antiquity of phosphate based biochemistry and the catalytic activity of RNA we have exploring the hypothesis of an RNA World as an early stage in the emergence of life. This concept is now rather generally considered, but has been questioned due to the earlier lack of an experimentally demonstrated successful scheme for the spontaneous formation of ribose phosphate, the key backbone molecule in RNA. That impediment has now been removed. This has been achieved by demonstrating probable sources of activated (condensed) highly soluble and strongly sorbed phosphates in nature (Refs. 1,2) and effective condensation of aldehyde phosphates to form ribose phosphate in high yield (ref.6), thereby placing the RNA World concept on a somewhat safer experimental footing. Like all work in this field these experiments are oversimplifications that largely ignore competing side reactions with other compounds expected to be present. None the less our choice of experimental conditions aim at selective processes that eliminate interfering reactions. We have also sought to narrow the credibility gap by simulating geophysically and geochemically plausible conditions surrounding the putative prebiotic reactions.

The effect of pH on phosphorus availability and speciation in an aquaponics nutrient solution.

PubMed

Cerozi, Brunno da Silva; Fitzsimmons, Kevin

2016-11-01

The interaction between the main ions in aquaponics nutrient solutions affects chemical composition and availability of nutrients, and nutrient uptake by plant roots. This study determined the effect of pH on phosphorus (P) speciation and availability in an aquaponics nutrient solution and used Visual MINTEQ to simulate P species and P activity. In both experimental and simulated results, P availability decreased with increase in pH of aquaponics nutrient solutions. According to simulations, P binds to several cations leaving less free phosphate ions available in solution. High pH values resulted in the formation of insoluble calcium phosphate species. The study also demonstrated the importance of organic matter and alkalinity in keeping free phosphate ions in solution at high pH ranges. It is recommended though that pH in aquaponics systems is maintained at a 5.5-7.2 range for optimal availability and uptake by plants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of a Recombinant Escherichia coli Strain that Uses the Sarin Simulant Isopropylmethylphosphonic Acid (IMPA) as a Sole Carbon and Phosphate Source

DTIC Science & Technology

2016-04-01

phosphate use by these recombinant strains was evaluated because carbon use by these strains is still undergoing optimization by LBNL. The E . coli ...plasmids, had successful growth when transformed into a different E . coli background, which correlated with IMPA degradation. Ultimately, the...transformed E . coli strains, optimized at ECBC, were able to grow using IMPA as the phosphate source. 15. SUBJECT TERMS Acetylcholinesterase (AChE

Chesapeake Bay Sediment Flux Model

DTIC Science & Technology

1993-06-01

1988; Van der Molen , -88- 1991; Yoshida, 1981.) The model developed below is based on both of these approaches. It incorporates the diagenetic...288: pp. 289-333. Van der Molen , D.T. (1991): A simple, dynamic model for the simulation of the release of phosphorus from sediments in shallow...1974; Berner, 1980; van Cappellen and Berner, 1988). These relate the diagenetic production of phosphate to the resulting pore water concentration

Rapid Countermeasure Discovery against Francisella tularensis Based on a Metabolic Network Reconstruction

DTIC Science & Technology

2013-05-21

minimum inhibitory concentrations and mammalian cell cytotoxicities. The most promising compound had a low molecular weight, was non-toxic, and abolished... molecular weight, was non-toxic, and abolished bacterial growth at 13 mM, with putative activity against pantetheine-phosphate adenylyltransferase, an...time period. Metabolic genome-scale models of bacteria have provided a computational framework for in silico simulations to evaluate how metabolic

Dual-Function Metal-Organic Framework as a Versatile Catalyst for Detoxifying Chemical Warfare Agent Simulants.

PubMed

Liu, Yangyang; Moon, Su-Young; Hupp, Joseph T; Farha, Omar K

2015-12-22

The nanocrystals of a porphyrin-based zirconium(IV) metal-organic framework (MOF) are used as a dual-function catalyst for the simultaneous detoxification of two chemical warfare agent simulants at room temperature. Simulants of nerve agent (such as GD, VX) and mustard gas, dimethyl 4-nitrophenyl phosphate and 2-chloroethyl ethyl sulfide, have been hydrolyzed and oxidized, respectively, to nontoxic products via a pair of pathways catalyzed by the same MOF. Phosphotriesterase-like activity of the Zr6-containing node combined with photoactivity of the porphyrin linker gives rise to a versatile MOF catalyst. In addition, bringing the MOF crystals down to the nanoregime leads to acceleration of the catalysis.

Phosphate metabolite concentrations and ATP hydrolysis potential in normal and ischaemic hearts

PubMed Central

Wu, Fan; Zhang, Eric Y; Zhang, Jianyi; Bache, Robert J; Beard, Daniel A

2008-01-01

To understand how cardiac ATP and CrP remain stable with changes in work rate – a phenomenon that has eluded mechanistic explanation for decades – data from 31phosphate-magnetic resonance spectroscopy (31P-MRS) are analysed to estimate cytoplasmic and mitochondrial phosphate metabolite concentrations in the normal state, during high cardiac workstates, during acute ischaemia and reactive hyperaemic recovery. Analysis is based on simulating distributed heterogeneous oxygen transport in the myocardium integrated with a detailed model of cardiac energy metabolism. The model predicts that baseline myocardial free inorganic phosphate (Pi) concentration in the canine myocyte cytoplasm – a variable not accessible to direct non-invasive measurement – is approximately 0.29 mm and increases to 2.3 mm near maximal cardiac oxygen consumption. During acute ischaemia (from ligation of the left anterior descending artery) Pi increases to approximately 3.1 mm and ATP consumption in the ischaemic tissue is reduced quickly to less than half its baseline value before the creatine phosphate (CrP) pool is 18% depleted. It is determined from these experiments that the maximal rate of oxygen consumption of the heart is an emergent property and is limited not simply by the maximal rate of ATP synthesis, but by the maximal rate at which ATP can be synthesized at a potential at which it can be utilized. The critical free energy of ATP hydrolysis for cardiac contraction that is consistent with these findings is approximately −63.5 kJ mol−1. Based on theoretical findings, we hypothesize that inorganic phosphate is both the primary feedback signal for stimulating oxidative phosphorylation in vivo and also the most significant product of ATP hydrolysis in limiting the capacity of the heart to hydrolyse ATP in vivo. Due to the lack of precise quantification of Piin vivo, these hypotheses and associated model predictions remain to be carefully tested experimentally. PMID:18617566

Method for producing chemically bonded phosphate ceramics and for stabilizing contaminants encapsulated therein utilizing reducing agents

DOEpatents

Singh, Dileep; Wagh, Arun S.; Jeong, Seung-Young

2000-01-01

Known phosphate ceramic formulations are improved and the ability to produce iron-based phosphate ceramic systems is enabled by the addition of an oxidizing or reducing step during the acid-base reactions that form the phosphate ceramic products. The additives allow control of the rate of the acid-base reactions and concomitant heat generation. In an alternate embodiment, waste containing metal anions are stabilized in phosphate ceramic products by the addition of a reducing agent to the phosphate ceramic mixture. The reduced metal ions are more stable and/or reactive with the phosphate ions, resulting in the formation of insoluble metal species within the phosphate ceramic matrix, such that the resulting chemically bonded phosphate ceramic product has greater leach resistance.

Polarizable Multipole-Based Force Field for Dimethyl and Trimethyl Phosphate

PubMed Central

2015-01-01

Phosphate groups are commonly observed in biomolecules such as nucleic acids and lipids. Due to their highly charged and polarizable nature, modeling these compounds with classical force fields is challenging. Using quantum mechanical studies and liquid-phase simulations, the AMOEBA force field for dimethyl phosphate (DMP) ion and trimethyl phosphate (TMP) has been developed. On the basis of ab initio calculations, it was found that ion binding and the solution environment significantly impact both the molecular geometry and the energy differences between conformations. Atomic multipole moments are derived from MP2/cc-pVQZ calculations of methyl phosphates at several conformations with their chemical environments taken into account. Many-body polarization is handled via a Thole-style induction model using distributed atomic polarizabilities. van der Waals parameters of phosphate and oxygen atoms are determined by fitting to the quantum mechanical interaction energy curves for water with DMP or TMP. Additional stretch-torsion and angle-torsion coupling terms were introduced in order to capture asymmetry in P–O bond lengths and angles due to the generalized anomeric effect. The resulting force field for DMP and TMP is able to accurately describe both the molecular structure and conformational energy surface, including bond and angle variations with conformation, as well as interaction of both species with water and metal ions. The force field was further validated for TMP in the condensed phase by computing hydration free energy, liquid density, and heat of vaporization. The polarization behavior between liquid TMP and TMP in water is drastically different. PMID:26574325

Computer Folding of RNA Tetraloops: Identification of Key Force Field Deficiencies.

PubMed

Kührová, Petra; Best, Robert B; Bottaro, Sandro; Bussi, Giovanni; Šponer, Jiří; Otyepka, Michal; Banáš, Pavel

2016-09-13

The computer-aided folding of biomolecules, particularly RNAs, is one of the most difficult challenges in computational structural biology. RNA tetraloops are fundamental RNA motifs playing key roles in RNA folding and RNA-RNA and RNA-protein interactions. Although state-of-the-art Molecular Dynamics (MD) force fields correctly describe the native state of these tetraloops as a stable free-energy basin on the microsecond time scale, enhanced sampling techniques reveal that the native state is not the global free energy minimum, suggesting yet unidentified significant imbalances in the force fields. Here, we tested our ability to fold the RNA tetraloops in various force fields and simulation settings. We employed three different enhanced sampling techniques, namely, temperature replica exchange MD (T-REMD), replica exchange with solute tempering (REST2), and well-tempered metadynamics (WT-MetaD). We aimed to separate problems caused by limited sampling from those due to force-field inaccuracies. We found that none of the contemporary force fields is able to correctly describe folding of the 5'-GAGA-3' tetraloop over a range of simulation conditions. We thus aimed to identify which terms of the force field are responsible for this poor description of TL folding. We showed that at least two different imbalances contribute to this behavior, namely, overstabilization of base-phosphate and/or sugar-phosphate interactions and underestimated stability of the hydrogen bonding interaction in base pairing. The first artifact stabilizes the unfolded ensemble, while the second one destabilizes the folded state. The former problem might be partially alleviated by reparametrization of the van der Waals parameters of the phosphate oxygens suggested by Case et al., while in order to overcome the latter effect we suggest local potentials to better capture hydrogen bonding interactions.

Transmission performance analysis of WDM systems based on bismuth-doped phosphate glass fiber amplifiers

NASA Astrophysics Data System (ADS)

Ji, Jianhua; Huang, Qian; Wang, Ke; Xu, Ming; Jiang, Chun

2018-01-01

In this paper transmission performance of Allwave fiber WDM systems cascaded by bismuth-doped phosphate glass fiber amplifiers pumped by 808 nm lasers is analyzed for the first time, to the best of our knowledge. The rate and power propagation equations of a three-level system are used to model the signal amplification and noise figure in the doped fibers. The simulation results show that the channels in the 1460-1470 nm wavelength region in 32 × 40 Gbit/s WDM system with 10 nm channel space can reach a BER less than 1 × 10-9 with the transmission distance more than 600 km, but when the channel space is reduced to 1 nm, the performance of the system is degraded greatly.

Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Guohui; Um, Wooyong; Wang, Zheming

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford’s cribs, USA. During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitatedmore » as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67E-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42E-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.« less

Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments.

PubMed

Wang, Guohui; Um, Wooyong; Wang, Zheming; Reinoso-Maset, Estela; Washton, Nancy M; Mueller, Karl T; Perdrial, Nicolas; O'Day, Peggy A; Chorover, Jon

2017-10-03

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO 2 )(PO 4 )·3H 2 O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K 2 (UO 2 ) 6 O 4 (OH) 6 ·7H 2 O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10 -12 mol g -1 s -1 . In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10 -10 mol g -1 s -1 . The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

Influence of high-conductivity buffer composition on field-enhanced sample injection coupled to sweeping in CE.

PubMed

Anres, Philippe; Delaunay, Nathalie; Vial, Jérôme; Thormann, Wolfgang; Gareil, Pierre

2013-02-01

The aim of this work was to clarify the mechanism taking place in field-enhanced sample injection coupled to sweeping and micellar EKC (FESI-Sweep-MEKC), with the utilization of two acidic high-conductivity buffers (HCBs), phosphoric acid or sodium phosphate buffer, in view of maximizing sensitivity enhancements. Using cationic model compounds in acidic media, a chemometric approach and simulations with SIMUL5 were implemented. Experimental design first enabled to identify the significant factors and their potential interactions. Simulation demonstrates the formation of moving boundaries during sample injection, which originate at the initial sample/HCB and HCB/buffer discontinuities and gradually change the compositions of HCB and BGE. With sodium phosphate buffer, the HCB conductivity increased during the injection, leading to a more efficient preconcentration by staking (about 1.6 times) than with phosphoric acid alone, for which conductivity decreased during injection. For the same injection time at constant voltage, however, a lower amount of analytes was injected with sodium phosphate buffer than with phosphoric acid. Consequently sensitivity enhancements were lower for the whole FESI-Sweep-MEKC process. This is why, in order to maximize sensitivity enhancements, it is proposed to work with sodium phosphate buffer as HCB and to use constant current during sample injection. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The increase of apatite layer formation by the poly(3-hydroxybutyrate) surface modification of hydroxyapatite and β-tricalcium phosphate.

PubMed

Szubert, M; Adamska, K; Szybowicz, M; Jesionowski, T; Buchwald, T; Voelkel, A

2014-01-01

The aim of this study was the surface modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) grafting and characterization of modificates. The bioactivity examination was carried out by the determination to grow an apatite layer on modified materials during incubation in simulated body fluid at 37°C. The additional issue taken up in this paper was to investigate the influence of fluid replacement. The process of the surface modification of biomaterials was evaluated by means of infrared and Raman spectroscopy. Formation of the apatite layer was assessed by means of scanning electron microscopy and confirmed by energy dispersive, Raman and Fourier transformed infrared spectroscopy. During exposure in simulated body fluid, the variation of the zeta potential, pH measurement and relative weight was monitored. Examination of scanning electron microscopy micrographs suggests that modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) significantly increases apatite layer formation. Raman spectroscopy evaluation revealed that the formation of the apatite layer was more significant in the case of hydroxyapatite modificate, when compared to the β-tricalcium phosphate modificate. Both modificates were characterized by stable pH, close to the natural pH of human body fluids. Furthermore, we have shown that a weekly changed, simulated body fluid solution increases apatite layer formation. © 2013.

Bioavailable dietary phosphate, a mediator of cardiovascular disease, may be decreased with plant-based diets, phosphate binders, niacin, and avoidance of phosphate additives.

PubMed

McCarty, Mark F; DiNicolantonio, James J

2014-01-01

Increased fasting serum phosphate within the normal physiological range has been linked to increased cardiovascular risk in prospective epidemiology; increased production of fibroblast growth factor 23, and direct vascular effects of phosphate, may mediate this risk. Although dietary phosphate intake does not clearly influence fasting serum phosphate in individuals with normal renal function, increased phosphate intake can provoke a rise in fibroblast growth factor 23, and in diurnal phosphate levels, and hence may adversely influence vascular health. Dietary phosphate absorption can be moderated by emphasizing plant-based dietary choices (which provide phosphate in less bioavailable forms); avoidance of processed foods containing inorganic phosphate food additives; and by ingestion of phosphate-binder drugs, magnesium supplements, or niacin, which precipitate phosphate or suppress its gastrointestinal absorption. The propensity of dietary phosphate to promote vascular calcification may be opposed by optimal intakes of magnesium, vitamin K, and vitamin D; the latter should also counter the tendency of phosphate to elevate parathyroid hormone. Copyright © 2014 Elsevier Inc. All rights reserved.

Role of the Active Site Guanine in the glmS Ribozyme Self-Cleavage Mechanism: Quantum Mechanical/Molecular Mechanical Free Energy Simulations

PubMed Central

2015-01-01

The glmS ribozyme catalyzes a self-cleavage reaction at the phosphodiester bond between residues A-1 and G1. This reaction is thought to occur by an acid–base mechanism involving the glucosamine-6-phosphate cofactor and G40 residue. Herein quantum mechanical/molecular mechanical free energy simulations and pKa calculations, as well as experimental measurements of the rate constant for self-cleavage, are utilized to elucidate the mechanism, particularly the role of G40. Our calculations suggest that an external base deprotonates either G40(N1) or possibly A-1(O2′), which would be followed by proton transfer from G40(N1) to A-1(O2′). After this initial deprotonation, A-1(O2′) starts attacking the phosphate as a hydroxyl group, which is hydrogen-bonded to deprotonated G40, concurrent with G40(N1) moving closer to the hydroxyl group and directing the in-line attack. Proton transfer from A-1(O2′) to G40 is concomitant with attack of the scissile phosphate, followed by the remainder of the cleavage reaction. A mechanism in which an external base does not participate, but rather the proton transfers from A-1(O2′) to a nonbridging oxygen during nucleophilic attack, was also considered but deemed to be less likely due to its higher effective free energy barrier. The calculated rate constant for the favored mechanism is in agreement with the experimental rate constant measured at biological Mg2+ ion concentration. According to these calculations, catalysis is optimal when G40 has an elevated pKa rather than a pKa shifted toward neutrality, although a balance among the pKa’s of A-1, G40, and the nonbridging oxygen is essential. These results have general implications, as the hammerhead, hairpin, and twister ribozymes have guanines at a similar position as G40. PMID:25526516

Interpretation of leaching data for cementitious waste forms using analytical solutions based on mass transport theory and empiricism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spence, R.D.; Godbee, H.W.; Tallent, O.K.

1989-01-01

The analysis of leaching data using analytical solutions based on mass transport theory and empiricism is presented. The waste forms leached to generate the data used in this analysis were prepared with a simulated radioactive waste slurry with traces of potassium ion, manganese ions, carbonate ions, phosphate ions, and sulfate ions solidified with several blends of cementitious materials. Diffusion coefficients were estimated from the results of ANS - 16.1 tests. Data of fraction leached versus time is presented and discussed.

Characteristics of optical parametric oscillator synchronously pumped by Yb:KGW laser and based on periodically poled potassium titanyl phosphate crystal

NASA Astrophysics Data System (ADS)

Vengelis, Julius; Tumas, Adomas; Pipinytė, Ieva; Kuliešaitė, Miglė; Tamulienė, Viktorija; Jarutis, Vygandas; Grigonis, Rimantas; Sirutkaitis, Valdas

2018-03-01

We present experimental data and numerical simulation results obtained during investigation of synchronously pumped optical parametric oscillator (SPOPO) pumped by femtosecond Yb:KGW laser (central wavelength at 1033 nm). The nonlinear medium for parametric generation was periodically poled potassium titanyl phosphate crystal (PPKTP). Maximum parametric light conversion efficiency from pump power to signal power was more than 37.5% at λs=1530 nm wavelength, whereas the achieved signal wave continuous tuning range was from 1470 nm to 1970 nm with signal pulse durations ranging from 91 fs to roughly 280 fs. We demonstrated wavelength tuning by changing cavity length and PPKTP crystal grating period and also discussed net cavity group delay dispersion (GDD) influence on SPOPO output radiation characteristics. The achieved high pump to signal conversion efficiency and easy wavelength tuning make this device a very promising alternative to Ti:sapphire based SPOPOs as a source of continuously tunable femtosecond laser radiation in the near and mid-IR range.

Resorption Rate Tunable Bioceramic: Si, Zn-Modified Tricalcium Phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Xiang

2006-01-01

This dissertation is organized in an alternate format. Several manuscripts which have already been published or are to be submitted for publication have been included as separate chapters. Chapter 1 is a general introduction which describes the dissertation organization and introduces the human bone and ceramic materials as bone substitute. Chapter 2 is the background and literature review on dissolution behavior of calcium phosphate, and discussion of motivation for this research. Chapter 3 is a manuscript entitled ''Si,Zn-modified tricalcium phosphate: a phase composition and crystal structure study'', which was published in ''Key Engineering Materials'' [1]. Chapter 4 gives more crystalmore » structure details by neutron powder diffraction, which identifies the position for Si and Zn substitution and explains the stabilization mechanism of the structure. A manuscript entitled ''Crystal structure analysis of Si, Zn-modified Tricalcium phosphate by Neutron Powder Diffraction'' will be submitted to Biomaterials [2]. Chapter 5 is a manuscript, entitled ''Dissolution behavior and cytotoxicity test of Si, Zn-modified tricalcium phosphate'', which is to be submitted to Biomaterials [3]. This paper discusses the additives effect on the dissolution behavior of TCP, and cytotoxicity test result is also included. Chapter 6 is the study of hydrolysis process of {alpha}-tricalcium phosphate in the simulated body fluid, and the phase development during drying process is discussed. A manuscript entitled ''Hydrolysis of {alpha}-tricalcium phosphate in simulated body fluid and phase transformation during drying process'' is to be submitted to Biomaterials [4]. Ozan Ugurlu is included as co-authors in these two papers due to his TEM contributions. Appendix A is the general introduction of the materials synthesis, crystal structure and preliminary dissolution result. A manuscript entitled ''Resorption rate tunable bioceramic: Si and Zn-modified tricalcium phosphate'' was published in Ceramic Engineering and Science Proceedings (the 29th International Conference on Advanced Ceramics and Composites - Advances in Bioceramics and Biocomposites) [5].« less

Model of early self-replication based on covalent complementarity for a copolymer of glycerate-3-phosphate and glycerol-3-phosphate

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1989-01-01

Glyceraldehyde-3-phosphate acts as the substrate in a model of early self-replication of a phosphodiester copolymer of glycerate-3-phosphate and glycerol-3-phosphate. This model of self-replication is based on covalent complementarity in which information transfer is mediated by a single covalent bond, in contrast to multiple weak interactions that establish complementarity in nucleic acid replication. This replication model is connected to contemporary biochemistry through its use of glyceraldehyde-3-phosphate, a central metabolite of glycolysis and photosynthesis.

IN-SITU REMEDIATION OF ARSENIC IN SIMULATED GROUNDWATER USING ZEROVALENT IRON: LABORATORY COLUMN TESTS ON COMBINED EFFECTS OF PHOSPHATE AND SILICATE

EPA Science Inventory

We performed three column tests to study the behavior of permeable reactive barrier (PRB) materials to remove arsenic under dynamic flow conditions in the absence, as well as in the presence, of added phosphate and silicate. The column consisted of a 10.3-cm depth of 50 : 50 (w :...

Vehicle influence on permeation through intact and compromised skin.

PubMed

Gujjar, Meera; Banga, Ajay K

2014-09-10

The purpose of this study was to compare the transdermal permeation of a model compound, diclofenac diethylamine, from a hydrophilic and lipophilic vehicle across in vitro models simulating compromised skin. Mineral oil served as a lipophilic vehicle while 10mM phosphate buffered saline served as a hydrophilic vehicle. Compromised skin was simulated by tape stripping, delipidization, or microneedle application and compared with intact skin as a control. Transepidermal water loss was measured to assess barrier function. Skin compromised with tape stripping and delipidization significantly (p<0.05) increased permeation of diclofenac diethylamine compared to intact and microneedle treated skin with phosphate buffered saline vehicle. A similar trend in permeation was observed with mineral oil as the vehicle. For both vehicles, permeation across skin increased in the same order and correlated with degree of barrier impairment as indicated by transepidermal water loss values: intact

Development of the 2007 Chemical Decontaminant Source Document

DTIC Science & Technology

2009-03-01

Chemical Agent Simulant Specific DEM diethyl malonate MeS methyl salicylate PEG200 Polyethylene glycol 200 TEP triethyl phosphate Group 6...simulants • H-agent simulants o Methyl salicylate (MeS) o Chloroethyl phenyl sulfide (CEPS) o Chloroethyl ethyl sulfide (CEES) • VX simulants... Methyl bromide Ethyl phosphonothioic dichloride Sulfur dioxide Methyl chloroformate Ethyl phosphonic dichloride Sulfuric acid Methyl chlorosilane

Structure-based design of diverse inhibitors of Mycobacterium tuberculosis N-acetylglucosamine-1-phosphate uridyltransferase: combined molecular docking, dynamic simulation, and biological activity.

PubMed

Soni, Vijay; Suryadevara, Priyanka; Sriram, Dharmarajan; Kumar, Santhosh; Nandicoori, Vinay Kumar; Yogeeswari, Perumal

2015-07-01

Persistent nature of Mycobacterium tuberculosis is one of the major factors which make the drug development process monotonous against this organism. The highly lipophilic cell wall, which constituting outer mycolic acid and inner peptidoglycan layers, acts as a barrier for the drugs to enter the bacteria. The rigidity of the cell wall is imparted by the peptidoglycan layer, which is covalently linked to mycolic acid by arabinogalactan. Uridine diphosphate-N-acetylglucosamine (UDP-GlcNAc) serves as the starting material in the biosynthesis of this peptidoglycan layers. This UDP-GlcNAc is synthesized by N-acetylglucosamine-1-phosphate uridyltransferase (GlmU(Mtb)), a bi-functional enzyme with two functional sites, acetyltransferase site and uridyltransferase site. Here, we report design and screening of nine inhibitors against UTP and NAcGlc-1-P of uridyltransferase active site of glmU(Mtb). Compound 4 was showing good inhibition and was selected for further analysis. The isothermal titration calorimetry (ITC) experiments showed the binding energy pattern of compound 4 to the uridyltransferase active site is similar to that of substrate UTP. In silico molecular dynamics (MD) simulation studies, for compound 4, carried out for 10 ns showed the protein-compound complex to be stable throughout the simulation with relative rmsd in acceptable range. Hence, these compounds can serve as a starting point in the drug discovery processes against Mycobacterium tuberculosis.

Fabrication of mineralized electrospun PLGA and PLGA/gelatin nanofibers and their potential in bone tissue engineering.

PubMed

Meng, Z X; Li, H F; Sun, Z Z; Zheng, W; Zheng, Y F

2013-03-01

Surface mineralization is an effective method to produce calcium phosphate apatite coating on the surface of bone tissue scaffold which could create an osteophilic environment similar to the natural extracellular matrix for bone cells. In this study, we prepared mineralized poly(D,L-lactide-co-glycolide) (PLGA) and PLGA/gelatin electrospun nanofibers via depositing calcium phosphate apatite coating on the surface of these nanofibers to fabricate bone tissue engineering scaffolds by concentrated simulated body fluid method, supersaturated calcification solution method and alternate soaking method. The apatite products were characterized by the scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), and X-ray diffractometry (XRD) methods. A large amount of calcium phosphate apatite composed of dicalcium phosphate dihydrate (DCPD), hydroxyapatite (HA) and octacalcium phosphate (OCP) was deposited on the surface of resulting nanofibers in short times via three mineralizing methods. A larger amount of calcium phosphate was deposited on the surface of PLGA/gelatin nanofibers rather than PLGA nanofibers because gelatin acted as nucleation center for the formation of calcium phosphate. The cell culture experiments revealed that the difference of morphology and components of calcium phosphate apatite did not show much influence on the cell adhesion, proliferation and activity. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrospinning of calcium phosphate-poly (d,l-lactic acid) nanofibers for sustained release of water-soluble drug and fast mineralization

PubMed Central

Fu, Qi-Wei; Zi, Yun-Peng; Xu, Wei; Zhou, Rong; Cai, Zhu-Yun; Zheng, Wei-Jie; Chen, Feng; Qian, Qi-Rong

2016-01-01

Calcium phosphate-based biomaterials have been well studied in biomedical fields due to their outstanding chemical and biological properties which are similar to the inorganic constituents in bone tissue. In this study, amorphous calcium phosphate (ACP) nanoparticles were prepared by a precipitation method, and used for preparation of ACP-poly(d,l-lactic acid) (ACP-PLA) nanofibers and water-soluble drug-containing ACP-PLA nanofibers by electrospinning. Promoting the encapsulation efficiency of water-soluble drugs in electrospun hydrophobic polymer nanofibers is a common problem due to the incompatibility between the water-soluble drug molecules and hydrophobic polymers solution. Herein, we used a native biomolecule of lecithin as a biocompatible surfactant to overcome this problem, and successfully prepared water-soluble drug-containing ACP-PLA nanofibers. The lecithin and ACP nanoparticles played important roles in stabilizing water-soluble drug in the electrospinning composite solution. The electrospun drug-containing ACP-PLA nanofibers exhibited fast mineralization in simulated body fluid. The ACP nanoparticles played the key role of seeds in the process of mineralization. Furthermore, the drug-containing ACP-PLA nanofibers exhibited sustained drug release which simultaneously occurred with the in situ mineralization in simulated body fluid. The osteoblast-like (MG63) cells with spreading filopodia were well observed on the as-prepared nanofibrous mats after culturing for 24 hours, indicating a high cytocompatibility. Due to the high biocompatibility, sustained drug release, and fast mineralization, the as-prepared composite nanofibers may have potential applications in water-soluble drug loading and release for tissue engineering. PMID:27785016

Phosphine and methylphosphine production by simulated lightning—a study for the volatile phosphorus cycle and cloud formation in the earth atmosphere

NASA Astrophysics Data System (ADS)

Glindemann, Dietmar; Edwards, Marc; Schrems, Otto

Phosphine (PH 3), was recently found worldwide even in the remote atmosphere (Naturwissenschaften83(1996a)131; Atmos. Environ. 37(2003)24 29). It is of interest to find natural mechanisms which could produce phosphine gas and drive a volatile link of the atmospheric phosphorus cycle and the formation of phosphoric acid as possible condensation nuclei for clouds. Here, we report on simulated lightning exposing sodium phosphate in a reducing medium (methane model atmosphere or organic matter) for 5 s to a spark induced by microwave. The gas product analyzed by gas chromatography contained phosphine (yield up to 0.6 g kg -1 phosphate P) and methylphosphine (CH 3)PH 2 (yield up to 0.02 g kg -1 phosphate P). We suggest a plasma-chemical formation mechanism where organic compounds or methane or secondary hydrogen thereof reduce phosphate to phosphine of which a small fraction can subsequently react with methyl radicals to form methylphosphine. A small yield of 6 mg phosphine per kg phosphate P was even obtained in methane free medium, by simple plasmatic recombination of inorganic phosphorus. We believe that methane and hydrogen are useful model substances of pyrolytic gases with high reducing power which may form if lightning strikes biomass, soil and aerosol. These results suggest evidence that phosphine and methylphosphine (detectable in the field by intense garlic odor) are produced when atmospheric lightning strikes the ground or aerosol which is containing oxidized forms of phosphorus and chemical reductants. Additional reviewed data show that laboratory lightning was able to reduce a much more significant portion of phosphate to phosphite (up to 25% yield), methylphosphonic acid (up to 8.5% yield) and traces of hypophosphite in a matter of seconds.

Ultrafast phosphate hydration dynamics in bulk H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Costard, Rene, E-mail: costard@mbi-berlin.de; Tyborski, Tobias; Fingerhut, Benjamin P., E-mail: fingerhut@mbi-berlin.de

2015-06-07

Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H{sub 2}PO{sub 4}{sup −} ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. Two-dimensional infrared spectra of the symmetric (ν{sub S}(PO{sub 2}{sup −})) and asymmetric (ν{sub AS}(PO{sub 2}{sup −})) PO{sub 2}{sup −} stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH){sub 2}) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decaymore » and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the ν{sub S}(PO{sub 2}{sup −}) and ν{sub AS}(PO{sub 2}{sup −}) transition frequencies with larger frequency excursions for ν{sub AS}(PO{sub 2}{sup −}). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO{sub 2}{sup −}) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H{sub 2}PO{sub 4}{sup −}/H{sub 2}O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water.« less

Recovery of phosphate from aqueous solution by magnesium oxide decorated magnetic biochar and its potential as phosphate-based fertilizer substitute.

PubMed

Li, Ronghua; Wang, Jim J; Zhou, Baoyue; Awasthi, Mukesh Kumar; Ali, Amjad; Zhang, Zengqiang; Lahori, Altaf Hussain; Mahar, Amanullah

2016-09-01

The present study deals with the preparation of a novel MgO-impregnated magnetic biochar (MMSB) for phosphate recovery from aqueous solution. The MMSB was evaluated against sugarcane harvest residue biochar (SB) and magnetic biochar without Mg (MSB). The results showed that increasing Mg content in MMSB greatly improved the phosphate adsorption compared to SB and MSB, with 20% Mg-impregnated MMSB (20MMSB) recovering more than 99.5% phosphate from aqueous solution. Phosphate adsorption capacity of 20MMSB was 121.25mgP/g at pH 4 and only 37.53% of recovered phosphate was desorbed by 0.01mol/L HCl solutions. XRD and FTIR analysis showed that phosphate sorption mechanisms involved predominately with surface electrostatic attraction and precipitation with impregnated MgO and surface inner-sphere complexation with Fe oxide. The 20MMSB exhibited both maximum phosphate sorption and strong magnetic separation ability. Overall, phosphate-loaded 20MMSB significantly enhanced plant growth and could be used as a potential substitute for phosphate-based fertilizer. Copyright © 2016 Elsevier Ltd. All rights reserved.

Phosphoric acid addition effect on the microstructure and magnetic properties of iron-based soft magnetic composites

NASA Astrophysics Data System (ADS)

Hsiang, Hsing-I.; Fan, Liang-Fang; Hung, Jia-Jing

2018-02-01

The phosphoric acid addition effect on phosphate insulation coating microstructure was investigated in this study. The relationships between the phosphate insulation coating microstructure and temperature resistance, corrosion resistance and magnetic properties of iron-based soft magnetic composites (SMCs) were studied by using SEM, TEM/EDS and FTIR. It was observed that an iron phosphate/carbonyl iron core/shell structure is formed with carbonyl iron powder after phosphatizing treatment. The iron phosphate phase was identified as amorphous and its thickness increased from 30 nm to 60 nm as the phosphoric acid concentration was increased from 1 wt% to 2 wt%. When the phosphoric acid concentration was further increased to 5 wt%, the excess iron phosphate precipitates between the soft magnetic composite particles. The temperature and corrosion resistance and resistivity of the iron-based SMCs can be effectively improved using carbonyl iron powders after phosphatizing. The initial permeability of the iron-based SMCs decreased with increasing phosphoric acid concentration due to thicker insulation layer formation. However, the imaginary permeability below the domain wall displacement resonance frequency decreased with increasing phosphoric acid concentration. The DC-bias superposition characteristic can also be improved by increasing the phosphoric acid concentration. Iron-based SMCs with superior temperature and corrosion resistance, initial permeability, magnetic loss and DC-bias superposition characteristics can be obtained by controlling the phosphoric acid concentration during phosphatizing to adjust the iron phosphate precipitate thickness on the iron powder surface.

Bioactive Polymeric Nanoparticles for Periodontal Therapy

PubMed Central

Alfonso-Rodríguez, Camilo Andrés; Medina-Castillo, Antonio L.; Alaminos, Miguel; Toledano, Manuel

2016-01-01

Aims to design calcium and zinc-loaded bioactive and cytocompatible nanoparticles for the treatment of periodontal disease. Methods PolymP-nActive nanoparticles were zinc or calcium loaded. Biomimetic calcium phosphate precipitation on polymeric particles was assessed after 7 days immersion in simulated body fluid, by scanning electron microscopy attached to an energy dispersive analysis system. Amorphous mineral deposition was probed by X-ray diffraction. Cell viability analysis was performed using oral mucosa fibroblasts by: 1) quantifying the liberated deoxyribonucleic acid from dead cells, 2) detecting the amount of lactate dehydrogenase enzyme released by cells with damaged membranes, and 3) by examining the cytoplasmic esterase function and cell membranes integrity with a fluorescence-based method using the Live/Dead commercial kit. Data were analyzed by Kruskal-Wallis and Mann-Whitney tests. Results Precipitation of calcium and phosphate on the nanoparticles surfaces was observed in calcium-loaded nanoparticles. Non-loaded nanoparticles were found to be non-toxic in all the assays, calcium and zinc-loaded particles presented a dose dependent but very low cytotoxic effect. Conclusions The ability of calcium-loaded nanoparticles to promote precipitation of calcium phosphate deposits, together with their observed non-toxicity may offer new strategies for periodontal disease treatment. PMID:27820866

Secondary metabolism in simulated microgravity: beta-lactam production by Streptomyces clavuligerus

NASA Technical Reports Server (NTRS)

Fang, A.; Pierson, D. L.; Mishra, S. K.; Koenig, D. W.; Demain, A. L.

1997-01-01

Rotating bioreactors designed at NASA's Johnson Space Center were used to simulate a microgravity environment in which to study secondary metabolism. The system examined was beta-lactam antibiotic production by Streptomyces clavuligerus. Both growth and beta-lactam production occurred in simulated microgravity. Stimulatory effects of phosphate and L-lysine, previously detected in normal gravity, also occurred in simulated microgravity. The degree of beta-lactam antibiotic production was markedly inhibited by simulated microgravity.

The Mechanism of Anaerobic (Microbial) Corrosion.

DTIC Science & Technology

1982-12-01

hydrogen sulfide reacts with hypophosphite (as well as phosphate and phosphite ) .to form, in the presence of mild steel, iron phosphide, simulating the...of phosphate and phosphite , but not hypophosphite, were observed to have become yellow in 24 hours. The yellow color disap- peared upon exposure to... product is an amorphous type of iron phosphide which can be !- detected b the formation of phos hine upon its acidification. Phosphine( in M IFO, 1473

Silane surface modification effects on the electromagnetic properties of phosphatized iron-based SMCs

NASA Astrophysics Data System (ADS)

Fan, Liang-Fang; Hsiang, Hsing-I.; Hung, Jia-Jing

2018-03-01

It is difficult to achieve homogeneous phosphatized iron powder dispersion in organic resins during the preparation of soft magnetic composites (SMCs). Inhomogeneous iron powder mixing in organic resins generally leads to the formation of micro-structural defects in SMCs and hence causes the magnetic properties to become worse. Phosphatized iron powder dispersion in organic resins can be improved by coating the phosphatized iron powder surfaces with a coupling agent. This study investigated the (3-aminopropyl) triethoxysilane (APTES) surface modification effects on the electromagnetic properties of phosphatized iron-based soft magnetic composites (SMCs). The results showed that the phosphatized iron powder surface can be modified using APTES to improve the phosphatized iron powder and epoxy resin compatibility and hence enhance phosphate iron powder epoxy mixing. The tensile strength, initial permeability, rated current under DC-bias superposition and magnetic loss in SMCs prepared using phosphatized iron powders can be effectively improved using APTES surface modification, which provides a promising candidate for power chip inductor applications.

Experimental examination of ultraviolet Raman cross sections of chemical warfare agent simulants

NASA Astrophysics Data System (ADS)

Kullander, F.; Landström, L.; Lundén, H.; Wästerby, Pär.

2015-05-01

Laser induced Raman scattering from the commonly used chemical warfare agent simulants dimethyl sulfoxide, tributyl phosphate, triethyl phosphonoacetate was measured at excitation wavelengths ranging from 210 to 410 nm using a pulsed laser based spectrometer system with a probing distance of 1.4 m and with a field of view on the target of less than 1mm. For the purpose of comparison with well explored reference liquids the Raman scattering from simulants was measured in the form of an extended liquid surface layer on top of a silicon wafer. This way of measuring enabled direct comparison to the Raman scattering strength from cyclohexane. The reference Raman spectra were used to validate the signal strength of the simulants and the calibration of the experimental set up. Measured UV absorbance functions were used to calculate Raman cross sections. Established Raman cross sections of the simulants make it possible to use them as reference samples when measuring on chemical warfare agents in droplet form.

Effects of phosphate-enhanced ozone/biofiltration on formation of disinfection byproducts and occurrence of opportunistic pathogens in drinking water distribution systems.

PubMed

Xing, Xueci; Wang, Haibo; Hu, Chun; Liu, Lizhong

2018-08-01

The effects of ozone-biologically activated carbon (O 3 -BAC) treatment with various phosphate doses (0, 0.3 or 0.6 mg/L) were investigated on the formation of disinfection by-products (DBPs) and occurrence of opportunistic pathogens (OPs) in drinking water distribution systems (DWDSs) simulated by annular reactors (ARs). It was found that the lowest DBPs and the highest inactivation of OPs such as Mycobacterium spp., Mycobacterium avium, Aeromonas spp., Pseudomonas aeruginosa and Hartmanella vermiformis, occurred in the effluent of the AR with 0.6 mg/L phosphate addition. Based on the results of different characterization techniques, for the AR with 0.6 mg/L phosphate-enhanced O 3 -BAC treatment, dissolved organic carbon in the influent exhibited the lowest concentration and most stable fraction due to the improved biodegradation effect. Moreover, the total amount of suspended extracellular polymeric substances (EPS) in the bulk water of the AR decreased greatly, resulting in the lowest chlorine consumption and DBPs formation in the AR. In Fourier transform infrared spectra of the suspended EPS, the amide II band (1600-1500 cm -1 ) disappeared and the protein/polysaccharide ratio decreased remarkably, indicating the destruction of protein and a decrease in hydrophobicity. Moreover, β-sheets and α-helices in the protein secondary structures were degraded while the random coils increased sharply as phosphate addition increased to 0.6 mg/L, inhibiting microbial aggregation and hence weakening the chlorine-resistance capability. Thus, most of the OPs in suspended biofilms were more easily inactivated by residual chlorine, resulting in the lowest OPs occurrence in the effluent of the AR. Our findings indicated that enhancing the efficiency of the BAC filter by adding phosphate is a promising method for improving water quality in DWDSs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preclinical studies of VS‐505: a non‐absorbable highly effective phosphate binder

PubMed Central

Chen, Yung‐wu; Wong, Jonathan T; Wessale, Jerry L

2016-01-01

Abstract Background and Purpose Phosphate imbalance is often present in chronic kidney disease (CKD), and it contributes to a higher cardiovascular mortality rate. A phosphate binder is typically part of a treatment strategy for controlling phosphate imbalance. However, safety concerns and low compliance are two well‐recognized disadvantages of on‐market phosphate binders. This report describes the preclinical studies of VS‐505, a non‐absorbable, calcium‐ and aluminum‐free, plant‐derived polymer currently being evaluated in haemodialysis patients in Australia. Experimental Approach Normal Sprague Dawley (SD) rats or uraemic SD rats induced by 5/6 nephrectomy fed a high‐phosphate diet were treated with VS‐505 or sevelamer (0.05–10% in food) for 5 and 28 days respectively. Key Results Urinary and serum phosphate levels were significantly elevated in untreated rats, and were decreased by VS‐505 and sevelamer. VS‐505 increased faecal phosphate levels in a dose‐dependent manner. High‐phosphate diet also caused an increase in serum FGF‐23 and parathyroid hormone in nephrectomized (NX) rats, effects prevented by VS‐505 or sevelamer. Significant aortic calcification was observed in NX rats treated with 5% sevelamer, whereas VS‐505 at all doses tested did not show effects. VS‐505 had no effects on small intestine histomorphology and intestinal sodium‐dependent phosphate cotransporter gene expression. In vitro characterizations showed that VS‐505 has a relatively high density and low expansion volume when exposed to simulated gastric fluid. Conclusions and Implications VS‐505 is a safe and effective phosphate binder and may offer the advantage of having a reduced pill burden and minimal GI side effects for CKD patients. PMID:27156057

Phosphate removal from aqueous solutions using raw and activated red mud and fly ash.

PubMed

Li, Yanzhong; Liu, Changjun; Luan, Zhaokun; Peng, Xianjia; Zhu, Chunlei; Chen, Zhaoyang; Zhang, Zhongguo; Fan, Jinghua; Jia, Zhiping

2006-09-01

The effect of acidification and heat treatment of raw red mud (RM) and fly ash (FA) on the sorption of phosphate was studied in parallel experiments. The result shows that a higher efficiency of phosphate removal was acquired by the activated samples than by the raw ones. The sample prepared by using the RM stirred with 0.25 M HCl for 2h (RM0.25), as well as another sample prepared by heating the RM at 700 degrees C for 2h (RM700), registered the maximum removal of phosphate (99% removal of phosphate). This occurred when they were used in the phosphate sorption studies conducted at pH 7.0 and 25 degrees C with the initial PO(4)(3-) concentration of 155 mg P/l. The FA samples treated in the same way described above can achieve 7.0 and 8.2 mg P/l phosphate removal for FA0.25 and FA700 respectively, corresponding to 45.2% and 52.9% removal. The activated materials performed higher phosphate removal over broader pH range compared with the raw ones. The influences of various factors, such as initial pH and initial phosphate concentration on the sorption capacity were also studied in batch equilibration technique. Solution pH significantly influenced the sorption. Each sample achieved the maximal removal of phosphate at pH 7.0. The amount of phosphate removal increased with the solute concentration. The Freundlich and Langmuir models were used to simulate the sorption equilibrium. The results indicate that the Langmuir model has a better correlation with the experimental data than the Freundlich model.

Surface characterization and corrosion behavior of calcium phosphate-base composite layer on titanium and its alloys via plasma electrolytic oxidation: A review paper.

PubMed

Rafieerad, A R; Ashra, M R; Mahmoodian, R; Bushroa, A R

2015-12-01

In recent years, calcium phosphate-base composites, such as hydroxyapatite (HA) and carbonate apatite (CA) have been considered desirable and biocompatible coating layers in clinical and biomedical applications such as implants because of the high resistance of the composites. This review focuses on the effects of voltage, time and electrolytes on a calcium phosphate-base composite layer in case of pure titanium and other biomedical grade titanium alloys via the plasma electrolytic oxidation (PEO) method. Remarkably, these parameters changed the structure, morphology, pH, thickness and crystallinity of the obtained coating for various engineering and biomedical applications. Hence, the structured layer caused improvement of the biocompatibility, corrosion resistance and assignment of extra benefits for Osseo integration. The fabricated layer with a thickness range of 10 to 20 μm was evaluated for physical, chemical, mechanical and tribological characteristics via XRD, FESEM, EDS, EIS and corrosion analysis respectively, to determine the effects of the applied parameters and various electrolytes on morphology and phase transition. Moreover, it was observed that during PEO, the concentration of calcium, phosphor and titanium shifts upward, which leads to an enhanced bioactivity by altering the thickness. The results confirm that the crystallinity, thickness and contents of composite layer can be changed by applying thermal treatments. The corrosion behavior was investigated via the potentiodynamic polarization test in a body-simulated environment. Here, the optimum corrosion resistance was obtained for the coating process condition at 500 V for 15 min in Ringer solution. This review has been summarized, aiming at the further development of PEO by producing more adequate titanium-base implants along with desired mechanical and biomedical features. Copyright © 2015 Elsevier B.V. All rights reserved.

Role of magnesium on the biomimetic deposition of calcium phosphate

NASA Astrophysics Data System (ADS)

Sarma, Bimal K.; Sarma, Bikash

2016-10-01

Biomimetic depositions of calcium phosphate (CaP) are carried out using simulated body fluid (SBF), calcifying solution and newly developed magnesium containing calcifying solution. Calcium phosphate has a rich phase diagram and is well known for its excellent biocompatibility and bioactivity. The most common phase is hydroxyapatite (HAp), an integral component of human bone and tooth, widely used in orthopedic and dental applications. In addition, calcium phosphate nanoparticles show promise for the targeted drug delivery. The doping of calcium phosphate by magnesium, zinc, strontium etc. can change the protein uptake by CaP nanocrystals. This work describes the role of magnesium on the nucleation and growth of CaP on Ti and its oxide substrates. X-ray diffraction studies confirm formation of HAp nanocrystals which closely resemble the structure of bone apatite when grown using SBF and calcifying solution. It has been observed that magnesium plays crucial role in the nucleation and growth of calcium phosphate. A low magnesium level enhances the crystallinity of HAp while higher magnesium content leads to the formation of amorphous calcium phosphate (ACP) phase. Interestingly, the deposition of ACP phase is rapid when magnesium ion concentration in the solution is 40% of calcium plus magnesium ions concentration. Moreover, high magnesium content alters the morphology of CaP films.

Lead iron phosphate glass as a containment medium for disposal of high-level nuclear waste

DOEpatents

Boatner, Lynn A.; Sales, Brian C.

1989-01-01

Lead-iron phosphate glasses containing a high level of Fe.sub.2 O.sub.3 for use as a storage medium for high-level radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste, a highly corrosion resistant, homogeneous, easily processed glass can be formed. For corroding solutions at 90.degree. C., with solution pH values in the range between 5 and 9, the corrosion rate of the lead-iron phosphate nuclear waste glass is at least 10.sup.2 to 10.sup.3 times lower than the corrosion rate of a comparable borosilicate nuclear waste glass. The presence of Fe.sub.2 O.sub.3 in forming the lead-iron phosphate glass is critical. Lead-iron phosphate nuclear waste glass can be prepared at temperatures as low as 800.degree. C., since they exhibit very low melt viscosities in the 800.degree. to 1050.degree. C. temperature range. These waste-loaded glasses do not readily devitrify at temperatures as high as 550.degree. C. and are not adversely affected by large doses of gamma radiation in H.sub.2 O at 135.degree. C. The lead-iron phosphate waste glasses can be prepared with minimal modification of the technology developed for processing borosilicate glass nuclear wasteforms.

Reductions in mitochondrial O(2) consumption and preservation of high-energy phosphate levels after simulated ischemia in chronic hibernating myocardium.

PubMed

Hu, Qingsong; Suzuki, Gen; Young, Rebeccah F; Page, Brian J; Fallavollita, James A; Canty, John M

2009-07-01

We performed the present study to determine whether hibernating myocardium is chronically protected from ischemia. Myocardial tissue was rapidly excised from hibernating left anterior descending coronary regions (systolic wall thickening = 2.8 +/- 0.2 vs. 5.4 +/- 0.3 mm in remote myocardium), and high-energy phosphates were quantified by HPLC during simulated ischemia in vitro (37 degrees C). At baseline, ATP (20.1 +/- 1.0 vs. 26.7 +/- 2.1 micromol/g dry wt, P < 0.05), ADP (8.1 +/- 0.4 vs. 10.3 +/- 0.8 micromol/g, P < 0.05), and total adenine nucleotides (31.2 +/- 1.3 vs. 40.1 +/- 2.9 micromol/g, P < 0.05) were depressed compared with normal myocardium, whereas total creatine, creatine phosphate, and ATP-to-ADP ratios were unchanged. During simulated ischemia, there was a marked attenuation of ATP depletion (5.6 +/- 0.9 vs. 13.7 +/- 1.7 micromol/g at 20 min in control, P < 0.05) and mitochondrial respiration [145 +/- 13 vs. 187 +/- 11 ng atoms O(2).mg protein(-1).min(-1) in control (state 3), P < 0.05], whereas lactate accumulation was unaffected. These in vitro changes were accompanied by protection of the hibernating heart from acute stunning during demand-induced ischemia. Thus, despite contractile dysfunction at rest, hibernating myocardium is ischemia tolerant, with reduced mitochondrial respiration and slowing of ATP depletion during simulated ischemia, which may maintain myocyte viability.

Leaching of Cu, Cd, Pb, and phosphorus and their availability in the phosphate-amended contaminated soils under simulated acid rain.

PubMed

Cui, Hongbiao; Zhang, Shiwen; Li, Ruyan; Yi, Qitao; Zheng, Xuebo; Hu, Youbiao; Zhou, Jing

2017-09-01

Phosphate amendments have been used to immobilize heavy metal-contaminated soils. However, phosphate amendments contain large amounts of phosphorus, which could leach out to potentially contaminate groundwater and surface water. A laboratory column leaching experiment was designed to study the effects of simulated acid rain (SAR) on the potential release of copper (Cu), lead (Pb), cadmium (Cd), and phosphorus (P), and their availability after immobilizing with hydroxyapatite (HAP) and potassium dihydrogen phosphate (PDP). The application of HAP and PDP enhanced the leachate electrical conductivity, total organic carbon, and pH. Higher P was found in the PDP- (>4.29 mg L -1 ) and HAP-treated (>1.69 mg L -1 ) columns than that in untreated (<0.2 mg L -1 ) columns, and they were both over the class V limit (0.4 mg L -1 ) mandated by the Chinese National Quality Standards for Surface Waters (GB 3838-2002). PDP application decreased the leachate Cu, Pb, and Cd effectively; however, HAP addition increased leachate Cu and Pb. HAP and PDP applications decreased the soil CaCl 2 -extractable and exchangeable fraction of Cu, Pb, and Cd, and increased resin P. However, eluviations transformed the heavy metals from inactive to active fractions and reduced soil labile P. These findings showed that HAP and PDP had a potential risk of excessive P-induced eutrophication. Meanwhile, more attention should be paid to the leaching loss of multiple metals because phosphate amendments might promote the leaching of some metals while immobilizing others.

Computer Simulations Reveal Substrate Specificity of Glycosidic Bond Cleavage in Native and Mutant Human Purine Nucleoside Phosphorylase.

PubMed

Isaksen, Geir Villy; Hopmann, Kathrin Helen; Åqvist, Johan; Brandsdal, Bjørn Olav

2016-04-12

Purine nucleoside phosphorylase (PNP) catalyzes the reversible phosphorolysis of purine ribonucleosides and 2'-deoxyribonucleosides, yielding the purine base and (2'-deoxy)ribose 1-phosphate as products. While this enzyme has been extensively studied, several questions with respect to the catalytic mechanism have remained largely unanswered. The role of the phosphate and key amino acid residues in the catalytic reaction as well as the purine ring protonation state is elucidated using density functional theory calculations and extensive empirical valence bond (EVB) simulations. Free energy surfaces for adenosine, inosine, and guanosine are fitted to ab initio data and yield quantitative agreement with experimental data when the surfaces are used to model the corresponding enzymatic reactions. The cognate substrates 6-aminopurines (inosine and guanosine) interact with PNP through extensive hydrogen bonding, but the substrate specificity is found to be a direct result of the electrostatic preorganization energy along the reaction coordinate. Asn243 has previously been identified as a key residue providing substrate specificity. Mutation of Asn243 to Asp has dramatic effects on the substrate specificity, making 6-amino- and 6-oxopurines equally good as substrates. The principal effect of this particular mutation is the change in the electrostatic preorganization energy between the native enzyme and the Asn243Asp mutant, clearly favoring adenosine over inosine and guanosine. Thus, the EVB simulations show that this particular mutation affects the electrostatic preorganization of the active site, which in turn can explain the substrate specificity.

A hybrid QM/MM simulation study of intramolecular proton transfer in the pyridoxal 5'-phosphate in the active site of transaminase: influence of active site interaction on proton transfer.

PubMed

Dutta Banik, Sindrila; Chandra, Amalendu

2014-09-25

Pyridoxal 5'-phosphate (PLP) Schiff base, a versatile cofactor, exhibits a tautomeric equilibrium that involves an intramolecular proton transfer between the N-protonated zwitterionic ketoenamine tautomer and the O-protonated covalent enolimine tautomer. It has been postulated that for the catalytic activity, the PLP has to be in the zwitterionic ketoenamine tautomeric form. However, the exact position of the tautomeric equilibrium of Schiff base in the active site of PLP-dependent enzyme is not known yet. In the present work, we investigated the tautomeric equilibrium for the external aldimine state of PLP aspartate (PLP-Asp) Schiff base in the active site of aspartate aminotransferase (AspAT) using combined quantum mechanical and molecular mechanical simulations. The main focus of the present study is to analyze the factors that control the tautomeric equilibrium in the active sites of various PLP-dependent enzymes. The results show that the ketoenamine tautomer is more preferred than the enolimine tautomer both in the gas and aqueous phases as well as in the active site of AspAT. Current simulations show that the active site of AspAT is more suitable for the ketoenamine tautomer compared to the enolimine tautomer. Interestingly, the Tyr225 acts as a proton donor to the phenolic oxygen in the ketoenamine tautomer, while in the covalent enolimine tautomer, it acts as a proton acceptor to the phenolic oxygen. Finally, the metadynamics study confirms this result. The calculated free energy barrier is about 7.5 kcal/mol. A comparative analysis of the microenvironment created by the active site residues of three different PLP-dependent enzymes (aspartate aminotransferase, Dopa decarboxylase, and Ala-racemase) has been carried out to understand the controlling factor(s) of the tautomeric equilibrium. The analysis shows that the intermolecular hydrogen bonding between active site residues and the phenolic oxygen of PLP shifts the tautomeric equilibrium toward the N-protonated ketoenamine tautomeric form.

Remnants of an Ancient Metabolism without Phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldford, Joshua E.; Hartman, Hyman; Smith, Temple F.

Phosphate is essential for all living systems, serving as a building block of genetic and metabolic machinery. However, it is unclear how phosphate could have assumed these central roles on primordial Earth, given its poor geochemical accessibility. We used systems biology approaches to explore the alternative hypothesis that a protometabolism could have emerged prior to the incorporation of phosphate. Surprisingly, we identified a cryptic phosphate-independent core metabolism producible from simple prebiotic compounds. This network is predicted to support the biosynthesis of a broad category of key biomolecules. Its enrichment for enzymes utilizing iron-sulfur clusters, and the fact that thermodynamic bottlenecksmore » are more readily overcome by thioester rather than phosphate couplings, suggest that this network may constitute a ‘‘metabolic fossil’’ of an early phosphate-free nonenzymatic biochemistry. Thus, our results corroborate and expand previous proposals that a putative thioester-based metabolism could have predated the incorporation of phosphate and an RNA-based genetic system.« less

Remnants of an Ancient Metabolism without Phosphate

DOE PAGES

Goldford, Joshua E.; Hartman, Hyman; Smith, Temple F.; ...

2017-03-09

Phosphate is essential for all living systems, serving as a building block of genetic and metabolic machinery. However, it is unclear how phosphate could have assumed these central roles on primordial Earth, given its poor geochemical accessibility. We used systems biology approaches to explore the alternative hypothesis that a protometabolism could have emerged prior to the incorporation of phosphate. Surprisingly, we identified a cryptic phosphate-independent core metabolism producible from simple prebiotic compounds. This network is predicted to support the biosynthesis of a broad category of key biomolecules. Its enrichment for enzymes utilizing iron-sulfur clusters, and the fact that thermodynamic bottlenecksmore » are more readily overcome by thioester rather than phosphate couplings, suggest that this network may constitute a ‘‘metabolic fossil’’ of an early phosphate-free nonenzymatic biochemistry. Thus, our results corroborate and expand previous proposals that a putative thioester-based metabolism could have predated the incorporation of phosphate and an RNA-based genetic system.« less

Manure derived biochar can successfully replace phosphate rock amendment in peatland restoration.

PubMed

Pouliot, Rémy; Hugron, Sandrine; Rochefort, Line; Godbout, Stéphane; Palacios, Joahnn H; Groeneveld, Elisabeth; Jarry, Isabelle

2015-07-01

Phosphate rock fertilization is commonly used in peatland restoration to promote the growth of Polytrichum strictum, a nurse plant which aids the establishment of Sphagnum mosses. The present study tested whether 1) phosphorus fertilization facilitates the germination of P. strictum spores and 2) biochar derived from local pig manure can replace imported phosphate rock currently used in peatland restoration. Various doses of biochar were compared to phosphate rock to test its effect directly on P. strictum stem regeneration (in Petri dishes in a growth chamber) and in a simulation of peatland restoration with the moss layer transfer technique (in mesocoms in a greenhouse). Phosphorus fertilization promoted the germination of P. strictum spores as well as vegetative stem development. Biochar can effectively replace phosphate rock in peatland restoration giving a new waste management option for rural regions with phosphorus surpluses. As more available phosphorus was present in biochar, an addition of only 3-9 g m(-2) of pig manure biochar is recommended during the peatland restoration process, which is less than the standard dose of phosphate rock (15 g m(-2)). Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of Phosphate, Fluoride, and Nitrate on Gibbsite Dissolution Rate and Solubility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herting, Daniel L.

2014-01-29

Laboratory tests have been completed with simulated tank waste samples to investigate the effects of phosphate, fluoride, and nitrate on the dissolution rate and equilibrium solubility of gibbsite in sodium hydroxide solution at 22 and 40{degrees}C. Results are compared to relevant literature data and to computer model predictions. The presence of sodium nitrate (3 M) caused a reduction in the rate of gibbsite dissolution in NaOH, but a modest increase in the equilibrium solubility of aluminum. The increase in solubility was not as large, though, as the increase predicted by the computer model. The presence of phosphate, either as sodiummore » phosphate or sodium fluoride phosphate, had a negligible effect on the rate of gibbsite dissolution, but caused a slight increase in aluminum solubility. The magnitude of the increased solubility, relative to the increase caused by sodium nitrate, suggests that the increase is due to ionic strength (or water activity) effects, rather than being associated with the specific ion involved. The computer model predicted that phosphate would cause a slight decrease in aluminum solubility, suggesting some Al-PO4 interaction. No evidence was found of such an interaction.« less

Phosphate Treatment of Lead-Contaminated Soil: Effects on ...

EPA Pesticide Factsheets

Water quality threats associated with using phosphate-based amendments to remediate Pb-contaminated soils are a concern, particularly in riparian areas. This study investigated the effects of P application rates to a Pb-contaminated alluvial soil on Pb and P loss via surface water runoff, Pb accumulation in tall fescue (Festuca arundinacea Schreb; Kentucky 31), and Pb speciation. An alluvial soil was treated with triple superphosphate at P to Pb molar ratios of 0:1(control), 4:1, 8:1, and 16:1. After a 6- mo reaction period, rainfall simulation (RFS) studies were conducted, followed by tall fescue establishment and a second set of RFS studies (1 yr after treatment). Results from the first RFS (unvegetated) demonstrated that the total Pb and P concentrations in the effluents of 8:1 and 16:1 (P:Pb molar ratio) treatment levels were significantly greater (p 55%. X-ray absorption near-edge structure spectroscopy data showed that pyromorphite [Pb5(PO4)3OH,Cl,F] abundance ranged from 0% (control) to 32% (16:1 P:Pb; 1 yr after treatment) of the total soil Pb. Although P treatment stimulated pyromorphite formation, pyromorphite abundance was comparable between the P-treated soils. These findings suggest that a 4:1 (P:Pb molar ratio) P treatment may be a sufficient means of reducing Pb bioavailability while minimizing concerns related to P loss in an alluvial setting. The purpose of the current research was to examine the feasability of using phosphate based ammend

Degradation processes of reinforced concretes by combined sulfate–phosphate attack

DOE Office of Scientific and Technical Information (OSTI.GOV)

Secco, Michele, E-mail: michele.secco@unipd.it; Department of Civil, Environmental and Architectural Engineering; Lampronti, Giulio Isacco, E-mail: gil21@cam.ac.uk

2015-02-15

A novel form of alteration due to the interaction between hydrated cement phases and sulfate and phosphate-based pollutants is described, through the characterization of concrete samples from an industrial reinforced concrete building. Decalcification of the cement matrices was observed, with secondary sulfate and phosphate-based mineral formation, according to a marked mineralogical and textural zoning. Five alteration layers may be detected: the two outermost layers are characterized by the presence of gypsum–brushite solid solution phases associated with anhydrous calcium sulfates and phosphates, respectively, while a progressive increase in apatite and ammonium magnesium phosphates is observable in the three innermost layers, associatedmore » with specific apatite precursors (brushite, octacalcium phosphate and amorphous calcium phosphate, respectively). The heterogeneous microstructural development of secondary phases is related to the chemical, pH and thermal gradients in the attacked cementitious systems, caused by different sources of pollutants and the exposure to the sun's radiation.« less

DFT based vibrational spectroscopic investigations and biological activity of toxic material monocrotophos

NASA Astrophysics Data System (ADS)

Nimmi, D. E.; Sam, S. P. Chandhini; Praveen, S. G.; Binoy, J.

2018-05-01

Many organophosphate compounds exhibiting toxicity are widely used as pesticides and insecticides whose structural features can be explained excellently using geometric simulation using density functional theory and vibrational spectrum. In this work, the molecular structural parameters and vibrational frequencies of the fundamental modes of Monocrotophoshave been obtained using Density functional theory (DFT), using B3LYP functional with 6-311++G(d, p) basis sets and the detailed vibrational analysis of FT-IR and FT-Ramanspectral bands have been carried out using potential energy distribution (PED). The deviation from the resonance structure of phosphate group due to `bridging of oxygen' and π-resonance of amides has been investigated based on the spectral and geometric data. The molecular docking simulation of Monocrotophos with BSA and DNA has been performed to find the mode of binding and the interactions with BSA has been investigated with UV-Visible spectroscopic method, to assess the strength of binding.

Thermal properties and surface reactivity in simulated body fluid of new strontium ion-containing phosphate glasses.

PubMed

Massera, J; Petit, L; Cardinal, T; Videau, J J; Hupa, M; Hupa, L

2013-06-01

In this paper, we investigate the effect of SrO substitution for CaO in 50P₂O₅-10Na₂-(40-x)CaO-xSrO glass system (x from 0 to 40) on the thermal and structural properties and also on the glass reactivity in simulated body fluid (SBF) in order to find new glass candidates for biomedical glass fibers. The addition of SrO at the expense of CaO seems to restrain the leaching of phosphate ions in the solution limiting the reduction of the solution pH. We observed the formation of an apatite layer at the surface of the glasses when in contact with SBF. SrO and MgO were found in the apatite layer of the strontium ion-containing glasses, the concentration of which increases with an increase of SrO content. We think that it is the presence of MgO and SrO in the layer which limits the leaching of phosphate in the solution and thus the glass dissolution in SBF.

Dual Mechanism of Ion Permeation through VDAC Revealed with Inorganic Phosphate Ions and Phosphate Metabolites

PubMed Central

Krammer, Eva-Maria; Vu, Giang Thi; Homblé, Fabrice; Prévost, Martine

2015-01-01

In the exchange of metabolites and ions between the mitochondrion and the cytosol, the voltage-dependent anion channel (VDAC) is a key element, as it forms the major transport pathway for these compounds through the mitochondrial outer membrane. Numerous experimental studies have promoted the idea that VDAC acts as a regulator of essential mitochondrial functions. In this study, using a combination of molecular dynamics simulations, free-energy calculations, and electrophysiological measurements, we investigated the transport of ions through VDAC, with a focus on phosphate ions and metabolites. We showed that selectivity of VDAC towards small anions including monovalent phosphates arises from short-lived interactions with positively charged residues scattered throughout the pore. In dramatic contrast, permeation of divalent phosphate ions and phosphate metabolites (AMP and ATP) involves binding sites along a specific translocation pathway. This permeation mechanism offers an explanation for the decrease in VDAC conductance measured in the presence of ATP or AMP at physiological salt concentration. The binding sites occur at similar locations for the divalent phosphate ions, AMP and ATP, and contain identical basic residues. ATP features a marked affinity for a central region of the pore lined by two lysines and one arginine of the N-terminal helix. This cluster of residues together with a few other basic amino acids forms a “charged brush” which facilitates the passage of the anionic metabolites through the pore. All of this reveals that VDAC controls the transport of the inorganic phosphates and phosphate metabolites studied here through two different mechanisms. PMID:25860993

Chemical changes in DMP1-null murine bone & silica based pecvd coatings for titanium implant osseoapplications

NASA Astrophysics Data System (ADS)

Maginot, Megen

In order to improve clinical outcomes in bone-implant systems, a thorough understanding of both local bone chemistry and implant surface chemistry is necessary. This study consists, therefore, of two main parts: one focused on determining the nature of the changes in bone chemistry in a DMP1-null transgenic disease model and the other on the development of amorphous silica-based coatings for potential use as titanium bone implant coatings. For the study of bone mineral in the DMP1 transgenic model, which is known to have low serum phosphate levels, transgenic DMP1-null and wild type mice were fed a high phosphate diet, sacrificed, and had their long bone harvested. This bone was characterized using SEM, FTIR, microCT and XANES and compared to DMP1-null and wild type control groups to assess the therapeutic effect of high Pi levels on the phenotype and the role of DMP1 in mineralization in vivo. Findings suggest that though the high phosphate diet results in restoring serum phosphate levels, it does not completely rescue the bone mineral phenotype at an ultrastructural level and implicates DMP1 in phosphate nucleation. Since plasma enhanced chemical vapor deposition (PECVD) silica like coatings have not previously been fabricated for use in oessoapplications, the second part of this study initially focused on the characterization of novel SiOx chemistries fabricated via a chemical vapor deposition process that were designed specifically to act as bioactive coatings with a loose, hydrogenated structure. These coatings were then investigated for their potential initial stage response to bone tissue through immersion in a simulated body fluid and through the culture of MC3T3 cells on the coating surfaces. Coating surfaces were characterized by SEM, FTIR, contact angle measurements, and XANES. Coating dissolution and ionic release were also investigated by ICP-OES. Findings suggest that some SiOx chemistries may form a bioactive coating while more highly substituted chemistries may form a bioresorbable coating, similar to commercially available bioactive glasses.

Impact of the uranium (VI) speciation in mineralised urines on its extraction by calix[6]arene bearing hydroxamic groups used in chromatography columns.

PubMed

Baghdadi, S; Bouvier-Capely, C; Ritt, A; Peroux, A; Fevrier, L; Rebiere, F; Agarande, M; Cote, G

2015-11-01

Actinides determination in urine samples is part of the analyses performed to monitor internal contamination in case of an accident or a terrorist attack involving nuclear matter. Mineralisation is the first step of any of these analyses. It aims at reducing the sample volume and at destroying all organic compounds present. The mineralisation protocol is usually based on a wet ashing step, followed by actinides co-precipitation and a furnace ashing step, before redissolution and the quantification of the actinides by the appropriate techniques. Amongst the existing methods to perform the actinides co-precipitation, alkali-earth (typically calcium) precipitation is widely used. In the present work, the extraction of uranium(VI), plutonium(IV) and americium(III) from the redissolution solutions (called "mineralised urines") on calix[6]arene columns bearing hydroxamic groups was investigated as such an extraction is a necessary step before their determination by ICP-MS or alpha spectrometry. Difficulties were encountered in the transfer of uranium(VI) from raw to mineralised urines, with yield of transfer ranging between 0% and 85%, compared to about 90% for Pu and Am, depending on the starting raw urines. To understand the origin of such a difficulty, the speciation of uranium (VI) in mineralised urines was investigated by computer simulation using the MEDUSA software and the associated HYDRA database, compiled with recently published data. These calculations showed that the presence of phosphates in the "mineralised urines" leads to the formation of strong uranyl-phosphate complexes (such as UO2HPO4) which compete with the uranium (VI) extraction by the calix[6]arene bearing hydroxamic groups. The extraction constant of uranium (VI) by calix[6]arene bearing hydroxamic groups was determined in a 0.04 mol L(-1) sodium nitrate solution (logK=4.86±0.03) and implemented in an extraction model taking into account the speciation in the aqueous phase. This model allowed to simulate satisfactorily the experimental uranium extraction data and to support the preliminary conclusions about the role of the phosphates present in mineralised urines. These calculations also showed that the phosphate/calcium ratio is a key parameter as far as the efficiency of the uranium (VI) extraction by the calix[6]arene columns is concerned. It predicted that the addition of CaCl2 in mineralised urines would release uranium (VI) from phosphates by forming calcium (II)-phosphate complexes and thus facilitate the uranium (VI) extraction on calix[6]arene columns. These predictions were confirmed experimentally as the addition of 0.1 mol L(-1) CaCl2 to a mineralised urine containing naturally a high concentration of phosphate (typically 0.04 mol L(-1)) significantly increased the percentage of uranium (VI) extraction on the calix[6]arene columns. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of phosphates on microstructure and bioactivity of micro-arc oxidized calcium phosphate coatings on Mg-Zn-Zr magnesium alloy.

PubMed

Pan, Y K; Chen, C Z; Wang, D G; Zhao, T G

2013-09-01

Calcium phosphate (CaP) coatings were prepared on Mg-Zn-Zr magnesium alloy by micro-arc oxidation (MAO) in electrolyte containing calcium acetate monohydrate (CH3COO)2Ca·H2O) and different phosphates (i.e. disodium hydrogen phosphate dodecahydrate (Na2HPO4·12H2O), sodium phosphate (Na3PO4·H2O) and sodium hexametaphosphate((NaPO3)6)). Scanning electron microscope (SEM), energy-dispersive X-ray spectrometry (EDS) and X-ray diffractometer (XRD) were employed to characterize the microstructure, elemental distribution and phase composition of the CaP coatings. Simulated body fluid (SBF) immersion test was used to evaluate the coating bioactivity and degradability. Systemic toxicity test was used to evaluate the coating biocompatibility. Fluoride ion selective electrode (ISE) was used to measure F(-) ions concentration during 30 days SBF immersion. The CaP coatings effectively reduced the corrosion rate and the surfaces of CaP coatings were covered by a new layer formed of numerous needle-like and scale-like apatites. The formation of these calcium phosphate apatites indicates that the coatings have excellent bioactivity. The coatings formed in (NaPO3)6-containging electrolyte exhibit thicker thickness, higher adhesive strength, slower degradation rate, better apatite-inducing ability and biocompatibility. Copyright © 2013 Elsevier B.V. All rights reserved.

Construction material

DOEpatents

Wagh, Arun S [Orland Park, IL; Antink, Allison L [Bolingbrook, IL

2008-07-22

A structural material of a polystyrene base and the reaction product of the polystyrene base and a solid phosphate ceramic is applied as a slurry which includes one or more of a metal oxide or a metal hydroxide with a source of phosphate to produce a phosphate ceramic and a poly (acrylic acid or acrylate) or combinations or salts thereof and polystyrene or MgO applied to the polystyrene base and allowed to cure so that the dried aqueous slurry chemically bonds to the polystyrene base. A method is also disclosed of applying the slurry to the polystyrene base.

The comparison of phosphate-titanate-silicate layers on the titanium and Ti6Al4V alloy base.

PubMed

Rokita, M

2011-08-15

The studied layers were composed of two parts: titanate-silicate underlayer for better adhesion and titanate-phosphate-silicate layers for potential bioparameters. The layers with different amounts of hydroxyapatite were deposited on titanium and Ti6Al4V alloy substrates using dipping sol-gel method and electrophoresis. The selection of sol/suspension composition, deposition time and heat treatment conditions have the decisive influence on the layers parameters. The obtained layers should be very thin and almost amorphous. The specific nature of ceramic layers on the metal substrates excludes the use of some measurements methods or makes it difficult to interpret the measurement results. All the obtained samples were compared using XRD analysis data (GID technique), SEM with EDX measurements and FTIR spectroscopy (transmission and reflection techniques) before and after soaking in simulated body fluid. FTIR spectroscopy with mathematical treatment of the spectra (BIO-RAD Win-IR program, Arithmetic-subtract function) was used to detect the increase or decrease of any phosphate phases during SBF soaking. Based on the FTIR results the processes of hydroxyapatite (HAp) growth or layer dissolution were estimated. The layers deposited on titanium substrate are more crystalline then the ones deposited on Ti6Al4V. During SBF soaking process the growth of small amount of microcrystalline carbonate hydroxyapatite was observed on titanium substrate. The layer on Ti6Al4V base contained amorphous carbonate apatite. During heating treatment above about 870-920 K this apatite transforms into carbonate hydroxyapatite. The Ti6Al4V substrate seems to be more advantageous in context of potentially bioactive materials obtaining. Copyright © 2010 Elsevier B.V. All rights reserved.

The comparison of phosphate-titanate-silicate layers on the titanium and Ti6Al4V alloy base

NASA Astrophysics Data System (ADS)

Rokita, M.

2011-08-01

The studied layers were composed of two parts: titanate-silicate underlayer for better adhesion and titanate-phosphate-silicate layers for potential bioparameters. The layers with different amounts of hydroxyapatite were deposited on titanium and Ti6Al4V alloy substrates using dipping sol-gel method and electrophoresis. The selection of sol/suspension composition, deposition time and heat treatment conditions have the decisive influence on the layers parameters. The obtained layers should be very thin and almost amorphous. The specific nature of ceramic layers on the metal substrates excludes the use of some measurements methods or makes it difficult to interpret the measurement results. All the obtained samples were compared using XRD analysis data (GID technique), SEM with EDX measurements and FTIR spectroscopy (transmission and reflection techniques) before and after soaking in simulated body fluid. FTIR spectroscopy with mathematical treatment of the spectra (BIO-RAD Win-IR program, Arithmetic-subtract function) was used to detect the increase or decrease of any phosphate phases during SBF soaking. Based on the FTIR results the processes of hydroxyapatite (HAp) growth or layer dissolution were estimated. The layers deposited on titanium substrate are more crystalline then the ones deposited on Ti6Al4V. During SBF soaking process the growth of small amount of microcrystalline carbonate hydroxyapatite was observed on titanium substrate. The layer on Ti6Al4V base contained amorphous carbonate apatite. During heating treatment above about 870-920 K this apatite transforms into carbonate hydroxyapatite. The Ti6Al4V substrate seems to be more advantageous in context of potentially bioactive materials obtaining.

Microwave assisted coating of bioactive amorphous magnesium phosphate (AMP) on polyetheretherketone (PEEK).

PubMed

Ren, Yufu; Sikder, Prabaha; Lin, Boren; Bhaduri, Sarit B

2018-04-01

Polyetheretherketone (PEEK) with great thermal and chemical stability, desirable mechanical properties and promising biocompatibility is being widely used as orthopedic and dental implant materials. However, the bioinert surface of PEEK can hinder direct osseointegration between the host tissue and PEEK based implants. The important signatures of this paper are as follows. First, we report for the formation of osseointegrable amorphous magnesium phosphate (AMP) coating on PEEK surface using microwave energy. Second, coatings consist of nano-sized AMP particles with a stacked thickness of 800nm. Third, coatings enhance bioactivity in-vitro and induce significantly high amount of bone-like apatite coating, when soaked in simulated body fluid (SBF). Fourth, the as-deposited AMP coatings present no cytotoxicity effects and are beneficial for cell adhesion at early stage. Finally, the high levels of expression of osteocalcin (OCN) in cells cultured on AMP coated PEEK samples indicate that AMP coatings can promote new bone formation and hence osseointegration. Copyright © 2017 Elsevier B.V. All rights reserved.

Glasses of three alkyl phosphates show a range of kinetic stabilities when prepared by physical vapor deposition

NASA Astrophysics Data System (ADS)

Beasley, M. S.; Tylinski, M.; Chua, Y. Z.; Schick, C.; Ediger, M. D.

2018-05-01

In situ AC nanocalorimetry was used to characterize vapor-deposited glasses of three phosphates with increasing lengths of alkyl side chains: trimethyl phosphate, triethyl phosphate, and tributyl phosphate. The as-deposited glasses were assessed in terms of their reversing heat capacity, onset temperature, and isothermal transformation time. Glasses with a range of kinetic stabilities were prepared, including kinetically stable glasses, as indicated by high onset temperatures and long transformation times. Trimethyl phosphate forms kinetically stable glasses, similar to many other organic molecules, while triethyl phosphate and tributyl phosphate do not. Triethyl phosphate and tributyl phosphate present the first examples of non-hydrogen bonding systems that are unable to form stable glasses via vapor deposition at 0.2 nm/s. Based on experiments utilizing different deposition rates, we conclude that triethyl phosphate and tributyl phosphate lack the surface mobility required for stable glass formation. This may be related to their high enthalpies of vaporization and the internal structure of the liquid state.

Advances in quantum simulations of ATPase catalysis in the myosin motor.

PubMed

Kiani, Farooq Ahmad; Fischer, Stefan

2015-04-01

During its contraction cycle, the myosin motor catalyzes the hydrolysis of ATP. Several combined quantum/classical mechanics (QM/MM) studies of this step have been published, which substantially contributed to our thinking about the catalytic mechanism. The methodological difficulties encountered over the years in the simulation of this complex reaction are now understood: (a) Polarization of the protein peptide groups surrounding the highly charged ATP(4-) cannot be neglected. (b) Some unsuspected protein groups need to be treated QM. (c) Interactions with the γ-phosphate versus the β-phosphate favor a concurrent versus a sequential mechanism, respectively. Thus, these practical aspects strongly influence the computed mechanism, and should be considered when studying other catalyzed phosphor-ester hydrolysis reactions, such as in ATPases or GTPases. Copyright © 2015 Elsevier Ltd. All rights reserved.

Long-term behaviors of phosphate-based rapid repairing material for concrete shafts in coal mines.

PubMed

Lei, Feng; Zhen-Ya, Zhang; Xiao-Dong, Wen; Chao, Xin; Dong-Yuan, Hu

2018-04-01

Concrete structures in shaft linings are apt to deteriorate prematurely and therefore prompt restoration is required. In considering this, desulphurization fly ash and machine-made tuff sand are employed to fabricate a phosphate-based rapid repairing material. The long-term efficiency of the material is evaluated based on combined factors, so drying shrinkage, interfacial bonding strength, corrosion resistance, and combustibility of the specimens are tested and researched in this paper. Experimental results showed that, under a dry circumstance, the material goes through a minor expansion at an early stage. It goes into a stage of rapid contraction after one day and a stable contraction after seven days. After 28 days, the total deformation is 67 micro-strains. On the other hand, the fabricated material manifests an excellent mechanical property. The one hour bending strength and compressive strength were 9.2 MPa and 32.6 MPa, respectively. A long-term mine water flushing simulation demonstrates that only 10% bending strength is lost and the corrosion resistance coefficient stays above 0.8, so a very good corrosion resistance is thus achieved. What is more, this repairing material retains its stability even at a high temperature of 1000°C, revealing its good thermo-stability. All these prominent properties make it a good prospective material for real restoration applications.

The international phosphate resource data base; development and maintenance

USGS Publications Warehouse

Bridges, Nancy J.

1983-01-01

The IPRDB (International Phosphate Resource Data Base) was developed to provide a single computerized source of geologic information about phosphate deposits worldwide. It is expected that this data base will encourage more thorough scientific analyses of phosphate deposits and assessments of undiscovered phosphate resources, and that methods of data collection and storage will be streamlined. Because the database was intended to serve as a repository for diverse and detailed data, a large amount of the early research effort was devoted to the design and development of the system. To date (1982), the file remains incomplete. All development work and file maintenance work on IPRDB was suspended as of October 1, 1982; this paper is intended to document the steps taken up to that date. The computer programs listed in the appendices were written specifically for the IPRDB phosbib file and are of limited future use.

RNA polymerase II trigger loop residues stabilize and position the incoming nucleotide triphosphate in transcription

PubMed Central

Huang, Xuhui; Wang, Dong; Weiss, Dahlia R.; Bushnell, David A.; Kornberg, Roger D.; Levitt, Michael

2010-01-01

A structurally conserved element, the trigger loop, has been suggested to play a key role in substrate selection and catalysis of RNA polymerase II (pol II) transcription elongation. Recently resolved X-ray structures showed that the trigger loop forms direct interactions with the β-phosphate and base of the matched nucleotide triphosphate (NTP) through residues His1085 and Leu1081, respectively. In order to understand the role of these two critical residues in stabilizing active site conformation in the dynamic complex, we performed all-atom molecular dynamics simulations of the wild-type pol II elongation complex and its mutants in explicit solvent. In the wild-type complex, we found that the trigger loop is stabilized in the “closed” conformation, and His1085 forms a stable interaction with the NTP. Simulations of point mutations of His1085 are shown to affect this interaction; simulations of alternative protonation states, which are inaccessible through experiment, indicate that only the protonated form is able to stabilize the His1085-NTP interaction. Another trigger loop residue, Leu1081, stabilizes the incoming nucleotide position through interaction with the nucleotide base. Our simulations of this Leu mutant suggest a three-component mechanism for correctly positioning the incoming NTP in which (i) hydrophobic contact through Leu1081, (ii) base stacking, and (iii) base pairing work together to minimize the motion of the incoming NTP base. These results complement experimental observations and provide insight into the role of the trigger loop on transcription fidelity. PMID:20798057

Construction Material And Method

DOEpatents

Wagh, Arun S.; Antink, Allison L.

2006-02-21

A structural material of a polystyrene base and the reaction product of the polystyrene base and a solid phosphate ceramic. The ceramic is applied as a slurry which includes one or more of a metal oxide or a metal hydroxide with a source of phosphate to produce a phosphate ceramic and a poly (acrylic acid or acrylate) or combinations or salts thereof and polystyrene or MgO applied to the polystyrene base and allowed to cure so that the dried aqueous slurry chemically bonds to the polystyrene base. A method is also disclosed of applying the slurry to the polystyrene base.

Method of binding structural material

DOEpatents

Wagh, Arun S.; Antink, Allison L.

2007-12-25

A structural material of a polystyrene base and the reaction product of the polystyrene base and a solid phosphate ceramic. The ceramic is applied as a slurry which includes one or more of a metal oxide or a metal hydroxide with a source of phosphate to produce a phosphate ceramic and a poly (acrylic acid or acrylate) or combinations or salts thereof and polystyrene or MgO applied to the polystyrene base and allowed to cure so that the dried aqueous slurry chemically bonds to the polystyrene base. A method is also disclosed of applying the slurry to the polystyrene base.

Effect of surface treatment on the corrosion properties of magnesium-based fibre metal laminate

NASA Astrophysics Data System (ADS)

Zhang, X.; Zhang, Y.; Ma, Q. Y.; Dai, Y.; Hu, F. P.; Wei, G. B.; Xu, T. C.; Zeng, Q. W.; Wang, S. Z.; Xie, W. D.

2017-02-01

The surface roughness, weight of phosphating film and wettability of magnesium alloy substrates after abrasion and phosphating treatment were investigated in this work. The interfacial bonding and corrosion properties of a magnesium-based fibre metal laminate (MgFML) were analysed. The results showed that the wettability of the magnesium alloy was greatly influenced by the surface roughness, and the rough surface possessed a larger surface energy and better wettability. The surface energy and wettability of the magnesium alloy were significantly improved by the phosphating treatment. After phosphating for 5 min, a phosphating film with a double-layer structure was formed on the magnesium substrate, and the weight of the phosphating film and the surface energy reached their maximum values. The surface energies of the phosphated substrate after abrasion with #120 and #3000 grit abrasive papers were 84.31 mJ/m2 and 83.65 mJ/m2, respectively. The wettability of the phosphated magnesium was significantly better than the abraded magnesium. The phosphated AZ31B sheet had a better corrosion resistance than the abraded AZ31B sheet within short times. The corrosion resistance of the magnesium alloy was greatly increased by being composited with glass fibre/epoxy prepregs.

The effect of Sinabung volcanic ash and rock phosphate nanoparticle on CEC (cation exchange capacity) base saturation exchange (K, Na, Ca, Mg) and base saturation at Andisol soils Ciater, West Java

NASA Astrophysics Data System (ADS)

Yuniarti, Anni; Arifin, Mahfud; Sofyan, Emma Trinurasi; Natalie, Betty; Sudirja, Rija; Dahliani, Dewi

2018-02-01

Andisol, soil orders which covers an upland area dominantly. The aim of this research is to know the effect between the ameliorant of Sinabung volcanic ashes with the ameliorant of rock phosphatenanoparticle towards CEC and base saturation exchange (K, Na, Ca, Mg) and the base saturation on Ciater's Andisols, West Java. A randomized complete block design (RCBD) factorial with two factors was used in this research. The first factor is the volcanic ash and the second factor is rock phosphate which consists of four levels each amount of 0%, 2.5%, 5%, 7.5% with three replications. The result showed that there was no interaction between volcanic ash and rock phosphate nanoparticle formed in first month and fourth month towards the improvement of CEC and saturation base exchange rate unless magnesium cation exchange increased in fourth month. There was independent effect of volcanic ash formed nanoparticles towards base saturation exchange increased for 5% dose. There was independent effect of rock phosphate formed nanoparticles towards base saturation exchange and increased for 5% dose. The dose combination of volcanic ashes 7.5% with phosphate rock, 5% increased the base saturation in the first month incubation.

Effect of simulated ambient particulate matter exposure on performance, rectal temperature, and leukocytosis of young Spanish goats with or without tilmicosin phosphate.

PubMed

Chirase, N K; Purdy, C W; Avampato, J M

2004-04-01

Dust is an environmental stressor and can become extensive in agricultural production systems. Thirty-six female, Spanish goats (average BW 21.1 kg, SEM = 1.31; age = 4 mo) were randomly assigned to simulated dust events or no dust, with or without tilmicosin phosphate treatment in a 2 x 2 factorial arrangement of treatments to determine effects on performance, rectal temperature, and leukocyte changes. All goats were fed a standard growing diet (13.6% CP) consisting of 37% roughage and 63% concentrate (DM basis). Feed intake was measured daily, and BW (unshrunk) measured individually every 7 d. The tilmicosin-treated group received tilmicosin phosphate (10 mg/kg BW s.c.) before starting the study. Goats exposed to dust were enclosed as a group inside a canvass tent for 4 h each day and ground feed yard manure dust (mean particle size 100 microm) was aerosolized inside the tent to simulate a dust event. There was one single dust event (Phase I) followed by rectal temperature measurement, and heparinized blood collection for complete cell counts at 0 (pretrial), 4, 12, 20, 44, 68, and 210 h after dust exposure. This was followed by 21 d of chronic dust events (Phase II). The sampling procedures for Phase II were exactly the same as in Phase I, except that samples were obtained daily at 0 (before dust application), 4, 8, and 12 h after each dust event. Dust treatment had no effect (P > 0.05) on feed intake or ADG, but the gain:feed (G:F) ratio was lower (P < 0.05) in the control goats than the dust exposed group. Tilmicosin phosphate-treated goats had a higher (P < 0.05) G:F ratio than untreated goats. Dust exposure increased (P < 0.002), but tilmicosin treatment decreased (P < 0.05) rectal temperature at 4 and 8 h. Dust exposure increased (P < 0.02) blood lymphocyte counts compared with controls. These results suggest that simulated dust events altered rectal temperature and leukocyte counts of goats.

Possible Phosphate Redistribution on the Martian Surface: Implication From Simulation Experiments

NASA Astrophysics Data System (ADS)

Dreibus, G.; Haubold, R.; Jagoutz, E.

2001-12-01

The chemical composition of Martian rocks and soils as measured with the APXS (Alpha Proton X-ray Spectrometer) of the Mars Pathfinder Mission are very different [1]. Surprisingly, only small differences of the phosphorous concentrations between soils and rocks were found. The P concentration of about 4000 ppm is similar to that measured in basaltic shergottites. Phosphates are the host mineral for the REE, Th and U. Leach experiments with slightly acidified brines on basaltic shergottites easily dissolved more than a half of the REEs and U whereas K remained insoluble. Therefore, we suggested the possibility of alteration and mobilization of phosphates in the Martian environment with the result of an enrichment of U, Th, and consequently P on the surface. However, the APXS measured no P enrichment in rocks and soil of the Martian crust, whereas a high Th concentration on the surface was measured with the gamma-spectroscopy from orbit by Mars-5 and Phobos-2 [2]. With leach experiments on terrestrial samples we studied the solubility of U and Th as in the case of shergottites, but also that of phosphorous. Furthermore, simulation experiments of reactions between slightly acidified calcium-phosphate solution and different terrestrial rock types were performed to clarify the redistribution of P at the Martian surface with its complex weathering history. Ref.: [1] Brueckner J. et al. (2001) Lunar Planet. Science. XXXII, 1293; [2] Surkov Yu. A. et al. (1989) Nature 341, 595.

[Effects of simulated body fluid flowing rate on bone-like apatite formation on porous calcium phosphate ceramics].

PubMed

Duan, You-rong; Liu, Ke-wei; Chen, Ji-yong; Zhang, Xing-dong

2002-06-01

Objective. Bone-like apatite formation on the surface of calcium phosphate ceramics was believed to be the necessary step that new bone grows on the ceramics and to be relative to the osteoinductivity of the material. This study aimed at investigating the influence of the flow rate of simulated body fluid (SBF) (2 ml/min) in skeletal muscle upon the formation of bone-like apatite on porous calcium phosphate ceramics. Method. The dynamic condition was realized by controlling the SBF flowing in/out of the sample chamber of 100 ml. The flow rate of 2 ml/min is close to that in human muscle environment. The pH and inorganic ionic composition of SBF are close to those of human body fluid. Result. Bone-like apatite formation was relatively easier to occur in static SBF than in dynamic SBF. Experiment with flowing SBF (dynamic SBF) is better in mimicking the living body fluid than static SBF. Conclusion. The results from dynamic SBF may more truly show the relation between apatite layer formation and osteoinduction in biomaterials than that from in vitro experiments before.

Mechanical properties of calcium phosphate scaffolds fabricated by robocasting.

PubMed

Miranda, Pedro; Pajares, Antonia; Saiz, Eduardo; Tomsia, Antoni P; Guiberteau, Fernando

2008-04-01

The mechanical behavior under compressive stresses of beta-tricalcium phosphate (beta-TCP) and hydroxyapatite (HA) scaffolds fabricated by direct-write assembly (robocasting) technique is analyzed. Concentrated colloidal inks prepared from beta-TCP and HA commercial powders were used to fabricate porous structures consisting of a 3-D tetragonal mesh of interpenetrating ceramic rods. The compressive strength and elastic modulus of these model scaffolds were determined by uniaxial testing to compare the relative performance of the selected materials. The effect of a 3-week immersion in simulated body fluid (SBF) on the strength of the scaffolds was also analyzed. The results are compared with those reported in the literature for calcium phosphate scaffolds and human bone. The robocast calcium phosphate scaffolds were found to exhibit excellent mechanical performances in terms of strength, especially the HA structures after SBF immersion, indicating a great potential of this type of scaffolds for use in load-bearing bone tissue engineering applications. Copyright 2007 Wiley Periodicals, Inc.

Dutch dairy farms after milk quota abolition: Economic and environmental consequences of a new manure policy.

PubMed

Klootwijk, C W; Van Middelaar, C E; Berentsen, P B M; de Boer, I J M

2016-10-01

The abolition of the Dutch milk quota system has been accompanied by the introduction of a new manure policy to limit phosphate production (i.e., excretion via manure) on expanding dairy farms. The objective of this study was to evaluate the effect of these recent policy changes on the farm structure, management, labor income, nitrogen and phosphate surpluses, and greenhouse gas emissions of an average Dutch dairy farm. The new manure policy requires that any increase in phosphate production be partly processed and partly applied to additional farmland. In addition, phosphate quotas have been introduced. Herein, we used a whole-farm optimization model to simulate an average farm before and after quota abolition and introduction of the new manure policy. The objective function of the model maximized labor income. We combined the model with a farm nutrient balance and life-cycle assessment to determine environmental impact. Based on current prices, increasing the number of cows after quota abolition was profitable until manure processing or additional land was required to comply with the new manure policy. Manure processing involved treatment so that phosphate was removed from the national manure market. Farm intensity in terms of milk per hectare increased by about 4%, from 13,578kg before quota abolition to 14,130kg after quota abolition. Labor income increased by €505/yr. When costs of manure processing decreased from €13 to €8/t of manure or land costs decreased from €1,187 to €573/ha, farm intensity could increase up to 20% until the phosphate quota became limiting. Farms that had already increased their barn capacity to prepare for expansion after milk quota abolition could benefit from purchasing extra phosphate quota to use their full barn capacity. If milk prices increased from €355 to €420/t, farms could grow unlimited, provided that the availability of external inputs such as labor, land, barn capacity, feed, and phosphate quota at current prices were also unlimited. The milk quota abolition, accompanied by a new manure policy, will slightly increase nutrient losses per hectare, due to an increase in farm intensity. Greenhouse gas emissions per unit of milk will hardly change, so at a given milk production per cow, total greenhouse gas emissions will increase linearly with an increase in the number of cows. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Preferable removal of phosphate from water using hydrous zirconium oxide-based nanocomposite of high stability.

PubMed

Chen, Liang; Zhao, Xin; Pan, Bingcai; Zhang, Weixian; Hua, Ming; Lv, Lu; Zhang, Weiming

2015-03-02

In this study, we employed a new nanocomposite adsorbent HZO-201, which featured high stability under varying solution chemistry, for preferable removal of phosphate from synthetic solution and a real effluent. An anion exchange resin (D-201) was employed as the host of HZO-201, where nano-hydrous zirconium oxide (HZO) was encapsulated as the active species. D-201 binds phosphate through nonspecific electrostatic affinity, whereas the loaded HZO nanoparticles capture phosphate through formation of the inner-sphere complexes. Quantitative contribution of both species to phosphate adsorption was predicted based on the double-Langmuir model. Preferable removal of phosphate by HZO-201 was observed in the presence of the competing anions at higher levels (Cl(-), NO3(-), SO4(2-), HCO3(-)). Fixed-bed adsorption indicated that the effective volume capacity of a synthetic water (2.0 mg P-PO4(3-)/L) by using HZO-201 was ∼1600 BV in the first run (<0.5mg P-PO4(3-)/L), comparable to Fe(III)-based nanocomposite HFO-201 (∼1500 BV) and much larger than D-201 (<250 BV). The exhausted HZO-201 can be in situ regenerated by using a binary NaOH-NaCl solution for cyclic runs, whether fed with the synthetic solution or real effluent. In general, HZO-201 is a promising alternative to Fe(III)-based adsorbents for trace phosphate removal from effluent particularly at acidic pH. Copyright © 2014 Elsevier B.V. All rights reserved.

In vitro investigation of biodegradable polymeric coating for corrosion resistance of Mg-6Zn-Ca alloy in simulated body fluid.

PubMed

Gaur, Swati; Singh Raman, R K; Khanna, A S

2014-09-01

A silane-based biodegradable coating was developed and investigated to improve corrosion resistance of an Mg-6Zn-Ca magnesium alloy to delay the biodegradation of the alloy in the physiological environment. Conditions were optimized to develop a stable and uniform hydroxide layer on the alloys surface-known to facilitate silane-substrate adhesion. A composite coating of two silanes, namely, diethylphosphatoethyltriethoxysilane (DEPETES) and bis-[3-(triethoxysilyl) propyl] tetrasulfide (BTESPT), was developed, by the sol-gel route. Corrosion resistance of the coated alloy was characterized in a modified-simulated body fluid (m-SBF), using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The silane coating provided significant and durable corrosion resistance. During the course of this, hydrogen evolution and pH variation, if any, were monitored for both bare and coated alloys. The coating morphology was characterized using scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) and the cross-linking in the coating was studied using Fourier transform infrared spectroscopy (FTIR). As indicated by X-ray diffraction (XRD) results, an important finding was the presence of hydrated magnesium phosphate on the sample that was subjected to immersion in m-SBF for 216h. Magnesium phosphate is reported to support osteoblast formation and tissue healing. Copyright © 2014 Elsevier B.V. All rights reserved.

Phosphate Reduction in Emulsified Meat Products: Impact of Phosphate Type and Dosage on Quality Characteristics.

PubMed

Glorieux, Seline; Goemaere, Olivier; Steen, Liselot; Fraeye, Ilse

2017-09-01

Phosphate reduction is of important industrial relevance in the manufacturing of emulsified meat products because it may give rise to a healthier product. The effect of seven different phosphate types was tested on the physicochemical and quality characteristics to select the most promising phosphate type for further cooked sausage manufacturing. Next, phosphate mass fraction was gradually reduced. Tetrasodium di- or pyrophosphate (TSPP) and sodium tripolyphosphate (STPP) increased pH, reduced structural properties, resulted in the highest emulsion stability, lowest cooking loss and had little effect on hardness. Based on the viscoelastic properties, a minimum mass fraction of 0.06% TSPP was sufficient to obtain an acceptable quality product. Rheology proved to be a very useful tool to evaluate the quality of meat products, as it gives insight in the structure of the meat product and especially the functional properties of meat proteins. Based on the obtained results, it can be concluded that the current amount of phosphate added to emulsified meat products can be significantly reduced with minimal loss of product quality.

Phosphate Reduction in Emulsified Meat Products: Impact of Phosphate Type and Dosage on Quality Characteristics

PubMed Central

2017-01-01

Summary Phosphate reduction is of important industrial relevance in the manufacturing of emulsified meat products because it may give rise to a healthier product. The effect of seven different phosphate types was tested on the physicochemical and quality characteristics to select the most promising phosphate type for further cooked sausage manufacturing. Next, phosphate mass fraction was gradually reduced. Tetrasodium di- or pyrophosphate (TSPP) and sodium tripolyphosphate (STPP) increased pH, reduced structural properties, resulted in the highest emulsion stability, lowest cooking loss and had little effect on hardness. Based on the viscoelastic properties, a minimum mass fraction of 0.06% TSPP was sufficient to obtain an acceptable quality product. Rheology proved to be a very useful tool to evaluate the quality of meat products, as it gives insight in the structure of the meat product and especially the functional properties of meat proteins. Based on the obtained results, it can be concluded that the current amount of phosphate added to emulsified meat products can be significantly reduced with minimal loss of product quality. PMID:29089852

Lithium batteries using poly(ethylene oxide)-based non-aqueous electrolytes

DOEpatents

Chen, Zonghai; Amine, Khalil

2015-09-08

Lithium-air cells employing poly(ethyleneoxide) phosphate-based electrolytes may be prepared and exhibit improved charge carrying capacity. Such PEO phosphates generally have the formulas IIa, IIb, IIc, where: ##STR00001##

[In vitro drug release behavior of carrier made of porous glass ceramics].

PubMed

Wang, De-ping; Huang, Wen-hai; Zhou, Nai

2002-09-01

To conduct the in vitro test on drug release of rifampin encapsulated in a carrier made of porous phosphate glass ceramics and to analyze main factors which affect the drug release rate. A certain quantitative of rifampin was sealed in a hollow cylindrical capsule which consisted of chopped calcium phosphate crystal fiber obtained from glass crystallization. The rifampin concentration was measured in the simulated physiological solution in which the capsule soaked. Rifampin could be released in a constant rate from the porous glass ceramic carrier in a long time. The release rate was dependent on the size of crystal fiber and the wall thickness of the capsule. This kind of calcium phosphate glass ceramics can be a candidate of the carrier materials used as long term drug therapy after osteotomy surgery.

The impact of reduced gastric acid secretion on dissolution of salts of weak bases in the fasted upper gastrointestinal lumen: Data in biorelevant media and in human aspirates.

PubMed

Litou, Chara; Vertzoni, Maria; Xu, Wei; Kesisoglou, Filippos; Reppas, Christos

2017-06-01

To propose media for simulating the intragastric environment under reduced gastric acid secretion in the fasted state at three levels of simulation of the gastric environment and evaluate their usefulness in evaluating the intragastric dissolution of salts of weak bases. To evaluate the importance of bicarbonate buffer in biorelevant in vitro dissolution testing when using Level II biorelevant media simulating the environment in the fasted upper small intestine, regardless of gastric acid secretions. Media for simulating the hypochlorhydric and achlorhydric conditions in stomach were proposed using phosphates, maleates and bicarbonates buffers. The impact of bicarbonates in Level II biorelevant media simulating the environment in upper small intestine was evaluated so that pH and bulk buffer capacity were maintained. Dissolution data were collected using two model compounds, pioglitazone hydrochloride and semifumarate cocrystal of Compound B, and the mini-paddle dissolution apparatus in biorelevant media and in human aspirates. Simulated gastric fluids proposed in this study were in line with pH, buffer capacity, pepsin content, total bile salt/lecithin content and osmolality of the fasted stomach under partial and under complete inhibition of gastric acid secretion. Fluids simulating the conditions under partial inhibition of acid secretion were useful in simulating concentrations of both model compounds in gastric aspirates. Bicarbonates in Level III biorelevant gastric media and in Level II biorelevant media simulating the composition in the upper intestinal lumen did not improve simulation of concentrations in human aspirates. Level III biorelevant media for simulating the intragastric environment under hypochlorhydric conditions were proposed and their usefulness in the evaluation of concentrations of two model salts of weak bases in gastric aspirates was shown. Level II biorelevant media for simulating the environment in upper intestinal lumen led to underestimation of concentrations in aspirates, even when bicarbonate buffer was used. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular Docking Studies of Catechin and Its Derivatives as Anti-bacterial Inhibitor for Glucosamine-6-Phosphate Synthase

NASA Astrophysics Data System (ADS)

Fikrika, H.; Ambarsari, L.; Sumaryada, T.

2016-01-01

Molecular docking simulation of catechin and its derivatives on Glucosamine-6- Phosphate Synthase (GlmS) has been performed in this research. GlmS inhibition by a particular ligand will suppress the production of bacterial cell wall and significantly reduce the population of invading bacteria. In this study, catechin derivatives i.e epicatechin, galloatechin and epigalloatechin were found to have stronger binding affinities as compared to natural ligand of GlmS, Fructose-6-Phosphate (F6P). Those three ligands were docked on the same pocket in GlmS target as F6P, with 70% binding sites similarity. Based on the docking results, gallocatechin turns out to be the most potent ligand for anti-bacterial agent with ΔG= -8.00 kcal/mol. The docking between GlmS and catechin derivatives are characterized by a constant present of a strong hydrogen bond between functional group O3 and Ser-349. This hydrogen bond most likely plays a significant role in the docking mechanism and binding modes selection. The surprising result is catechin itself exhibited a quite strong binding with GlmS (ΔG= -7.80 kcal.mol), but docked on a completely different pocket compared to other ligands. This results suggest that catechin might still have a curing effect but with a completely different pathway and mechanism as compared to its derivatives.

Drug Release as a function of bioactivity, incubation regime, liquid, and initial load: Release of bortezomib from calcium phosphate-containing silica/collagen xerogels.

PubMed

Kruppke, Benjamin; Hose, Dirk; Schnettler, Reinhard; Seckinger, Anja; Rößler, Sina; Hanke, Thomas; Heinemann, Sascha

2018-04-01

The ability of silica-/collagen-based composite xerogels to act as drug delivery systems was evaluated by taking into account the initial drug concentration, bioactivity of the xerogels, liquid, and incubation regime. The proteasome inhibitor bortezomib was chosen as a model drug, used for the systemic treatment of multiple myeloma. Incubation during 14 days in phosphate-buffered saline (PBS) or simulated body fluid (SBF) showed a weak initial burst and was identified to be of first order with subsequent release being independent from the initial load of 0.1 or 0.2 mg bortezomib per 60 mg monolithic sample. Faster drug release occurred during incubation in SBF compared to PBS, and during static incubation without changing the liquid, compared to dynamic incubation with daily liquid changes. Drug-loaded xerogels with hydroxyapatite as a third component exhibited enhanced bioactivity retarding drug release, explained by formation of a surface calcium phosphate layer. The fastest release of 50% of the total drug load was observed for biphasic xerogels after 7 days during dynamic incubation in SBF. As a result, the presented concept is suitable for the intended combination of the advantageous bone substitution properties of xerogels and local application of drugs exemplified by bortezomib. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1165-1173, 2018. © 2017 Wiley Periodicals, Inc.

The Molecular Structure of a Phosphatidylserine Bilayer Determined by Scattering and Molecular Dynamics Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Jianjun; Cheng, Xiaolin; Monticelli, Luca

2014-01-01

Phosphatidylserine (PS) lipids play essential roles in biological processes, including enzyme activation and apoptosis. We report on the molecular structure and atomic scale interactions of a fluid bilayer composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylserine (POPS). A scattering density profile model, aided by molecular dynamics (MD) simulations, was developed to jointly refine different contrast small-angle neutron and X-ray scattering data, which yielded a lipid area of 62.7 A2 at 25 C. MD simulations with POPS lipid area constrained at different values were also performed using all-atom and aliphatic united-atom models. The optimal simulated bilayer was obtained using a model-free comparison approach. Examination of themore » simulated bilayer, which agrees best with the experimental scattering data, reveals a preferential interaction between Na+ ions and the terminal serine and phosphate moieties. Long-range inter-lipid interactions were identified, primarily between the positively charged ammonium, and the negatively charged carboxylic and phosphate oxygens. The area compressibility modulus KA of the POPS bilayer was derived by quantifying lipid area as a function of surface tension from area-constrained MD simulations. It was found that POPS bilayers possess a much larger KA than that of neutral phosphatidylcholine lipid bilayers. We propose that the unique molecular features of POPS bilayers may play an important role in certain physiological functions.« less

Determination of phosphorus fertilizer soil reactions by Raman and synchrotron infrared microspectroscopy.

PubMed

Vogel, Christian; Adam, Christian; Sekine, Ryo; Schiller, Tara; Lipiec, Ewelina; McNaughton, Don

2013-10-01

The reaction mechanisms of phosphate-bearing mineral phases from sewage sludge ash-based fertilizers in soil were determined by Raman and synchrotron infrared microspectroscopy. Different reaction mechanisms in wet soil were found for calcium and magnesium (pyro-) phosphates. Calcium orthophosphates were converted over time to hydroxyapatite. Conversely, different magnesium phosphates were transformed to trimagnesium phosphate. Since the magnesium phosphates are unable to form an apatite structure, the plant-available phosphorus remains in the soil, leading to better growth results observed in agricultural pot experiments. The pyrophosphates also reacted very differently. Calcium pyrophosphate is unreactive in soil. In contrast, magnesium pyrophosphate quickly formed plant-available dimagnesium phosphate.

Coating electrospun poly(epsilon-caprolactone) fibers with gelatin and calcium phosphate and their use as biomimetic scaffolds for bone tissue engineering.

PubMed

Li, Xiaoran; Xie, Jingwei; Yuan, Xiaoyan; Xia, Younan

2008-12-16

Electrospinning was employed to fabricate fibrous scaffolds of poly(epsilon-caprolactone) in the form of nonwoven mats. The surfaces of the fibers were then coated with gelatin through layer-by-layer self-assembly, followed by functionalization with a uniform coating of bonelike calcium phosphate by mineralization in the 10 times concentrated simulated body fluid for 2 h. Transmission electron microscopy, water contact angle, and scanning electron microscopy measurements confirmed the presence of gelatin and calcium phosphate coating layers, and X-ray diffraction results suggested that the deposited mineral phase was a mixture of dicalcium phosphate dehydrate (a precursor to apatite) and apatite. It was also demonstrated that the incorporation of gelatin promoted nucleation and growth of calcium phosphate. The porous scaffolds could mimic the structure, composition, and biological function of bone extracellular matrix. It was found that the preosteoblastic MC3T3-E1 cells attached, spread, and proliferated well with a flat morphology on the mineralized scaffolds. The proliferation rate of the cells on the mineralized scaffolds was significantly higher (by 1.9-fold) than that on the pristine fibrous scaffolds after culture for 7 days. These results indicated that the hybrid system containing poly(epsilon-caprolactone), gelatin, and calcium phosphate could serve as a new class of biomimetic scaffolds for bone tissue engineering.

Characterisation of Phosphate Accumulating Organisms and Techniques for Polyphosphate Detection: A Review

PubMed Central

Tarayre, Cédric; Nguyen, Huu-Thanh; Brognaux, Alison; Delepierre, Anissa; De Clercq, Lies; Charlier, Raphaëlle; Michels, Evi; Meers, Erik; Delvigne, Frank

2016-01-01

Phosphate minerals have long been used for the production of phosphorus-based chemicals used in many economic sectors. However, these resources are not renewable and the natural phosphate stocks are decreasing. In this context, the research of new phosphate sources has become necessary. Many types of wastes contain non-negligible phosphate concentrations, such as wastewater. In wastewater treatment plants, phosphorus is eliminated by physicochemical and/or biological techniques. In this latter case, a specific microbiota, phosphate accumulating organisms (PAOs), accumulates phosphate as polyphosphate. This molecule can be considered as an alternative phosphate source, and is directly extracted from wastewater generated by human activities. This review focuses on the techniques which can be applied to enrich and try to isolate these PAOs, and to detect the presence of polyphosphate in microbial cells. PMID:27258275

Grazing incidence synchrotron X-ray diffraction of marbles consolidated with diammonium hydrogen phosphate treatments: non-destructive probing of buried minerals

NASA Astrophysics Data System (ADS)

Possenti, Elena; Colombo, Chiara; Conti, Claudia; Gigli, Lara; Merlini, Marco; Plaisier, Jasper Rikkert; Realini, Marco; Gatta, G. Diego

2018-05-01

Diammonium hydrogen phosphate (DAP)-based consolidating treatments react with carbonatic stones and form calcium phosphates phases, whose composition depends on the availability of free calcium ions. In this work, an innovative non-destructive approach based on grazing incidence X-ray diffraction (GIXRD) with synchrotron radiation (SR) is used to investigate DAP-treated Carrara marble specimens and to study the influence of the substrate composition on the crystallization of calcium phosphate phases. The outcomes indicate that the presence of compositional micro-heterogeneity of Carrara marble favours the formation of specific phases. Dicalcium phosphate dihydrate, a calcium phosphate with a low Ca/P molar ratio, is formed on carbonatic phases with a low Ca amount, such as dolomite grains and Mg-containing veins. Furthermore, this study highlights the potentialities of SR-GIXRD as a powerful non-destructive tool for the diagnostic of Cultural Heritage objects since it allows investigating the conservation history of stone materials and their interaction with the environment.

Potential use of gallium-doped phosphate-based glass material for periodontitis treatment.

PubMed

Sahdev, Rohan; Ansari, Tahera I; Higham, Susan M; Valappil, Sabeel P

2015-07-01

This study aimed at evaluating the potential effect of gallium-incorporated phosphate-based glasses towards periodontitis-associated bacteria, Porphyromonas gingivalis, and matrix metalloproteinase-13. Periodontitis describes a group of inflammatory diseases of the gingiva and supporting structures of the periodontium. They are initiated by the accumulation of plaque bacteria, such as the putative periodontal pathogen Porphyromonas gingivalis, but the host immune response such as elevated matrix metalloproteinases are the major contributing factor for destruction of periodontal tissues. Antibacterial assays of gallium-incorporated phosphate-based glasses were conducted on Porphyromonas gingivalis ATCC 33277 using disc diffusion assay on fastidious anaerobe agar and liquid broth assay in a modified tryptic soy broth. In vitro study investigated the effect of gallium on purified recombinant human matrix metalloproteinase-13 activity using matrix metalloproteinase assay kit. In vivo biocompatibility of gallium-incorporated phosphate-based glass was evaluated in rats as subcutaneous implants. Antibacterial assay of gallium displayed activity against Porphyromonas gingivalis (inhibition zone of 22 ± 0.5 mm compared with 0 mm for control glass, c-PBG). Gallium in the glass contributed to growth inhibitory effect on Porphyromonas gingivalis (up to 1.30 reductions in log 10 values of the viable counts compared with control) in a modified tryptic soy broth. In vitro study showed gallium-incorporated phosphate-based glasses inhibited matrix metalloproteinase activity significantly (p ≤ 0.01) compared with c-PBG. Evaluation of in vivo biocompatibility of gallium-incorporated phosphate-based glasses in rats showed a non-toxic and foreign body response after 2 weeks of implantation. The results indicate that gallium ions might act on multiple targets of biological mechanisms underlying periodontal disease. Moreover, gallium-incorporated phosphate-based glasses are biocompatible in a rat model. The findings warrant further investigation and will have important clinical implications in the future treatment and management of periodontitis. © The Author(s) 2015 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Phosphate binders for the treatment of hyperphosphatemia in chronic kidney disease patients on dialysis: a comparison of safety profiles.

PubMed

Locatelli, Francesco; Del Vecchio, Lucia; Violo, Leano; Pontoriero, Giuseppe

2014-05-01

Hyperphosphatemia is common in the late stages of chronic kidney disease (CKD) and is associated with elevated parathormone levels, abnormal bone mineralization, extraosseous calcification and increased risk of cardiovascular events and death. Several classes of oral phosphate binders are available to help control phosphorus levels. Although effective at lowering serum phosphorus, they all have safety issues that need to be considered when selecting which one to use. This paper reviews the use of phosphate binders in patients with CKD on dialysis, with a focus on safety and tolerability. In addition to the more established agents, a new resin-based phosphate binder, colestilan, is discussed. Optimal phosphate control is still an unmet need in CKD. Nonetheless, we now have an extending range of phosphate binders available. Aluminium has potentially serious toxic risks. Calcium-based binders are still very useful but can lead to hypercalcemia and/or positive calcium balance and cardiovascular calcification. No long-term data are available for the new calcium acetate/magnesium combination product. Lanthanum is an effective phosphate binder, but there is insufficient evidence about possible long-term effects of tissue deposition. The resin-based binders, colestilan and sevelamer, appear to have profiles that would lead to less vascular calcification, and the main adverse events seen with these agents are gastrointestinal effects.

The interaction of zinc oxide-based dental cements with aqueous solutions of potassium fluoride.

PubMed

Pawluk, K; Booth, S E; Coleman, N J; Nicholson, J W

2008-09-01

The ability of zinc oxide-based dental cements (zinc phosphate and zinc polycarboxylate) to take up fluoride from aqueous solution has been studied. Only zinc phosphate cement was found to take up any measurable fluoride after 5 h exposure to the solutions. The zinc oxide filler of the zinc phosphate also failed to take up fluoride from solution. The key interaction for this uptake was thus shown to involve the phosphate groups of the set cement. However, whether this took the form of phosphate/fluoride exchange, or the formation of oxyfluoro-phosphate groups was not clear. Fluoride uptake followed radicaltime kinetics for about 2 h in some cases, but was generally better modelled by the Elovich equation, dq(t)/dt = alpha exp(-betaq(t)). Values for alpha varied from 3.80 to 2.48 x 10(4), and for beta from 7.19 x 10(-3) to 0.1946, though only beta showed any sort of trend, becoming smaller with increasing fluoride concentration. Fluoride was released from the zinc phosphate cements in processes that were diffusion based up to M(t)/M(infinity) of about 0.4. No further release occurred when specimens were placed in fresh volumes of deionised water. Only a fraction of the fluoride taken up was re-released, demonstrating that most of the fluoride taken up becomes irreversibly bound within the cement.

Synthesis of cytidine ribonucleotides by stepwise assembly of the heterocycle on a sugar phosphate.

PubMed

Ingar, Abdul-Aziz; Luke, Richard W A; Hayter, Barry R; Sutherland, John D

2003-06-06

Although various syntheses of the nucleic acid bases exist and ribose is a product of the formose reaction, no prebiotically plausible methods for attaching pyrimidine bases to ribose to give nucleosides have been described. Kinetic and thermodynamic factors are thought to mitigate against such condensation reactions in aqueous solution. This inability to produce pyrimidine nucleosides and hence nucleotides is a major stumbling block of the "RNA World" hypothesis and has led to suggestions of alternative nucleic acids as evolutionary precursors to RNA. Here, we show that a process in which the base is assembled in stages on a sugar phosphate can produce cytidine nucleotides. The sequential action of cyanamide and cyanoacetylene on arabinose-3-phosphate produces cytidine-2',3'-cyclophosphate and arabinocytidine-3'-phosphate.

A Novel Polymer-Synthesized Ceramic Composite Based System for Bone Repair: Osteoblast Growth on Scaffolds with Varied Calcium Phosphate Content

DTIC Science & Technology

2005-01-01

demongtrated the synthesis of degradable scaffolds from PLAGA /calcium phosphate composite microspheres in which an amorphous calcium phosphate is...EXPERIMENTAL DETAILS Scaffold Preparation Scaffolds were prepared as described in detail previously [3]. Briefly, PLAGA /calcium phosphate composite...culture polystyrene (TCPS) 2- pure PLAGA microspheres 64 3- composite microsphere matrices with a low polymer/ceramic ratio 4- composite microsphere

Molecular Dynamics Simulations of PIP2 and PIP3 in Lipid Bilayers: Determination of Ring Orientation, and the Effects of Surface Roughness on a Poisson-Boltzmann Description

PubMed Central

Li, Zheng; Venable, Richard M.; Rogers, Laura A.; Murray, Diana; Pastor, Richard W.

2009-01-01

Abstract Molecular dynamics (MD) simulations of phosphatidylinositol (4,5)-bisphosphate (PIP2) and phosphatidylinositol (3,4,5)-trisphosphate (PIP3) in 1-palmitoyl 2-oleoyl phosphatidylcholine (POPC) bilayers indicate that the inositol rings are tilted ∼40° with respect to the bilayer surface, as compared with 17° for the P-N vector of POPC. Multiple minima were obtained for the ring twist (analogous to roll for an airplane). The phosphates at position 1 of PIP2 and PIP3 are within an Ångström of the plane formed by the phosphates of POPC; lipids in the surrounding shell are depressed by 0.5–0.8 Å, but otherwise the phosphoinositides do not substantially perturb the bilayer. Finite size artifacts for ion distributions are apparent for systems of ∼26 waters/lipid, but, based on simulations with a fourfold increase of the aqueous phase, the phosphoinositide positions and orientations do not show significant size effects. Electrostatic potentials evaluated from Poisson-Boltzmann (PB) calculations show a strong dependence of potential height and ring orientation, with the maxima on the −25 mV surfaces (17.1 ± 0.1 Å for PIP2 and 19.4 ± 0.3 Å for PIP3) occurring near the most populated orientations from MD. These surfaces are well above the background height of 10 Å estimated for negatively charged cell membranes, as would be expected for lipids involved in cellular signaling. PB calculations on microscopically flat bilayers yield similar maxima as the MD-based (microscopically rough) systems, but show less fine structure and do not clearly indicate the most probable regions. Electrostatic free energies of interaction with pentalysine are also similar for the rough and flat systems. These results support the utility of a rigid/flat bilayer model for PB-based studies of PIP2 and PIP3 as long as the orientations are judiciously chosen. PMID:19580753

How do arbuscular mycorrhizal fungi handle phosphate? New insight into fine-tuning of phosphate metabolism.

PubMed

Ezawa, Tatsuhiro; Saito, Katsuharu

2018-04-27

Contents Summary I. Introduction II. Foraging for phosphate III. Fine-tuning of phosphate homeostasis IV. The frontiers: phosphate translocation and export V. Conclusions and outlook Acknowledgements References SUMMARY: Arbuscular mycorrhizal fungi form symbiotic associations with most land plants and deliver mineral nutrients, in particular phosphate, to the host. Therefore, understanding the mechanisms of phosphate acquisition and delivery in the fungi is critical for full appreciation of the mutualism in this association. Here, we provide updates on physical, chemical, and biological strategies of the fungi for phosphate acquisition, including interactions with phosphate-solubilizing bacteria, and those on the regulatory mechanisms of phosphate homeostasis based on resurveys of published genome sequences and a transcriptome with reference to the latest findings in a model fungus. For the mechanisms underlying phosphate translocation and export to the host, which are major research frontiers in this field, not only recent advances but also testable hypotheses are proposed. Lastly, we briefly discuss applicability of the latest tools to gene silencing in the fungi, which will be breakthrough techniques for comprehensive understanding of the molecular basis of fungal phosphate metabolism. © 2018 The Authors. New Phytologist © 2018 New Phytologist Trust.

Direct observation of the oxidation of DNA bases by phosphate radicals formed under radiation: a model of the backbone-to-base hole transfer.

PubMed

Ma, Jun; Marignier, Jean-Louis; Pernot, Pascal; Houée-Levin, Chantal; Kumar, Anil; Sevilla, Michael D; Adhikary, Amitava; Mostafavi, Mehran

2018-05-30

In irradiated DNA, by the base-to-base and backbone-to-base hole transfer processes, the hole (i.e., the unpaired spin) localizes on the most electropositive base, guanine. Phosphate radicals formed via ionization events in the DNA-backbone must play an important role in the backbone-to-base hole transfer process. However, earlier studies on irradiated hydrated DNA, on irradiated DNA-models in frozen aqueous solution and in neat dimethyl phosphate showed the formation of carbon-centered radicals and not phosphate radicals. Therefore, to model the backbone-to-base hole transfer process, we report picosecond pulse radiolysis studies of the reactions between H2PO4˙ with the DNA bases - G, A, T, and C in 6 M H3PO4 at 22 °C. The time-resolved observations show that in 6 M H3PO4, H2PO4˙ causes the one-electron oxidation of adenine, guanine and thymine, by forming the cation radicals via a single electron transfer (SET) process; however, the rate constant of the reaction of H2PO4˙ with cytosine is too low (<107 L mol-1 s-1) to be measured. The rates of these reactions are influenced by the protonation states and the reorganization energies of the base radicals and of the phosphate radical in 6 M H3PO4.

Modelling the temporal and spatial distribution of ecological variables in Beibu Gulf

NASA Astrophysics Data System (ADS)

Pan, H.; Huang, L.; Yang, S.; Shi, D.; Pan, W.

2017-12-01

Beibu Gulf is an important semi-enclosed gulf located in northern South China Sea. It is rich in natural resources and its coastal rim is undergoing a rapid economic growth in recent years. Study on the spatial and temporal distribution of ecological variables by the influence of physical and biological processes in Beibu Gulf can provide the theoretical basis for the utilization of resources and environmental protection. Based on the MEC three-dimensional hydrodynamic model, a nutrient-phytoplankton-zooplankton-detritus (NPZD) model was applied to simulate the distribution of ecological variables in Beibu Gulf. The result shows that the ecosystem in Beibu Gulf is significantly influenced by dynamic conditions. In autumn and winter, great amount of nutrient-rich water from western Guangdong coastal area passes through Qiongzhou Strait and flows into Beibu Gulf, with about 108.3×103 t of inorganic nitrogen and 3.7×103 t of phosphate annually, leading to phytoplankton bloom. In summer, most of the nutrients come from rivers so high concentrations of nutrients and chlorophyll-a appear on estuaries. The annual net nutrient inputs from South China Sea into Beibu Gulf are 66.6×103 t for inorganic nitrogen and 4.6×103 t for phosphate. Phytoplankton plays an important role in nutrients' refreshment: a) Absorption by the process of photosynthesis is the biggest nutrient sink. b) Cellular release from dead phytoplankton is the biggest source in inorganic budget, making up for 33.4% of nitrogen consumed by photosynthesis while the process of respiration is the biggest source in phosphate budget, making up for 32.4% of phosphorus consumed by photosynthesis. c) Mineralization from detritus is also a considerable supplement of inorganic nutrients. Overall, biological process has more influence than physical process on the nutrient cycle budget in Beibu Gulf. The comparison of the result with remote sensing and in-situ data indicates that the model is able to simulate the biogeochemical characteristics in Beibu Gulf.

Long-Range Vibrational Dynamics Are Directed by Watson-Crick Base Pairing in Duplex DNA.

PubMed

Hithell, Gordon; Shaw, Daniel J; Donaldson, Paul M; Greetham, Gregory M; Towrie, Michael; Burley, Glenn A; Parker, Anthony W; Hunt, Neil T

2016-05-05

Ultrafast two-dimensional infrared (2D-IR) spectroscopy of a 15-mer A-T DNA duplex in solution has revealed structure-dependent vibrational coupling and energy transfer processes linking bases with the sugar-phosphate backbone. Duplex melting induces significant changes in the positions of off-diagonal peaks linking carbonyl and ring-stretching vibrational modes of the adenine and thymine bases with vibrations of the phosphate group and phosphodiester linkage. These indicate that Watson-Crick hydrogen bonding and helix formation lead to a unique vibrational coupling arrangement of base vibrational modes with those of the phosphate unit. On the basis of observations from time-resolved 2D-IR data, we conclude that rapid energy transfer processes occur between base and backbone, mediated by additional modes located on the deoxyribose moiety within the same nucleotide. These relaxation dynamics are insensitive to duplex melting, showing that efficient intramolecular energy relaxation to the solvent via the phosphate groups is the key to excess energy dissipation in both single- and double-stranded DNA.

Phosphate adsorption using modified iron oxide-based sorbents

EPA Pesticide Factsheets

Phosphate RemovalThis dataset is associated with the following publication:Lalley , J., C. Han , G. RamMohan , T. Speth , J. Garland , M. Nadagouda , and D. Dionysiou. Phosphate Removal using Modified Bayoxide®E33 Adsorption Media. WATER RESEARCH. Elsevier Science Ltd, New York, NY, USA, issue}: 96-107, (2015).

Dental Composites with Calcium / Strontium Phosphates and Polylysine.

PubMed

Panpisut, Piyaphong; Liaqat, Saad; Zacharaki, Eleni; Xia, Wendy; Petridis, Haralampos; Young, Anne Margaret

2016-01-01

This study developed light cured dental composites with added monocalcium phosphate monohydrate (MCPM), tristrontium phosphate (TSrP) and antimicrobial polylysine (PLS). The aim was to produce composites that have enhanced water sorption induced expansion, can promote apatite precipitation and release polylysine. Experimental composite formulations consisted of light activated dimethacrylate monomers combined with 80 wt% powder. The powder phase contained a dental glass with and without PLS (2.5 wt%) and/or reactive phosphate fillers (15 wt% TSrP and 10 wt% MCPM). The commercial composite, Z250, was used as a control. Monomer conversion and calculated polymerization shrinkage were assessed using FTIR. Subsequent mass or volume changes in water versus simulated body fluid (SBF) were quantified using gravimetric studies. These were used, along with Raman and SEM, to assess apatite precipitation on the composite surface. PLS release was determined using UV spectroscopy. Furthermore, biaxial flexural strengths after 24 hours of SBF immersion were obtained. Monomer conversion of the composites decreased upon the addition of phosphate fillers (from 76 to 64%) but was always higher than that of Z250 (54%). Phosphate addition increased water sorption induced expansion from 2 to 4% helping to balance the calculated polymerization shrinkage of ~ 3.4%. Phosphate addition promoted apatite precipitation from SBF. Polylysine increased the apatite layer thickness from ~ 10 to 20 μm after 4 weeks. The novel composites showed a burst release of PLS (3.7%) followed by diffusion-controlled release irrespective of phosphate addition. PLS and phosphates decreased strength from 154 MPa on average by 17% and 18%, respectively. All formulations, however, had greater strength than the ISO 4049 requirement of > 80 MPa. The addition of MCPM with TSrP promoted hygroscopic expansion, and apatite formation. These properties are expected to help compensate polymerization shrinkage and help remineralize demineralized dentin. Polylysine can be released from the composites at early time. This may kill residual bacteria.

Iron Fertilization of the Southern Ocean: Regional Simulation and Analysis of C-Sequestration in the Ross Sea

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kevin Arrigo

2012-03-13

A modified version of the dynamic 3-dimensional mesoscale Coupled Ice, Atmosphere, and Ocean model (CIAO) of the Ross Sea ecosystem has been used to simulate the impact of environmental perturbations upon primary production and biogenic CO2 uptake. The Ross Sea supports two taxonomically, and spatially distinct phytoplankton populations; the haptophyte Phaeocystis antarctica and diatoms. Nutrient utilization ratios predict that P. antarctica and diatoms will be driven to nitrate and phosphate limitation, respectively. Model and field data have confirmed that the Ross Sea is iron limited with only two-thirds of the macronutrients consumed by the phytoplankton by the end of themore » growing season. In this study, the CIAO model was improved to simulate a third macronutrient (phosphate), dissolved organic carbon, air-sea gas exchange, and the carbonate system. This enabled us to effectively model pCO2 and subsequently oceanic CO2 uptake via gas exchange, allowing investigations into the affect of alleviating iron limitation on both pCO2 and nutrient drawdown.« less

Dissolution and precipitation behaviors of silicon-containing ceramic coating on Mg-Zn-Ca alloy in simulated body fluid.

PubMed

Pan, Yaokun; Chen, Chuanzhong; Wang, Diangang; Huang, Danlan

2014-10-01

We prepared Si-containing and Si-free coatings on Mg-1.74Zn-0.55Ca alloy by micro-arc oxidation. The dissolution and precipitation behaviors of Si-containing coating in simulated body fluid (SBF) were discussed. Corrosion products were characterized by scanning electron microscope (SEM), X-ray diffractometer (XRD), fourier transform infrared spectrometer (FT-IR) and X-ray photoelectron spectrometer (XPS). Electrochemical workstation, inductively coupled plasma atomic emission spectrometer (ICP-AES), flame atomic absorption spectrophotometer (AAS) and pH meter were employed to detect variations of electrochemical parameter and ions concentration respectively. Results indicate that the fast formation of calcium phosphates is closely related to the SiOx(n-) groups, which induce the heterogeneous nucleation of amorphous hydroxyapatite (HA) by sorption of calcium and phosphate ions. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of the local environment of Eu3+ in a silicophosphate glass using site-selective spectroscopy and Molecular Dynamics simulations

NASA Astrophysics Data System (ADS)

Ben Slimen, F.; Haouari, M.; Ben Ouada, H.; Guichaoua, D.; Raso, P.; Bidault, X.; Turlier, J.; Gaumer, N.; Chaussedent, S.

2017-02-01

Silicophosphate glasses (SiO2-P2O5) doped with Eu3+ ions were synthesized by the sol-gel process. Optical properties of these glasses were investigated by means of emission spectra and lifetime measurements. The Fluorescence Line Narrowing (FLN) technique was also used to explore the local structure around the Eu3+ ions in this host and to understand the role of phosphate as a codopant. As it is the case for aluminum, the ability of phosphate to avoid the rare earth clustering was investigated, and the role of this codopant in modifying the local order around the rare earth ion was evidenced. The analysis of the FLN spectra and lifetime measurements is consistent with this interpretation. Molecular Dynamics simulations were performed to evaluate and confirm these structural features. Two classes of europium sites were distinguished in agreement with the experimental characterization.

Observational study on the palatability and tolerability of oral prednisolone and oral dexamethasone in children in Saudi Arabia and the UK.

PubMed

Aljebab, Fahad; Alanazi, Mofadhi; Choonara, Imti; Conroy, Sharon

2018-01-01

Short-course oral corticosteroids are routinely used to treat acute asthma and croup. We evaluated their tolerability and palatability in Saudi Arabian (SA) and UK children. Prospective observational/interview study (3 months in each country). Palatability was evaluated using a 5-point facial Hedonicscale and tolerability by direct questioning of patient/parents. In SA, of 122 patients (2-10 years) recruited, 52 received prednisolone base tablets, 37 prednisolone sodium phosphate syrup and 33 received dexamethasone elixir. In the UK, of 133 patients (2-16 years), 38 received prednisolone base tablets (mainly crushed and dispersed), 42 prednisolone sodium phosphate soluble tablets and 53 received dexamethasone sodium phosphate oral solution.In both countries, dexamethasone had the highest palatability scores (SA mean: 1.97; UK mean: 3) and prednisolone base tablets had the lowest (SA mean: 1.12; UK mean: 1.39). Palatability scores improved for all formulations of prednisolone with each subsequent daily dose.In SA, prednisolone base tablets were associated with more nausea (24vs7 patients) and vomiting (5vs0 patients) than sodium phosphate syrup (p=0.008 and p=0.073, respectively). In the UK, vomiting occurred more frequently with prednisolone base (8 patients) than sodium phosphate soluble tablets (2 patients) (p=0.041).In both centres, dexamethasone was associated with less side effects. Vomiting (1vs0 patients), nausea (7vs3 patients) and abdominal pain (10vs8 patients) occurred more with dexamethasone sodium phosphate solution than dexamethasone elixir. Dexamethasone sodium phosphate solution was the most palatable preparation. Prednisolone base tablets were rated least palatable and were least well tolerated. Palatability scores improved with each dose taken. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Determination of ortho-cresyl phosphate isomers of tricresyl phosphate used in aircraft turbine engine oils by gas chromatography and mass spectrometry.

PubMed

De Nola, G; Kibby, J; Mazurek, W

2008-07-25

Tricresyl phosphate (TCP) is used as an anti-wear additive in aircraft turbine engine oil. Concerns about its toxicity are largely based on the tri-o-cresyl phosphate isomer content. However, the presence of other and more toxic isomers has been previously suggested. In this work, the structural isomers of TCP have been determined by two methods (experimental and semi-theoretical). First, the TCP isomers were separated by gas chromatography (GC) and identified by mass spectrometry (MS). Second, after base cleavage of TCP, GC was used to quantify the cresol precursors. These results were used to calculate the TCP isomer distribution based on the assumption of a statistical distribution of the TCP isomers. The results from the two determinations showed reasonable agreement for three of the four oils studied. The o-cresyl isomers were found to be present almost exclusively as the more toxic mono-o-cresyl isomers in the concentration range 13-150 mg/L. The ability to analyse for the mono-o-cresyl isomers allows the toxicity of TCP to be based on the latter isomers rather than on the less toxic tri-o-cresyl phosphate isomer.

Ultrastructure of hybrid chitosan-glycerol phosphate blood clots by environmental scanning electron microscopy.

PubMed

Iliescu, M; Hoemann, C D; Shive, M S; Chenite, A; Buschmann, M D

2008-03-01

Chitosan-based polymers have been extensively studied for biomedical applications. Recently, liquid solutions of chitosan in a glycerol phosphate buffer (chitosan-GP) with physiological pH and osmolality were mixed with autologous blood to form hybrid chitosan-GP/blood implants that improved the repair of articular cartilage lesions in a large animal model. The mixture of chitosan-GP and blood forms a viscous liquid, which solidifies in minutes via normal blood coagulation as well as chitosan-mediated mechanisms. Here we have examined the ultrastructure of these chitosan-GP/blood clots as well as regular blood clots and chitosan-GP gels, the latter produced by heating. Both unfixed and fixed samples of chitosan-GP/blood clots, regular blood clots, and chitosan-GP gels were investigated by environmental scanning electron microscopy (ESEM) in conjunction with energy dispersive X-ray spectrometry (EDS), the former permitting direct observation of the ultrastructure in hydrated conditions simulating the natural state. By examination of unfixed specimens using ESEM we found that chitosan formed a network structure in both chitosan-GP gels and chitosan-GP/blood clots; however this structure was altered by aldehyde fixation to produce artifactual aggregates of chitosan microparticles. We were also able to identify chitosan in chitosan-GP/blood clots by washing samples in low concentration NaCl solutions followed by local EDS analyses to identify excess chloride versus sodium, and thus presence of cationic chitosan in analyzed features. Additional results indicated that the majority of glycerol phosphate diffuses freely from chitosan-GP gels (by EDS of phosphorus) and that hyperosmotic paraformaldehyde-based fixatives (i.e. 4% w/v) significantly disturb erythrocyte morphology in fixed whole blood clots. (c) 2007 Wiley-Liss, Inc.

Calcium phosphate composite cements based on simple mixture of brushite and apatite phases

NASA Astrophysics Data System (ADS)

Egorov, A. A.; Fedotov, A. Yu; Pereloma, I. S.; Teterina, A. Yu; Sergeeva, N. S.; Sviridova, I. K.; Kirsanova, V. A.; Akhmedova, S. A.; Nesterova, A. V.; Reshetov, I. V.; Barinov, S. M.; Komlev, V. S.

2018-04-01

The composite cements based on simple mixtures brishite and apatite with ratio 70/30, 50/50, 30/70 were developed. The processes of phase formation, microstructure and mechanical properties were studied. The kinetics of degradation in simulated body fluid depending on the microstructure and the materials phase composition was carried out. The biological test in vitro were performed using the MTT-test on the human fibroblast immortalized (hFB) cell line and the human osteosarcoma cell line MG-63. The materials didn’t have acute cytoxicity and possessed surface matrix properties. It was determined that the both line of cells actively proliferated, with viable cells values higher 20-60 % then control at all observation periods.

Measuring phosphate with an inexpensive, easy to build photometer

NASA Astrophysics Data System (ADS)

Simeonov, Valentin; Weijs, Steven; Parlange, Marc

2013-04-01

In the context of a course for first year students to get hands-on experience with measuring in the environment, a photometric system for measuring phosphate concentration was developed. The system makes use of a single LED as a light source, a Si photodiode-based light to frequency conversion IC and an Arduino electronic card as acquisition system. The instrument is designed as an easy to assemble system and assembling and alignment is part of the exercise. The phosphate measurement is based on the formation of phosphor-molybdate complex which is eventually reduced to a blue component. The absorbance at 710 nm of a phosphate-containing fluid with added indicator is then measured and calibrated with a known solution. The initial test has demonstrated the ability of the instrument to detect phosphates in tap water. Other components as nitrates or chlorophyll could be easily measured with the instrument using LED emitting at the respective wavelengths.

Topography and nanostructural evaluation of chemically and thermally modified titanium substrates.

PubMed

Salemi, Hoda; Behnamghader, Aliasghar; Afshar, Abdollah

2016-10-01

In this research, the effects of chemical and thermal treatment on the morphological and compositional aspects of titanium substrates and so, potentially, on development of biomimetic bone like layers formation during simulated body fluid (SBF) soaking was investigated. The HF, HF/HNO3 and NaOH solutions were used for chemical treatment and some of alkali-treated samples followed a heat treatment at 600°C. The treated samples before and after soaking were subjected to material characterization tests using scanning electron microscopy (SEM), X-ray diffraction (XRD) and atomic force microscopy (AFM). White light interferometry (WLI) was used to determine the roughness parameters such as Ra, Rq, RKu and Rsk. The significance of the obtained data was assessed using ANOVA variance analysis between all samples. It was observed that the reaction at grain boundaries and sodium titanate intermediate layers play a great role in the nucleation of calcium phosphate layers. Based on the obtained results in this work, the calcium phosphate microstructure deposited on titanium substrates was more affected by chemical modification than surface topography.

Fabrication and characterization of carbon/oxygen-implanted waveguides in Nd3+-doped phosphate glasses

NASA Astrophysics Data System (ADS)

Liu, Chun-Xiao; Xu, Jun; Fu, Li-Li; Zheng, Rui-Lin; Zhou, Zhi-Guang; Li, Wei-Nan; Guo, Hai-Tao; Lin, She-Bao; Wei, Wei

2015-06-01

Optical planar waveguides in Nd3+-doped phosphate glasses are fabricated by a 6.0-MeV carbon ion implantation with a dose of 6.0×1014 ions/cm2 and a 6.0-MeV oxygen ion implantation at a fluence of 6.0×1014 ions/cm2, respectively. The guided modes and the corresponding effective refractive indices were measured by a modal 2010 prism coupler. The refractive index profiles of the waveguides were analyzed based on the stopping and range of ions in matter and the RCM reflectivity calculation method. The near-field light intensity distributions were measured and simulated by an end-face coupling method and a finite-difference beam propagation method, respectively. The comparison of optical properties between the carbon-implanted waveguide and the oxygen-implanted waveguide was carried out. The microluminescence and Raman spectroscopy investigations reveal that fluorescent properties of Nd3+ ions and glass microstructure are well preserved in the waveguide region, which suggests that the carbon/oxygen-implanted waveguide is a good candidate for integrated photonic devices.

Pumpable/injectable phosphate-bonded ceramics

DOEpatents

Singh, Dileep; Wagh, Arun S.; Perry, Lamar; Jeong, Seung-Young

2001-01-01

A pumpable ceramic composition is provided comprising an inorganic oxide, potassium phosphate, and an oxide coating material. Also provided is a method for preparing pumpable ceramic-based waste forms comprising selecting inorganic oxides based on solubility, surface area and morphology criteria; mixing the selected oxides with phosphate solution and waste to form a first mixture; combining an additive to the first mixture to create a second mixture; adding water to the second mixture to create a reactive mixture; homogenizing the reactive mixture; and allowing the reactive mixture to cure.

Partial reactions of d-glucose 6-phosphate–1 l-myoinositol 1-phosphate cyclase

PubMed Central

Barnett, J. E. G.; Rasheed, A.; Corina, D. L.

1973-01-01

After removal of tightly bound NAD+ by using charcoal, a preparation of d-glucose 6-phosphate–1 l-myoinositol 1-phosphate cyclase catalysed the reduction of 5-keto-d-glucitol 6-phosphate and 5-keto-d-glucose 6-phosphate by [4-3H]NADH to give [5-3H]-glucitol 6-phosphate and [5-3H]glucose 6-phosphate respectively. The position of the tritium atom in the latter was shown by degradation. Both enzyme-catalysed reductions were strongly inhibited by 2-deoxy-d-glucose 6-phosphate, a powerful competitive inhibitor of inositol cyclase. The charcoal-treated enzyme preparation also converted 5-keto-d-glucose 6-phosphate into [3H]myoinositol 1-phosphate in the presence of [4-3H]NADH, but less effectively. These partial reactions of inositol cyclase are interpreted as providing strong evidence for the formation of 5-keto-d-glucose 6-phosphate as an enzyme-bound intermediate in the conversion of d-glucose 6-phosphate into 1 l-myoinositol 1-phosphate. The enzyme was partially inactivated by NaBH4 in the presence of NAD+. Glucose 6-phosphate did not increase the inactivation, and there was no inactivation in the absence of NAD+. There was no evidence for Schiff base formation during the cyclization. d-Glucitol 6-phosphate (l-sorbitol 1-phosphate) was a good inhibitor of the overall reaction. It did not inactivate the enzyme. The apparent molecular weight of inositol cyclase as determined by Sephadex chromatography was 2.15×105. PMID:4352864

Fabrication of a Biomass-Based Hydrous Zirconium Oxide Nanocomposite for Preferable Phosphate Removal and Recovery.

PubMed

Qiu, Hui; Liang, Chen; Zhang, Xiaolin; Chen, Mindong; Zhao, Yunxia; Tao, Tao; Xu, Zhengwen; Liu, Gang

2015-09-23

Advanced removal of phosphate by low-cost adsorbents from municipal wastewater or industrial effluents is an effective and economic way to prevent the occurrence of eutrophication. Here, we proposed a novel method to immobilize hydrous zirconium oxide nanoparticle within quaternary-aminated wheat straw, and obtained an inexpensive, eco-friendly nanocomposite Ws-N-Zr. The biomass-based Ws-N-Zr exhibited higher preference toward phosphate than commercial anion exchanger IRA-900 when competing sulfate ions coexisted at relatively high levels. Such excellent performance of Ws-N-Zr resulted from its specific hybrid structure, the quaternary ammonium groups bonded on the host favor the preconcentration of phosphate ions inside the wheat straw based on Donnan effect, and the encapsulated HZO nanoparticle exhibits preferable sequestration of phosphate ions through specific interaction, as further demonstrated by FTIR and X-ray photoelectron spectroscopy. Cycle adsorption and regeneration experiments demonstrated that Ws-N-Zr could be employed for repeated use without significant capacity loss, when the binary NaOH-NaCl solution was employed as the regenerant. The influence of solution pH and contact time was also examined. The results suggested that Ws-N-Zr has a great potential in efficient removal of phosphate in contaminated waters.

Biomimetic Coating on Porous Alumina for Tissue Engineering: Characterisation by Cell Culture and Confocal Microscopy

PubMed Central

Kolos, Elizabeth; Ruys, Andrew J

2015-01-01

In this study porous alumina samples were prepared and then coated using the biomimetic coating technique using a five times Simulated Body Fluid (5.0SBF) as the growth solution. A coating was achieved after pre-treatment with concentrated acid. From elemental analysis, the coating contained calcium and phosphorous, but also sodium and chlorine. Halite was identified by XRD, a sodium chloride phase. Sintering was done to remove the halite phase. Once halite was burnt off, the calcium phosphate crystals were not covered with halite and, therefore, the apatite phases can be clearly observed. Cell culturing showed sufficient cell attachment to the less porous alumina, Sample B, that has more calcium phosphate growth, while the porous alumina, Sample A, with minimal calcium phosphate growth attained very little cell attachment. This is likely due to the contribution that calcium phosphate plays in the attachment of bone-like cells to a bioinert ceramic such as alumina. These results were repeated on both SEM and confocal microscopy analysis. Confocal microscopy was a novel characterisation approach which gave useful information and was a visual aid.

Effect of particle size of calcium phosphate based bioceramic drug delivery carrier on the release kinetics of ciprofloxacin hydrochloride: an in vitro study

NASA Astrophysics Data System (ADS)

Sasikumar, Swamiappan

2013-09-01

Hydroxyapatite (HAP) is the constituent of calcium phosphate based bone cement and it is extensively used as a bone substitute and drug delivery vehicle in various biomedical applications. In the present study we investigated the release kinetics of ciprofloxacin loaded HAP and analyzed its ability to function as a targeted and sustained release drug carrier. Synthesis of HAP was carried out by combustion method using tartaric acid as a fuel and nitric acid as an oxidizer. Powder XRD and FTIR techniques were employed to characterize the phase purity of the drug carrier and to verify the chemical interaction between the drug and carrier. The synthesized powders were sieve separated to make two different drug carriers with different particle sizes and the surface topography of the pellets of the drug carrier was imaged by AFM. Surface area and porosity of the drug carrier was carried out using surface area analyzer. The in-vitro drug release kinetics was performed in simulated body fluid, at 37.3°C. The amount of ciprofloxacin released is measured using UV-visible spectroscopy following the characteristic λ max of 278 nm. The release saturates around 450 h which indicates that it can be used as a targeted and sustained release carrier for bone infections.

Biological influence of Ca/P ratio on calcium phosphate coatings by sol-gel processing.

PubMed

Catauro, M; Papale, F; Sapio, L; Naviglio, S

2016-08-01

The objective of this work has been to develop low temperature sol-gel glass coatings to modify the substrate surface and to evaluate their bioactivity and biocompatibility. Glasses, based on SiO2·CaO·P2O5, were synthesized by the sol-gel technique using tetraethyl orthosilicate, calcium nitrate tetrahydrate and triethyl phosphate as precursors of SiO2, CaO and P2O5, respectively. Those materials, still in the sol phase, have been used to coat substrates by means of the dip-coating technique. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) has been used for characterize coatings and a microstructural analysis has been obtained using scanning electron microscopy (SEM). The potential applications of the coatings in the biomedical field were evaluated by bioactivity and biocompatibility tests. The coated substrate was immersed in simulated body fluid (SBF) for 21days and the hydroxyapatite deposition on its surface was subsequently evaluated via SEM-EDXS analysis, as an index of bone-bonding capability. In order to study the cell behavior and response to our silica based materials, prepared via the sol-gel method, with various Ca/P ratio and coating substrate, we have used the human osteoblast-like U2OS cell line. Copyright © 2016 Elsevier B.V. All rights reserved.

Fiber-enriched double-setting calcium phosphate bone cement.

PubMed

dos Santos, Luís Alberto; Carrodéguas, Raúl Garcia; Boschi, Anselmo Ortega; Fonseca de Arruda, Antônio Celso

2003-05-01

Calcium phosphate bone cements are useful in orthopedics and traumatology, their main advantages being their biocompatibility and bioactivity, which render bone tissue osteoconductive, providing in situ hardening and easy handling. However, their low mechanical strength, which, in the best of cases, is equal to the trabecular bone, and their very low toughness are disadvantages. Calcium phosphate cement compositions with mechanical properties more closely resembling those of human bone would broaden the range of applications, which is currently limited to sites subjected to low loads. This study investigated the influence of added polypropylene, nylon, and carbon fibers on the mechanical properties of double setting alpha-tricalcium phosphate-based cement, using calcium phosphate cement added to an in situ polymerizable acrylamide-based system recently developed by the authors. Although the addition of fibers was found to reduce the compression strength of the double-setting calcium phosphate cement because of increased porosity, it strongly increased the cement's toughness (J(IC)) and tensile strength. The composites developed in this work, therefore, have a potential application in shapes subjected to flexure. Copyright 2003 Wiley Periodicals, Inc.

Modified 5-fluorouracil: Uridine phosphorylase inhibitor

NASA Astrophysics Data System (ADS)

Lashkov, A. A.; Shchekotikhin, A. A.; Shtil, A. A.; Sotnichenko, S. E.; Mikhailov, A. M.

2016-09-01

5-Fluorouracil (5-FU) is a medication widely used in chemotherapy to treat various types of cancer. Being a substrate for the reverse reaction catalyzed by uridine phosphorylase (UPase), 5-FU serves as a promising prototype molecule (molecular scaffold) for the design of a selective UPase inhibitor that enhances the antitumor activity of 5-FU and exhibits intrinsic cytostatic effects on cancer cells. The chemical formula of the new compound, which binds to the uracil-binding site and, in the presence of a phosphate anion, to the phosphate-binding site of UPase, is proposed and investigated by molecular simulation methods.

Non-enzymatic synthesis of the coenzymes, uridine diphosphate glucose and cytidine diphosphate choline, and other phosphorylated metabolic intermediates

NASA Technical Reports Server (NTRS)

Mar, A.; Dworkin, J.; Oro, J.

1987-01-01

Using urea and cyanamide, the two condensing agents considered to have been present on the primitive earth, uridine diphosphate glucose (UDPG), cytidine diphosphate choline (CDP-choline), glucose-1-phosphate (G1P), and glucose-6-phosphate (G6P) were synthesized under simulated prebiotic conditions. The reaction products were separated and identified using paper chromatography, thin layer chromatography, enzymatic analyses, and ion-pair reverse-phase high performance liquid chromatography. The possibility of nonenzymatic synthesis of metabolic intermediates on the primitive earth from simple precursors was thus demonstrated.

Nanoporous sorbent material as an oral phosphate binder and for aqueous phosphate, chromate, and arsenate removal

PubMed Central

Sangvanich, Thanapon; Ngamcherdtrakul, Worapol; Lee, Richard; Morry, Jingga; Castro, David; Fryxell, Glen E.; Yantasee, Wassana

2014-01-01

Phosphate removal is both biologically and environmentally important. Biologically, hyperphosphatemia is a critical condition in end-stage chronic kidney disease patients. Patients with hyperphosphatemia are treated long-term with oral phosphate binders to prevent phosphate absorption to the body by capturing phosphate in the gastrointestinal (GI) tract followed by fecal excretion. Environmentally, phosphate levels in natural water resources must be regulated according to limits set forth by the US Environmental Protection Agency. By utilizing nanotechnology and ligand design, we developed a new material to overcome limitations of traditional sorbent materials such as low phosphate binding capacity, slow binding kinetics, and negative interference by other anions. A phosphate binder based on iron-ethylenediamine on nanoporous silica (Fe-EDA-SAMMS) has been optimized for substrates and Fe(III) deposition methods. The Fe-EDA-SAMMS material had a 4-fold increase in phosphate binding capacity and a broader operating pH window compared to other reports. The material had a faster phosphate binding rate and was significantly less affected by other anions than Sevelamer HCl, the gold standard oral phosphate binder, and AG® 1-X8, a commercially available anion exchanger. It had less cytotoxicity to Caco-2 cells than lanthanum carbonate, another prescribed oral phosphate binder. The Fe-EDA-SAMMS also had high capacity for arsenate and chromate, two of the most toxic anions in natural water. PMID:25554735

Binding affinity and decontamination of dermal decontamination gel to model chemical warfare agent simulants.

PubMed

Cao, Yachao; Elmahdy, Akram; Zhu, Hanjiang; Hui, Xiaoying; Maibach, Howard

2018-05-01

Six chemical warfare agent simulants (trimethyl phosphate, dimethyl adipate, 2-chloroethyl methyl sulfide, diethyl adipate, chloroethyl phenyl sulfide and diethyl sebacate) were studied in in vitro human skin to explore relationship between dermal penetration/absorption and the mechanisms of simulant partitioning between stratum corneum (SC) and water as well as between dermal decontamination gel (DDGel) and water. Both binding affinity to and decontamination of simulants using DDGel were studied. Partition coefficients of six simulants between SC and water (Log P SC/w ) and between DDGel and water (Log P DDGel/w ) were determined. Results showed that DDGel has a similar or higher binding affinity to each simulant compared to SC. The relationship between Log P octanol/water and Log P SC/w as well as between Log P octanol/water and Log P DDGel/w demonstrated that partition coefficient of simulants correlated to their lipophilicity or hydrophilicity. Decontamination efficiency results with DDGel for these simulants were consistent with binding affinity results. Amounts of percentage dose of chemicals in DDGel of trimethyl phosphate, dimethyl adipate, 2-chloroethyl methyl sulfide, diethyl adipate, chloroethyl phenyl sulfide and diethyl sebacate were determined to be 61.15, 85.67, 75.91, 53.53, 89.89 and 76.58, with corresponding amounts absorbed in skin of 0.96, 0.65, 1.68, 0.72, 0.57 and 1.38, respectively. In vitro skin decontamination experiments coupled with a dermal absorption study demonstrated that DDGel can efficiently remove chemicals from skin surface, back-extract from the SC, and significantly reduced chemical penetration into skin or systemic absorption for all six simulants tested. Therefore, DDGel offers a great potential as a NextGen skin Decon platform technology for both military and civilian use. Copyright © 2018 John Wiley & Sons, Ltd.

Impact of the river nutrient load variability on the North Aegean ecosystem functioning over the last decades

NASA Astrophysics Data System (ADS)

Tsiaras, K. P.; Petihakis, G.; Kourafalou, V. H.; Triantafyllou, G.

2014-02-01

The impact of river load variability on the North Aegean ecosystem functioning over the last decades (1980-2000) was investigated by means of a coupled hydrodynamic/biogeochemical model simulation. Model results were validated against available SeaWiFS Chl-a and in situ data. The simulated food web was found dominated by small cells, in agreement with observations, with most of the carbon channelled through the microbial loop. Diatoms and dinoflagellates presented a higher relative abundance in the more productive coastal areas. The increased phosphate river loads in the early 80s resulted in nitrogen and silicate deficiency in coastal, river-influenced regions. Primary production presented a decreasing trend for most areas. During periods of increased phosphate/nitrate inputs, silicate deficiency resulted in a relative decrease of diatoms, triggering an increase of dinoflagellates. Such an increase was simulated in the late 90s in the Thermaikos Gulf, in agreement with the observed increased occurrence of Harmful Algal Blooms. Microzooplankton was found to closely follow the relative increase of dinoflagellates under higher nutrient availability, showing a faster response than mesozooplankton. Sensitivity simulations with varying nutrient river inputs revealed a linear response of net primary production and plankton biomass. A stronger effect of river inputs was simulated in the enclosed Thermaikos Gulf, in terms of productivity and plankton composition, showing a significant increase of dinoflagellates relative abundance under increased nutrient loads.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Jianjun; Cheng, Xiaolin; Heberle, Frederick A

Cholesterol and ether lipids are ubiquitous in mammalian cell membranes, and their interactions are crucial in ether lipid mediated cholesterol trafficking. We report on cholesterol s molecular interactions with ether lipids as determined using a combination of small-angle neutron and Xray scattering, and all-atom molecular dynamics (MD) simulations. A scattering density profile model for an ether lipid bilayer was developed using MD simulations, which was then used to simultaneously fit the different experimental scattering data. From analysis of the data the various bilayer structural parameters were obtained. Surface area constrained MD simulations were also performed to reproduce the experimental data.more » This iterative analysis approach resulted in good agreement between the experimental and simulated form factors. The molecular interactions taking place between cholesterol and ether lipids were then determined from the validated MD simulations. We found that in ether membranes cholesterol primarily hydrogen bonds with the lipid headgroup phosphate oxygen, while in their ester membrane counterparts cholesterol hydrogen bonds with the backbone ester carbonyls. This different mode of interaction between ether lipids and cholesterol induces cholesterol to reside closer to the bilayer surface, dehydrating the headgroup s phosphate moiety. Moreover, the three-dimensional lipid chain spatial density distribution around cholesterol indicates anisotropic chain packing, causing cholesterol to tilt. These insights lend a better understanding of ether lipid-mediated cholesterol trafficking and the roles that the different lipid species have in determining the structural and dynamical properties of membrane associated biomolecules.« less

Alkaline Hydrothermal Vents as Electrochemical Reactors Driving an Auto-Trophic Origin of Life

NASA Astrophysics Data System (ADS)

Camprubi, E.; Lane, N.

2017-07-01

We report the reduction of CO2 to formaldehyde under simulated alkaline hydrothermal conditions. Formaldehyde is transformed into relevant sugars via the formose reaction. Acetyl phosphate can also be synthesised and phosphorylates organic molecules.

Interactions between Ether Phospholipids and Cholesterol as Determined by Scattering and Molecular Dynamics Simulations

PubMed Central

Pan, Jianjun; Cheng, Xiaolin; Heberle, Frederick A.; Mostofian, Barmak; Kučerka, Norbert; Drazba, Paul; Katsaras, John

2012-01-01

Cholesterol and ether lipids are ubiquitous in mammalian cell membranes, and their interactions are crucial in ether lipid mediated cholesterol trafficking. We report on cholesterol’s molecular interactions with ether lipids as determined using a combination of small-angle neutron and X-ray scattering, and all-atom molecular dynamics (MD) simulations. A scattering density profile model for an ether lipid bilayer was developed using MD simulations, which was then used to simultaneously fit the different experimental scattering data. From the analysis of the data the various bilayer structural parameters were obtained. Surface area constrained MD simulations were also performed to reproduce the experimental data. This iterative analysis approach resulted in good agreement between the experimental and simulated form factors. The molecular interactions taking place between cholesterol and ether lipids were then determined from the validated MD simulations. We found that in ether membranes, cholesterol primarily hydrogen bonds with the lipid headgroup phosphate oxygen, while in their ester membrane counterparts, cholesterol hydrogen bonds with the backbone ester carbonyls. This different mode of interaction between ether lipids and cholesterol induces cholesterol to reside closer to the bilayer surface, dehydrating the headgroup’s phosphate moiety. Moreover, the three-dimensional lipid chain spatial density distribution around cholesterol indicates anisotropic chain packing, causing cholesterol to tilt. These insights lend a better understanding of ether lipid mediated cholesterol trafficking and the roles that the different lipid species have in determining the structural and dynamical properties of membrane associated biomolecules. PMID:23199292

Prehistoric Agriculture and Soil Fertility on Lava Flows in Northern Arizona, USA: Results from the San Francisco Volcanic Field REU

NASA Astrophysics Data System (ADS)

Broadman, E.; Anderson, K. C.

2013-12-01

The San Francisco Volcanic Field in northern Arizona is home to ~600 cinder cones, the youngest of which is Sunset Crater (erupted ~AD 1100). This study documents trends in available phosphate and nitrate content with time, testing whether lowered soil pH from the addition of Sunset cinders increased soil fertility and became a factor in Anasazi agricultural success. Soil fertility is examined both before and after Sunset's eruption in soils of different ages that have developed from eolian deposition on top of lava flows. An increase in phosphate and nitrate levels following acidification would suggest that the presence of Sunset cinders brought the soils to the optimal pH for mobilization of these nutrients. The combined effects of the cinder layer retaining nutrients and water, wetter climates, and increases in phosphate and nitrate (both limiting nutrients for plant growth), would have contributed to Anasazi agricultural success after Sunset's eruption. Samples for this study were taken from eolian-derived soils of different ages atop lava flows in the San Francisco Volcanic Field. OSL data from these soils on Strawberry and SP Craters' lava flows yielded age estimates of ~12.3 ka (Strawberry) and ~32.7 ka (SP), on which a soil chronosequence was based. Results from the chronosequence supported these OSL ages, indicating that soils on the SP flow are older than those on the Strawberry flow. Field descriptions, Harden Development Indices, particle size analysis, and nutrient content analysis were used for this aspect of the project. An experimental acid wash method will be used to simulate the addition of Sunset's acidic cinders, and will yield data for phosphate and nitrate content after Sunset erupted. Preliminary results indicate that phosphate and nitrate accumulate in upper, eolian-derived horizons (Av, Bw) and in more deeply buried carbonate horizons (Bk). Higher concentrations of phosphate and nitrate were found in older (SP) soils than younger (Strawberry) soils, suggesting that these nutrients increase over time with eolian deposition and soil development. Results from this study will yield information on the impact of volcanic eruptions and soil development on prehistoric agriculture and soil fertility. This study contributes to our understanding of the interactions between eruptions and human populations.

Use of phosphorus-sorbing materials to remove phosphate from greenhouse wastewater.

PubMed

Dunets, C Siobhan; Zheng, Youbin; Dixon, Mike

2015-01-01

High phosphate content in wastewater is currently a major issue faced by the North American greenhouse industry. Phosphate-sorbing material filters could provide a means of removing phosphate from wastewater prior to discharge to the environment, but the characterization of economically viable materials and specific recommendations for greenhouse wastewater are not available. Batch and column experiments were used to examine the capacity of two calcium-based waste materials, basic oxygen furnace slag and a concrete waste material, to remove phosphate from greenhouse nutrient solution at varied operating conditions. Material columns operating at a hydraulic retention time (HRT) of 3 h consistently removed >99% of influent phosphate at a concentration of 60 mg/L over repeated applications and demonstrated high phosphate retention capacity (PRC) of 8.8 and 5.1 g P/kg for slag and concrete waste, respectively. Both materials also provided some removal of the micronutrients Fe, Mn and Zn. Increasing HRT to 24 h increased P retention capacity of slag to >10.5 g P/kg but did not improve retention by concrete waste. Decreasing influent phosphate concentration to 20 mg/L decreased PRC to 1.64 g P/kg in concrete waste columns, suggesting fluctuations in greenhouse wastewater composition will affect filter performance. The pH of filter effluent was closely correlated to final P concentration and can likely be used to monitor treatment effectiveness. This study demonstrated that calcium-based materials are promising for the removal of phosphate from greenhouse wastewater, and worthy of further research on scaling up the application to a full-sized system.

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters by use of solid-phase extraction, and its applications to brackish lake waters.

PubMed

Okumura, M; Tong, L; Fujinaga, K; Seike, Y

2001-05-01

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters has been developed for field analysis. This method is based on solid-phase extraction on a zirconium-loaded Sep-Pack Accell CM cartridge (Zr-SP) and is applicable to studies in which sampling is performed by use of a graduated syringe to prevent contamination and to ensure easy operation at sampling sites. The Zr-SP cartridge was prepared by passing 0.1 mol L(-1) zirconium solution through a Sep-Pak Accell CM cartridge, packed with cation exchange sorbent based on a silica matrix. The adsorption of phosphate and its desorption depend only on the pH of the solution. A water sample containing phosphate was adjusted to pH 2 and passed through the Zr-SP cartridge to collect it. The retained phosphate was quantitatively eluted with 0.5 mol L(-1) sodium hydroxide solution. The phosphate retained in the Zr-SP cartridge was stable for at least one month. The established preconcentration method was successfully applied to brackish lake waters to investigate seasonal changes in the distribution and behavior of phosphate in a brackish lake.

Preparation, mechanical property and cytocompatibility of freeze-cast porous calcium phosphate ceramics reinforced by phosphate-based glass.

PubMed

Yang, Yanqiu; He, Fupo; Ye, Jiandong

2016-12-01

In this study, phosphate-based glass (PG) was used as a sintering aid for freeze-cast porous biphasic calcium phosphate (BCP) ceramic, which was sintered under a lower temperature (1000°C). The phase composition, pore structure, compressive strength, and cytocompatibility of calcium phosphate composite ceramics (PG-BCP) were evaluated. The results indicated that PG additive reacted with calcium phosphate during the sintering process, forming β-Ca2P2O7; the ions of sodium and magnesium from PG partially substituted the calcium sites of β-calcium phosphate in BCP. The PG-BCP showed good cytocompatibility. The pore width of the porous PG-BCP ceramics was around 50μm, regardless of the amount of PG sintering aid. As the content of PG increased from 0wt.% to 15wt.%, the compressive strength of PG-BCP increased from 0.02 MP to 0.28MPa. When the PG additive was 17.5wt.%, the compressive strength of PG-BCP dramatically increased to 5.66MPa. Addition of 15wt.% PG was the critical point for the properties of PG-BCP. PG is considered as an effective sintering aid for freeze-cast porous bioceramics. Copyright © 2016 Elsevier B.V. All rights reserved.

Phosphate-based glass fiber vs. bulk glass: Change in fiber optical response to probe in vitro glass reactivity.

PubMed

Massera, J; Ahmed, I; Petit, L; Aallos, V; Hupa, L

2014-04-01

This paper investigates the effect of fiber drawing on the thermal and structural properties as well as on the glass reactivity of a phosphate glass in tris(hydroxymethyl)aminomethane-buffered (TRIS) solution and simulated body fluid (SBF). The changes induced in the thermal properties suggest that the fiber drawing process leads to a weakening and probable re-orientation of the POP bonds. Whereas the fiber drawing did not significantly impact the release of P and Ca, an increase in the release of Na into the solution was noticed. This was probably due to small structural reorientations occurring during the fiber drawing process and to a slight diffusion of Na to the fiber surface. Both the powders from the bulk and the glass fibers formed a Ca-P surface layer when immersed in SBF and TRIS. The layer thickness was higher in the calcium and phosphate supersaturated SBF than in TRIS. This paper for the first time presents the in vitro reactivity and optical response of a phosphate-based bioactive glass (PBG) fiber when immersed in SBF. The light intensity remained constant for the first 48h after which a decrease with three distinct slopes was observed: the first decrease between 48 and 200h of immersion could be correlated to the formation of the Ca-P layer at the fiber surface. After this a faster decrease in light transmission was observed from 200 to ~425h in SBF. SEM analysis suggested that after 200h, the surface of the fiber was fully covered by a thin Ca-P layer which is likely to scatter light. For immersion times longer than ~425h, the thickness of the Ca-P layer increased and thus acted as a barrier to the dissolution process limiting further reduction in light transmission. The tracking of light transmission through the PBG fiber allowed monitoring of the fiber dissolution in vitro. These results are essential in developing new bioactive fiber sensors that can be used to monitor bioresponse in situ. Copyright © 2014 Elsevier B.V. All rights reserved.

Modelling the impacts of altered management practices, land use and climate changes on the water quality of the Millbrook catchment-reservoir system in South Australia.

PubMed

Nguyen, Hong Hanh; Recknagel, Friedrich; Meyer, Wayne; Frizenschaf, Jacqueline; Shrestha, Manoj Kumar

2017-11-01

Sustainable management of drinking water reservoirs requires taking into account the potential effects of their catchments' development. This study is an attempt to estimate the daily patterns of nutrients transport in the catchment - reservoir systems through the application of the ensemble of complementary models SWAT-SALMO. SWAT quantifies flow, nitrate and phosphate loadings originating in catchments before entering downstream reservoirs meanwhile SALMO determines phosphate, nitrate, and chlorophyll-a concentrations within the reservoirs. The study applies to the semi-arid Millbrook catchment-reservoir system that supplies drinking water to north-eastern suburbs of Adelaide, South Australia. The catchment hosts viti- and horticultural land uses. The warm-monomictic, mesotrophic reservoir is artificially aerated in summer. After validating the simulation results for both Millbrook catchment and reservoir, a comprehensive scenario analysis has been conducted to reveal cascading effects of altered management practices, land uses and climate conditions on water quality in the reservoir. Results suggest that the effect on reservoir condition in summer would be severe, most likely resulting in chlorophyll-a concentrations of greater than 40 μg/l if the artificial destratification was not applied from early summer. A 50% curbing of water diversion from an external pipeline to the catchment will slightly limit chlorophyll-a concentrations by 1.22% as an effect of reduced inflow phosphate loads. The simulation of prospective land use scenarios converting 50% of present pasture in the Millbrook catchment into residential and orchards areas indicates an increase of summer chlorophyll-a concentrations by 9.5-107.9%, respectively in the reservoir. Global warming scenarios based on the high emission simulated by SWAT-SALMO did result in earlier growth of chlorophyll-a but overall the effects on water quality in the Millbrook reservoir was not significant. However scenarios combining global warming and land use changes resulted in significant eutrophication effects in the reservoir, especially in the unmanaged condition with stratification in summer. This study has demonstrated that complementary model ensembles like SWAT-SALMO allow to comprehend more realistically cascading effects of distinct catchment processes on internal reservoir's processes, and facilitate integrated management scenarios. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biomedical and sensing applications of a multi-mode biodegradable phosphate-based optical fiber

NASA Astrophysics Data System (ADS)

Podrazky, Ondřej; Peterka, Pavel; Vytykáčová, SoÅa.; Proboštová, Jana; Kuneš, Martin; Lyutakov, Oleksiy; Ceci-Ginistrelli, Edoardo; Pugliese, Diego; Boetti, Nadia G.; Janner, Davide; Milanese, Daniel

2018-02-01

We report on the employment of a biodegradable phosphate-based optical fiber as a pH sensing probe in physiological environment. The phosphate-based optical fiber preform was fabricated by the rod-in-tube technique. The fiber biodegradability was first tested in-vitro and then its biodegradability and toxicity were tested in-vivo. Optical probes for pH sensing were prepared by the immobilization of a fluorescent dye on the fiber tip by a sol-gel method. The fluorescence response of the pH-sensor was measured as a ratio of the emission intensities at the excitation wavelengths of 405 and 450 nm.

Analyses of plasma for metabolic and hormonal changes in rats flown aboard Cosmos 2044

NASA Technical Reports Server (NTRS)

Merrill, Alfred H., Jr.; Wang, Elaine; Mullins, Richard E.; Grindeland, Richard E.; Popova, Irina A.

1992-01-01

Plasmas samples from rats flown aboard Cosmos 2044 were analyzed for the levels of key metabolites, electrolytes, enzymes, and hormones. The major differences between the flight group and the synchronous control were elevations in glucose, cholesterol, phosphate, creatinine, blood urea nitrogen, lactate dehydrogenase, and aspartate aminotransferase and decreased levels of thyroxine. Most of these differences were not mimicked by tail suspension of ground-based rats; however, both flight and suspended rats exhibited inhibited testosterone secretion. Corticosterone, immunoreactive growth hormone, and prolactin showed inconsistent differences from the various control groups, suggesting that the levels of these hormones were not due to actual or simulated microgravity.

Efficient phosphate sequestration for water purification by unique sandwich-like MXene/magnetic iron oxide nanocomposites

NASA Astrophysics Data System (ADS)

Zhang, Qingrui; Teng, Jie; Zou, Guodong; Peng, Qiuming; Du, Qing; Jiao, Tifeng; Xiang, Jianyong

2016-03-01

Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene.Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09303a

Nuclear magnetic resonance studies of the regulation of the pentose phosphate pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolo, N.R.

1991-11-01

The goal of this work is to investigate the potential for and limitations of in vivo nuclear magnetic resonance (NMR) spectroscopy for quantitation of glucose flux through the pentose phosphate pathway (shunt). Interest in the shunt is motivated by the possibility that its activity may be greatly increased in cancer and in the pathological states of cardiac and cerebral ischemia. The ability to dynamically monitor flux through the pentose shunt can give new knowledge about metabolism in pathological states. {sup 13}C NMR spectroscopy was used to monitor shunt activity by determination of the ratios of ({sup 13}C-4) to ({sup 13}C-5)-glutamate,more » ({sup 13}C-3) to ({sup 13}C-2)-alanine or ({sup 13}C-3) to ({sup 13}C-2)-lactate produced when ({sup 13}C-2)-glucose is infused. These methods provide measures of the effect of oxidative stresses on shunt activity in systems ranging from cell free enzyme-substrate preparations to cell suspensions and whole animals. In anaerobic cell free preparations, the fraction of glucose flux through the shunt was monitored with a time resolution of 3 minutes. This work predicts the potential for in vivo human studies of pentose phosphate pathway activity based on the mathematical simulation of the {sup 13}C fractional enrichments of C4 and C5-glutamate as a function of shunt activity and on the signal-to- noise ratio acquired in {sup 13}C NMR human studies from the current literature.« less

Nuclear magnetic resonance studies of the regulation of the pentose phosphate pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolo, Nicolas Robin

1991-11-01

The goal of this work is to investigate the potential for and limitations of in vivo nuclear magnetic resonance (NMR) spectroscopy for quantitation of glucose flux through the pentose phosphate pathway (shunt). Interest in the shunt is motivated by the possibility that its activity may be greatly increased in cancer and in the pathological states of cardiac and cerebral ischemia. The ability to dynamically monitor flux through the pentose shunt can give new knowledge about metabolism in pathological states. 13C NMR spectroscopy was used to monitor shunt activity by determination of the ratios of [ 13C-4] to [ 13C-5]-glutamate, [more » 13C-3] to [ 13C-2]-alanine or [ 13C-3] to [ 13C-2]-lactate produced when [ 13C-2]-glucose is infused. These methods provide measures of the effect of oxidative stresses on shunt activity in systems ranging from cell free enzyme-substrate preparations to cell suspensions and whole animals. In anaerobic cell free preparations, the fraction of glucose flux through the shunt was monitored with a time resolution of 3 minutes. This work predicts the potential for in vivo human studies of pentose phosphate pathway activity based on the mathematical simulation of the 13C fractional enrichments of C4 and C5-glutamate as a function of shunt activity and on the signal-to- noise ratio acquired in 13C NMR human studies from the current literature.« less

Preferable adsorption of phosphate using lanthanum-incorporated porous zeolite: Characteristics and mechanism

NASA Astrophysics Data System (ADS)

He, Yinhai; Lin, Hai; Dong, Yingbo; Wang, Liang

2017-12-01

The adsorbent, where lanthanum oxide was incorporated onto porous zeolite (La-Z), of preferable adsorption towards phosphate was prepared by hydrothermal synthesis. Based on pH effect results, La-Z would effectively sequestrate phosphate over wider pH range of 3.0-7.0, alkaline conditions were unfavorable for phosphate. The adsorption of phosphate was not significantly influenced by ionic strength and by coexisting anions of chloride, nitrate and sulfate but bicarbonate showed slightly greater negative effects, indicating La-Z possessed highly selectivity to phosphate. Adsorption of phosphate could be well fitted by pseudo-second-order model and the process was mainly controlled by intra-particle diffusion. Equilibrium adsorption demonstrated that Langmuir model was more suitable than Freundlich model for description phosphate adsorption and the adsorption capacity was 17.2 mg P g-1, which exhibited 95% utilization of incorporated La. Over 95% phosphate was eliminated in real effluent treatment when the dose was 2 g L-1. The underlying mechanism for phosphate capture was probed with Zeta potential and X-ray photoelectron spectroscope analysis, and the formation of La-P inner-sphere complexation was testified to be the dominant pathway. All the results suggested that the porous zeolite-supported lanthanum oxide can serve as a promising adsorbent for phosphate removal in realistic application.

Phosphate-bonded ceramic–wood composites : R&D project overview and invitation to participate

Treesearch

Theodore L. Laufenberg; Matt Aro

2004-01-01

We are developing chemically bonded ceramic phosphate binders for the production of biofiber-based composite materials. These binders promise to have better processing and properties than some current cement and polymer resin binder systems. The ceramic phosphate binders (termed Ceramicrete), if used in place of cement and polymers, will significantly reduce the...

Efficient methods for enol phosphate synthesis using carbon-centred magnesium bases.

PubMed

Kerr, William J; Lindsay, David M; Patel, Vipulkumar K; Rajamanickam, Muralikrishnan

2015-10-28

Efficient conversion of ketones into kinetic enol phosphates under mild and accessible conditions has been realised using the developed methods with di-tert-butylmagnesium and bismesitylmagnesium. Optimisation of the quench protocol resulted in high yields of enol phosphates from a range of cyclohexanones and aryl methyl ketones, with tolerance of a range of additional functional units.

Computational modelling of ovine critical-sized tibial defects with implanted scaffolds and prediction of the safety of fixator removal.

PubMed

Doyle, Heather; Lohfeld, Stefan; Dürselen, Lutz; McHugh, Peter

2015-04-01

Computational model geometries of tibial defects with two types of implanted tissue engineering scaffolds, β-tricalcium phosphate (β-TCP) and poly-ε-caprolactone (PCL)/β-TCP, are constructed from µ-CT scan images of the real in vivo defects. Simulations of each defect under four-point bending and under simulated in vivo axial compressive loading are performed. The mechanical stability of each defect is analysed using stress distribution analysis. The results of this analysis highlights the influence of callus volume, and both scaffold volume and stiffness, on the load-bearing abilities of these defects. Clinically-used image-based methods to predict the safety of removing external fixation are evaluated for each defect. Comparison of these measures with the results of computational analyses indicates that care must be taken in the interpretation of these measures. Copyright © 2015 Elsevier Ltd. All rights reserved.

PHOSPHATE AND NITRATE MOVEMENT THROUGH SIMULATED GOLF GREENS. (R828007)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Development of chemically bonded phosphate ceramics for stabilizing low-level mixed wastes

NASA Astrophysics Data System (ADS)

Jeong, Seung-Young

1997-11-01

Novel chemically bonded phosphate ceramics have been developed by acid-base reactions between magnesium oxide and an acid phosphate at room temperature for stabilizing U.S. Department of Energy's low-level mixed waste streams that include hazardous chemicals and radioactive elements. Newberyite (MgHPOsb4.3Hsb2O)-rich magnesium phosphate ceramic was formed by an acid-base reaction between phosphoric acid and magnesium oxide. The reaction slurry, formed at room-temperature, sets rapidly and forms stable mineral phases of newberyite, lunebergite, and residual MgO. Rapid setting also generates heat due to exothermic acid-base reaction. The reaction was retarded by partially neutralizing the phosphoric acid solution by adding sodium or potassium hydroxide. This reduced the rate of reaction and heat generation and led to a practical way of producing novel magnesium potassium phosphate ceramic. This ceramic was formed by reacting stoichiometric amount of monopotassium dihydrogen phosphate crystals, MgO, and water, forming pure-phase of MgKPOsb4.6Hsb2O (MKP) with moderate exothermic reaction. Using this chemically bonded phosphate ceramic matrix, low-level mixed waste streams were stabilized, and superior waste forms in a monolithic structure were developed. The final waste forms showed low open porosity and permeability, and higher compression strength than the Land Disposal Requirements (LDRs). The novel MKP ceramic technology allowed us to develop operational size waste forms of 55 gal with good physical integrity. In this improved waste form, the hazardous contaminants such as RCRA heavy metals (Hg, Pb, Cd, Cr, Ni, etc) were chemically fixed by their conversion into insoluble phosphate forms and physically encapsulated by the phosphate ceramic. In addition, chemically bonded phosphate ceramics stabilized radioactive elements such U and Pu. This was demonstrated with a detailed stabilization study on cerium used as a surrogate (chemically equivalent but nonradioactive) of U and Pu as well as on actual U-contaminated waste water. In particular, the leaching level of mercury in the Toxicity Characteristic Leaching Procedure (TCLP) test was reduced from 5000 to 0.00085 ppm, and the leaching level of cerium in the long term leaching test (ANS 16.1 test) was below the detection limit. These results show that the chemically bonded phosphate ceramics process may be a simple, inexpensive, and efficient method for stabilizing low-level mixed waste streams.

Determination of phosphate phases in sewage sludge ash-based fertilizers by Raman microspectroscopy.

PubMed

Vogel, Christian; Adam, Christian; McNaughton, Don

2013-09-01

The chemical form of phosphate phases in sewage sludge ash (SSA)-based fertilizers was determined by Raman microspectroscopy. Raman mapping with a lateral resolution of 5 × 5 μm(2) easily detected different compounds present in the fertilizers with the help of recorded reference spectra of pure substances. Quartz and aluminosilicates showed Raman bands in the range of 450-520 cm(-1). Phosphates with apatite structure and magnesium triphosphate were determined at around 960 and 980 cm(-1), respectively. Furthermore, calcium/magnesium pyrophosphates were detected in some samples.

Catalysis of GTP Hydrolysis by Small GTPases at Atomic Detail by Integration of X-ray Crystallography, Experimental, and Theoretical IR Spectroscopy*

PubMed Central

Rudack, Till; Jenrich, Sarah; Brucker, Sven; Vetter, Ingrid R.; Gerwert, Klaus; Kötting, Carsten

2015-01-01

Small GTPases regulate key processes in cells. Malfunction of their GTPase reaction by mutations is involved in severe diseases. Here, we compare the GTPase reaction of the slower hydrolyzing GTPase Ran with Ras. By combination of time-resolved FTIR difference spectroscopy and QM/MM simulations we elucidate that the Mg2+ coordination by the phosphate groups, which varies largely among the x-ray structures, is the same for Ran and Ras. A new x-ray structure of a Ran·RanBD1 complex with improved resolution confirmed this finding and revealed a general problem with the refinement of Mg2+ in GTPases. The Mg2+ coordination is not responsible for the much slower GTPase reaction of Ran. Instead, the location of the Tyr-39 side chain of Ran between the γ-phosphate and Gln-69 prevents the optimal positioning of the attacking water molecule by the Gln-69 relative to the γ-phosphate. This is confirmed in the RanY39A·RanBD1 crystal structure. The QM/MM simulations provide IR spectra of the catalytic center, which agree very nicely with the experimental ones. The combination of both methods can correlate spectra with structure at atomic detail. For example the FTIR difference spectra of RasA18T and RanT25A mutants show that spectral differences are mainly due to the hydrogen bond of Thr-25 to the α-phosphate in Ran. By integration of x-ray structure analysis, experimental, and theoretical IR spectroscopy the catalytic center of the x-ray structural models are further refined to sub-Å resolution, allowing an improved understanding of catalysis. PMID:26272610

Catalysis of GTP hydrolysis by small GTPases at atomic detail by integration of X-ray crystallography, experimental, and theoretical IR spectroscopy.

PubMed

Rudack, Till; Jenrich, Sarah; Brucker, Sven; Vetter, Ingrid R; Gerwert, Klaus; Kötting, Carsten

2015-10-02

Small GTPases regulate key processes in cells. Malfunction of their GTPase reaction by mutations is involved in severe diseases. Here, we compare the GTPase reaction of the slower hydrolyzing GTPase Ran with Ras. By combination of time-resolved FTIR difference spectroscopy and QM/MM simulations we elucidate that the Mg(2+) coordination by the phosphate groups, which varies largely among the x-ray structures, is the same for Ran and Ras. A new x-ray structure of a Ran·RanBD1 complex with improved resolution confirmed this finding and revealed a general problem with the refinement of Mg(2+) in GTPases. The Mg(2+) coordination is not responsible for the much slower GTPase reaction of Ran. Instead, the location of the Tyr-39 side chain of Ran between the γ-phosphate and Gln-69 prevents the optimal positioning of the attacking water molecule by the Gln-69 relative to the γ-phosphate. This is confirmed in the RanY39A·RanBD1 crystal structure. The QM/MM simulations provide IR spectra of the catalytic center, which agree very nicely with the experimental ones. The combination of both methods can correlate spectra with structure at atomic detail. For example the FTIR difference spectra of RasA18T and RanT25A mutants show that spectral differences are mainly due to the hydrogen bond of Thr-25 to the α-phosphate in Ran. By integration of x-ray structure analysis, experimental, and theoretical IR spectroscopy the catalytic center of the x-ray structural models are further refined to sub-Å resolution, allowing an improved understanding of catalysis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Lead stabilization by phosphate amendments in soil impacted by paint residue.

PubMed

Schwab, A P; Lewis, K; Banks, M K

2006-01-01

The addition of phosphate was evaluated for contaminant stabilization in soils impacted by lead paint residue. Soils sampled from 15 highway bridge sites in Indiana were screened based on residual lead concentrations from paint contamination. Two appropriate bridge sites were identified in Tippecanoe County, Indiana. Soluble phosphate was added to the soil at a mole ratio of 3:1 P:Pb. The efficacy of phosphate treatment was evaluated by a physiologically based extraction test (PBET), uptake of lead by sunflowers, and leaching of lead from soil columns. Sunflowers were established on both field sites, and the mean Pb concentration in the above-ground biomass indicated that the rate of uptake was similar to plants growing in uncontaminated soil. The second bioavailability assessment was the physiologically based extraction test, designed to evaluate heavy metal availability during ingestion. After 1 year at both sites, the addition of phosphate significantly reduced the concentrations of lead extracted by PBET, indicating that the lead in the amended soils had lower bioavailability than in the unamended soils. In the column study, the contaminated soil produced the highest mass of leached Pb, and the addition of P reduced the mass of Pb in the leachate to similar levels found in the uncontaminated soil. Overall, the addition of soluble phosphate to these soils appears to be an effective approach for immobilizing Pb and reducing the associated bio-accessibility.

Effects of pH and phosphate on glyphosate adsorption to Argentina soils.

NASA Astrophysics Data System (ADS)

De Geronimo, Eduardo; Aparicio, Virginia; Costa, José Luis

2017-04-01

Glyphosate is a non-selective, post-emergence herbicide that is widely used in Argentina. Due to the similar molecular structures, glyphosate and phosphate compete for the same adsorption sites in soil. Soil pH has a strong influence in glyphosate and phosphate adsorption since it modifies the net charge of the molecules and, consequently, the force of the electrostatic interaction between these molecules and soil components. Glyphosate adsorption generally decreases as the soil pH was increased, although there were exceptions. In this work, we study the effects of pH and the presence of phosphate on the adsorption of glyphosate on six different types of Argentina soils. Batch equilibrium technique was employed to study the adsorption of glyphosate onto soils at different pH values (from 3 to 9) and phosphate content (0.5 and 1 mM). Stepwise multiple linear regression analysis was applied to obtain a relationship between the sorption parameters and soil properties. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients with Kf values range from 24.9 to 397.4. Clay contents and soil pH were found to be the most significant soil factors affecting the glyphosate adsorption process. The presence of phosphate significantly decreased the adsorption of glyphosate to soils. The Kf values obtained for all six soils decreased a 40% at 0.5 mM of phosphate and a 55% at 1 mM of phosphate. On the other hand, the affinity parameters of glyphosate to soils varied with changes in pH. A general trend of decrease in glyphosate adsorption with increase in pH was observed for all six studied soils. In turn, there appears to be a maximum glyphosate adsorption at pH close to 6 for most soils when the net charge of the molecule at this pH was approximately -1.7.

ENVIRONMENTAL RISK ASSESSMENT OF PHOSPHATE-BASED REMEDIAL TECHNOLOGY IN METAL CONTAMINATED URBAN AND MINING AREAS IN A SELECTED MISSOURI SUPERFUND SITE

EPA Science Inventory

This project provided important data on fundamental processes responsible for health and environmental risk reductions and environmental safety of the phosphate-based treatments in metal, specifically Pb, contaminated soils. By an integrated approach of environmental risk asse...

A Green's Function Approach to Simulate DNA Damage by the Indirect Effect

NASA Technical Reports Server (NTRS)

Plante, Ianik; Cicinotta, Francis A.

2013-01-01

The DNA damage is of fundamental importance in the understanding of the effects of ionizing radiation. DNA is damaged by the direct effect of radiation (e.g. direct ionization) and by indirect effect (e.g. damage by.OH radicals created by the radiolysis of water). Despite years of research, many questions on the DNA damage by ionizing radiation remains. In the recent years, the Green's functions of the diffusion equation (GFDE) have been used extensively in biochemistry [1], notably to simulate biochemical networks in time and space [2]. In our future work on DNA damage, we wish to use an approach based on the GFDE to refine existing models on the indirect effect of ionizing radiation on DNA. To do so, we will use the code RITRACKS [3] developed at the NASA Johnson Space Center to simulate the radiation track structure and calculate the position of radiolytic species after irradiation. We have also recently developed an efficient Monte-Carlo sampling algorithm for the GFDE of reversible reactions with an intermediate state [4], which can be modified and adapted to simulate DNA damage by free radicals. To do so, we will use the known reaction rate constants between radicals (OH, eaq, H,...) and the DNA bases, sugars and phosphates and use the sampling algorithms to simulate the diffusion of free radicals and chemical reactions with DNA. These techniques should help the understanding of the contribution of the indirect effect in the formation of DNA damage and double-strand breaks.

Calcium phosphate nanocoatings and nanocomposites, part 2: thin films for slow drug delivery and osteomyelitis.

PubMed

Ben-Nissan, Besim; Macha, Innocent; Cazalbou, Sophie; Choi, Andy H

2016-01-01

During the last two decades although many calcium phosphate based nanomaterials have been proposed for both drug delivery, and bone regeneration, their coating applications have been somehow slow due to the problems related to their complicated synthesis methods. In order to control the efficiency of local drug delivery of a biomaterial the critical pore sizes as well as good control of the chemical composition is pertinent. A variety of calcium phosphate based nanocoated composite drug delivery systems are currently being investigated. This review aims to give an update into the advancements of calcium phosphate nanocoatings and thin film nanolaminates. In particular recent research on PLA/hydroxyapatite composite thin films and coatings into the slow drug delivery for the possible treatment of osteomyelitis is covered.

Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rueff, Jean-Michel, E-mail: jean-michel.rueff@ensicaen.fr; Poienar, Maria; Guesdon, Anne

Novel physical or chemical properties are expected in a great variety of materials, in connection with the dimensionality of their structures and/or with their nanostructures, hierarchical superstructures etc. In the search of new advanced materials, the hydrothermal technique plays a crucial role, mimicking the nature able to produce fractal, hyperbranched, urchin-like or snow flake structures. In this short review including new results, this will be illustrated by examples selected in two types of materials, phosphates and phosphonates, prepared by this method. The importance of the synthesis parameters will be highlighted for a magnetic iron based phosphates and for hybrids containingmore » phosphonates organic building units crystallizing in different structural types. - Graphical abstract: Phosphate dendrite like and phosphonate platelet crystals.« less

Structural characterization of anion-calcium-humate complexes in phosphate-based fertilizers.

PubMed

Baigorri, Roberto; Urrutia, Oscar; Erro, Javier; Mandado, Marcos; Pérez-Juste, Ignacio; Garcia-Mina, José María

2013-07-01

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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The economic impact of improving phosphate binder therapy adherence and attainment of guideline phosphorus goals in hemodialysis patients: a Medicare cost-offset model.

PubMed

Ramakrishnan, Karthik; Braunhofer, Peter; Newsome, Britt; Lubeck, Deborah; Wang, Steven; Deuson, Jennifer; Claxton, Ami J

2014-12-01

Hyperphosphatemia (serum phosphorus >5.5 mg/dL) in hemodialysis patients is a key factor in mineral and bone disorders and is associated with increased hospitalization and mortality risks. Treatment with oral phosphate binders offers limited benefit in achieving target serum phosphorus concentrations due to high daily pill burden (7-10 pills/day) and associated poor medication adherence. The economic value of improving phosphate binder adherence and increasing percent time in range (PTR) for target phosphorus concentrations has not been previously assessed in dialysis patients. The current retrospective analysis was conducted to summarize health care cost savings to United States (US) payers associated with improved phosphate binder adherence and increased PTR for target phosphorus concentrations in adult end-stage renal disease (ESRD) patients receiving hemodialysis therapy. Phosphate binder adherence and PTR were derived from hemodialysis patients who were treated at a large dialysis organization between January 2007 and December 2011. Cost model inputs were derived from US Renal Data System data between July 2007 and December 2009. A cost-offset model was constructed to estimate monthly and annual incremental health care costs (total Medicare; inpatient, outpatient, and Medicare Part B) associated with different levels of phosphate binder adherence and PTR. Model inputs included number of ESRD patients, population adherence to phosphate binders, PTR associated with adherence to phosphate binders, and per-patient per-month cost associated with PTR. A base case model estimated monthly and annual costs of phosphate binder therapy in the population using estimated model inputs. The estimated adherence rate was used to determine number of patients in compliant and noncompliant groups. Monthly costs were calculated as the sum of per-patient per-month cost times the number of patients in adherent and nonadherent groups. Annual costs were monthly costs times 12 and assumed the same level of adherence, PTR, and per-patient per-month costs over time. To study the impact of improving phosphate binder adherence and PTR on cost outcomes, we hypothetically and simultaneously increased both base phosphate binders adherence and PTR for adherent patients (adherence/PTR: 10/20%, 20/40%, 30/60%). Monthly and annual costs were derived for each scenario and compared against the results of the base case model. One-way sensitivity analysis was performed to test model robustness. The base case model estimated total Medicare and inpatient costs of $5,152,342 and $1,435,644, respectively (N = 1,000). When base case model costs were compared to results of each extended model scenario, overall Medicare cost savings (range 0.3-1.9%) and inpatient cost savings (range 1.2-5.7%) were observed. The one-way sensitivity analysis indicated that results were sensitive to PTR for adherent and nonadherent patients and the factor used to increase adherence rate and PTR associated with adherence in the hypothetical scenarios. However, cost savings in overall Medicare costs and inpatient costs were still noted. Increasing phosphate binder adherence and improving phosphorus control were associated with increased cost savings in total Medicare costs and inpatient costs.

Phosphate rock resources of the United States

USGS Publications Warehouse

Cathcart, James Bachelder; Sheldon, Richard Porter; Gulbrandsen, Robert A.

1984-01-01

In 1980, the United States produced about 54 million tons of phosphate rock, or about 40 percent of the world's production, of which a substantial amount was exported, both as phosphate rock and as chemical fertilizer. During the last decade, predictions have been made that easily ruinable, low-cost reserves of phosphate rock would be exhausted, and that by the end of this century, instead of being a major exporter of phosphate rock, the United States might become a net importer. Most analysts today, however, think that exports will indeed decline in the next one or two decades, but that resources of phosphate are sufficient to supply domestic needs for a long time into the future. What will happen in the future depends on the actual availability of low-cost phosphate rock reserves in the United States and in the world. A realistic understanding of future phosphate rock reserves is dependent on an accurate assessment, now, of national phosphate rock resources. Many different estimates of resources exist; none of them alike. The detailed analysis of past resource estimates presented in this report indicates that the estimates differ more in what is being estimated than in how much is thought to exist. The phosphate rock resource classification used herein is based on the two fundamental aspects of a mineral resource(l) the degree of certainty of existence and (2) the feasibility of economic recovery. The comparison of past estimates (including all available company data), combined with the writers' personal knowledge, indicates that 17 billion metric tons of identified, recoverable phosphate rock exist in the United States, of which about 7 billion metric tons are thought to be economic or marginally economic. The remaining 10 billion metric tons, mostly in the Northwestern phosphate district of Idaho, are considered to be subeconomic, ruinable when some increase in the price of phosphate occurs. More than 16 billion metric tons probably exist in the southeastern Coastal Plain phosphate province, principally in Florida and North Carolina and offshore in the shallow Atlantic Ocean from North Carolina to southern Florida. This resource is considered to be hypothetical because it is based on geologic inference combined with sparse drilling data. Total resources of phosphate rock in the United States are sufficient to supply domestic demands for the foreseeable future, provided that drilling is done to confirm hypothetical resources and the chemistry of the deposits is determined. Mining and beneficiation techniques will have to be modified or improved, and new techniques will have to be developed so that these deposits can be profitably exploited.

Transport of U(VI) through sediments amended with phosphate to induce in situ uranium immobilization.

PubMed

Mehta, Vrajesh S; Maillot, Fabien; Wang, Zheming; Catalano, Jeffrey G; Giammar, Daniel E

2015-02-01

Phosphate amendments can be added to U(VI)-contaminated subsurface environments to promote in situ remediation. The primary objective of this study was to evaluate the impacts of phosphate addition on the transport of U(VI) through contaminated sediments. In batch experiments using sediments (<2 mm size fraction) from a site in Rifle, Colorado, U(VI) only weakly adsorbed due to the dominance of the aqueous speciation by Ca-U(VI)-carbonate complexes. Column experiments with these sediments were performed with flow rates that correspond to a groundwater velocity of 1.1 m/day. In the absence of phosphate, the sediments took up 1.68-1.98 μg U/g of sediments when the synthetic groundwater influent contained 4 μM U(VI). When U(VI)-free influents were then introduced with and without phosphate, substantially more uranium was retained within the column when phosphate was present in the influent. Sequential extractions of sediments from the columns revealed that uranium was uniformly distributed along the length of the columns and was primarily in forms that could be extracted by ion exchange and contact with a weak acid. Laser induced fluorescence spectroscopy (LIFS) analysis along with sequential extraction results suggest adsorption as the dominant uranium uptake mechanism. The response of dissolved uranium concentrations to stopped-flow events and the comparison of experimental data with simulations from a simple reactive transport model indicated that uranium adsorption to and desorption from the sediments was not always at local equilibrium. Copyright © 2014 Elsevier Ltd. All rights reserved.

Calcium phosphate/chitosan composite coating: Effect of different concentrations of Mg2+ in the m-SBF on its bioactivity

NASA Astrophysics Data System (ADS)

Zhang, Jie; Dai, Changsong; Wei, Jie; Wen, Zhaohui; Zhang, Shujuan; Lin, Lemin

2013-09-01

The purpose of this study was to investigate the effect of different concentration of Mg2+ in a modified simulated body fluid (m-SBF) on the bioactivity of calcium phosphate/chitosan composite coating. Calcium phosphate/chitosan composite coating was prepared on graphite substrate via electrophoretic deposition (EPD) followed by conversion in a phosphate buffer solution (PBS). The obtained samples were soaked in the m-SBF containing different concentration of Mg2+ for different times. And then, the composite coatings were assessed using X-ray diffractometer (XRD), Fourier-transformed infrared spectroscopy (FTIR), Raman spectra, and scanning electron microscope (SEM) with an energy dispersive spectrometer (EDS). The soaking solution was evaluated by inductively coupled plasma optical emission spectrometer (ICP-OES) test. The analytical results showed that hydroxyapatite (HA) and bone-like apatite (HCA) grew on the surface of calcium phosphate/chitosan composite coating after incubation in different m-SBF. With Mg2+ concentration in m-SBF increased from 1× Mg to 10× Mg, HA in the composite coating first presented a dissolving process and then a precipitating one slowly, while HCA presented a growing trend, continuously. The increasing of Mg2+ concentration in the m-SBF inhibited the total growing process of HA and HCA as a whole. The structure of the composite coating changed from spherical into irregular morphology with the concentration of Mg2+ increasing from 1× Mg to 10× Mg. Over all, with the Mg2+ concentration increasing, the bioactivity of calcium phosphate/chitosan composite coating tended to decrease.

Development and Validation of Different Ultraviolet-Spectrophotometric Methods for the Estimation of Besifloxacin in Different Simulated Body Fluids.

PubMed

Singh, C L; Singh, A; Kumar, S; Kumar, M; Sharma, P K; Majumdar, D K

2015-01-01

In the present study a simple, accurate, precise, economical and specific UV-spectrophotometric method for estimation of besifloxacin in bulk and in different pharmaceutical formulation has been developed. The drug shows maximum λmax289 nm in distilled water, simulated tears and phosphate buffer saline. The linearity range of developed methods were in the range of 3-30 μg/ml of drug with a correlation coefficient (r(2)) 0.9992, 0.9989 and 0.9984 with respect to distilled water, simulated tears and phosphate buffer saline, respectively. Reproducibility by repeating methods as %RSD were found to be less than 2%. The limit of detection in different media was found to be 0.62, 0.72 and 0.88 μg/ml, respectively. The limit of quantification was found to be 1.88, 2.10, 2.60 μg/ml, respectively. The proposed method was validated statically according to International Conference on Harmonization guidelines with respect to specificity, linearity, range, accuracy, precision and robustness. The proposed methods of validation were found to be accurate and highly specific for the estimation of besifloxacin in different pharmaceutical formulations.

Phosphate Recovery from Human Waste via the Formation of Hydroxyapatite during Electrochemical Wastewater Treatment

PubMed Central

2018-01-01

Electrolysis of toilet wastewater with TiO2-coated semiconductor anodes and stainless steel cathodes is a potentially viable onsite sanitation solution in parts of the world without infrastructure for centralized wastewater treatment. In addition to treating toilet wastewater, pilot-scale and bench-scale experiments demonstrated that electrolysis can remove phosphate by cathodic precipitation as hydroxyapatite at no additional energy cost. Phosphate removal could be predicted based on initial phosphate and calcium concentrations, and up to 80% total phosphate removal was achieved. While calcium was critical for phosphate removal, magnesium and bicarbonate had only minor impacts on phosphate removal rates at concentrations typical of toilet wastewater. Optimal conditions for phosphate removal were 3 to 4 h treatment at about 5 mA cm–2 (∼3.4 V), with greater than 20 m2 m–3 electrode surface area to reactor volume ratios. Pilot-scale systems are currently operated under similar conditions, suggesting that phosphate removal can be viewed as an ancillary benefit of electrochemical wastewater treatment, adding utility to the process without requiring additional energy inputs. Further value may be provided by designing reactors to recover precipitated hydroxyapatite for use as a low solubility phosphorus-rich fertilizer. PMID:29607266

Exploring the Link between Serum Phosphate Levels and Low Muscle Strength, Dynapenia, and Sarcopenia.

PubMed

Chen, Yuan-Yuei; Kao, Tung-Wei; Chou, Cheng-Wai; Wu, Chen-Jung; Yang, Hui-Fang; Lai, Ching-Huang; Wu, Li-Wei; Chen, Wei-Liang

2018-02-23

Emerging evidences addressed an association between phosphate and muscle function. Because little attention was focused on this issue, the objective of our study was to explore the relationship of phosphate with muscle strength, dynapenia, and sarcopenia. From the National Health and Nutrition Examination Survey, a total of 7421 participants aged 20 years or older were included in our study with comprehensive examinations included anthropometric parameters, strength of the quadriceps muscle, and appendicular lean masses. Within the normal range of serum phosphate, we used quartile-based analyses to determine the potential relationships of serum phosphate with dynapenia, and sarcopenia through multivariate regression models. After adjusting for the pertinent variables, an inverse association between the serum phosphate quartiles and muscle strength was observed and the linear association was stronger than other anthropometric parameters. Notably, the significant association between phosphate and muscle strength was existed in >65 years old age group, not in 20-65 years old. The higher quartiles of phosphate had higher likelihood for predicting the presence of dynapenia rather than sarcopenia in entire population. Our study highlighted that higher quartiles of phosphate had significant association with lower muscle strength and higher risks for predicting the presence of dynapenia.

Phosphate Recovery from Human Waste via the Formation of Hydroxyapatite during Electrochemical Wastewater Treatment.

PubMed

Cid, Clément A; Jasper, Justin T; Hoffmann, Michael R

2018-03-05

Electrolysis of toilet wastewater with TiO 2 -coated semiconductor anodes and stainless steel cathodes is a potentially viable onsite sanitation solution in parts of the world without infrastructure for centralized wastewater treatment. In addition to treating toilet wastewater, pilot-scale and bench-scale experiments demonstrated that electrolysis can remove phosphate by cathodic precipitation as hydroxyapatite at no additional energy cost. Phosphate removal could be predicted based on initial phosphate and calcium concentrations, and up to 80% total phosphate removal was achieved. While calcium was critical for phosphate removal, magnesium and bicarbonate had only minor impacts on phosphate removal rates at concentrations typical of toilet wastewater. Optimal conditions for phosphate removal were 3 to 4 h treatment at about 5 mA cm -2 (∼3.4 V), with greater than 20 m 2 m -3 electrode surface area to reactor volume ratios. Pilot-scale systems are currently operated under similar conditions, suggesting that phosphate removal can be viewed as an ancillary benefit of electrochemical wastewater treatment, adding utility to the process without requiring additional energy inputs. Further value may be provided by designing reactors to recover precipitated hydroxyapatite for use as a low solubility phosphorus-rich fertilizer.

Enhanced phosphorus reduction in simulated eutrophic water: a comparative study of submerged macrophytes, sediment microbial fuel cells, and their combination.

PubMed

Xu, Peng; Xiao, Enrong; Xu, Dan; Li, Juan; Zhang, Yi; Dai, Zhigang; Zhou, Qiaohong; Wu, Zhenbin

2018-05-01

The phosphorus reduction in water column was attempted by integrating sediment microbial fuel cells (SMFCs) with the submerged macrophyte Vallisneria spiralis. A comparative study was conducted to treat simulated water rich in phosphate with a control and three treatments: SMFC alone (SMFC), submerged macrophytes alone (macophyte), and combined macrophytes and fuel cells (M-SMFC). All treatments promoted phosphorus flux from the water column to sediments. Maximum phosphorus reduction was obtained in proportion to the highest stable phosphorus level in sediments in M-SMFC. For the initial phosphate concentrations of 0.2, 1, 2, and 4 mg/L, average phosphate values in the overlying water during four phases decreased by 33.3% (25.0%, 8.3%), 30.8% (5.1%, 17.9%), 36.5% (27.8%, 15.7%), and 36.2% (0.7%, 22.1%) for M-SMFC (macrophyte, SMFC), compared with the control. With macrophyte treatment, the obvious phosphorus release from sediments was observed during the declining period. However, such phenomenon was significantly inhibited with M-SMFC. The electrogenesis bacteria achieved stronger phosphorus adsorption and assimilation was significantly enriched on the closed-circuit anodes. The higher abundance of Geobacter and Pseudomonas in M-SMFC might in part explain the highest phosphorus reduction in the water column. M-SMFC treatment could be promising to control the phosphorus in eutrophic water bodies.

Polymeric additives to enhance the functional properties of calcium phosphate cements

PubMed Central

Perez, Roman A; Kim, Hae-Won

2012-01-01

The vast majority of materials used in bone tissue engineering and regenerative medicine are based on calcium phosphates due to their similarity with the mineral phase of natural bone. Among them, calcium phosphate cements, which are composed of a powder and a liquid that are mixed to obtain a moldable paste, are widely used. These calcium phosphate cement pastes can be injected using minimally invasive surgery and adapt to the shape of the defect, resulting in an entangled network of calcium phosphate crystals. Adding an organic phase to the calcium phosphate cement formulation is a very powerful strategy to enhance some of the properties of these materials. Adding some water-soluble biocompatible polymers in the calcium phosphate cement liquid or powder phase improves physicochemical and mechanical properties, such as injectability, cohesion, and toughness. Moreover, adding specific polymers can enhance the biological response and the resorption rate of the material. The goal of this study is to overview the most relevant advances in this field, focusing on the different types of polymers that have been used to enhance specific calcium phosphate cement properties. PMID:22511991

Molecular analysis of phosphate limitation in Geobacteraceae during the bioremediation of a uranium-contaminated aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

N'Guessan, L.A.; Elifantz, H.; Nevin, K.P.

2009-09-01

Nutrient limitation is an environmental stress that may reduce the effectiveness of bioremediation strategies, especially when the contaminants are organic compounds or when organic compounds are added to promote microbial activities such as metal reduction. Genes indicative of phosphate-limitation were identified via microarray analysis of chemostat cultures of Geobacter sulfureducens. This analysis revealed that genes in the pst-pho operon, which is associated with a high affinity phosphate uptake system in other microorganisms, had significantly higher transcript abundance under phosphate-limiting conditions, with the genes pstB and phoU the most up-regulated. Quantitative PCR analysis of pstB and phoU transcript levels in G.more » sulfurreducens grown in chemostats demonstrated that the expression of these genes increased when phosphate was removed from the culture medium. Transcripts of pstB and phoU within the subsurface Geobacter species predominating during an in situ uranium bioremediation field experiment were more abundant than in chemostat cultures of G. sulfurreducens that were not limited for phosphate. Addition of phosphate to incubations of subsurface sediments did not stimulate dissimilatory metal reduction. The added phosphate was rapidly adsorbed onto the sediments. The results demonstrate that Geobacter species can effectively reduce U(VI) even when experiencing suboptimal phosphate concentrations and that increasing phosphate availability with phosphate additions is difficult to achieve due to the high reactivity of this compound. This transcript-based approach developed for diagnosing phosphate limitation should be applicable to assessing the potential need for additional phosphate in other bioremediation processes.« less

Molecular Analysis of Phosphate Limitation in Geobacteraceae During the Bioremediation of a Uranium-Contaminated Aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

N'Guessan, A. Lucie; Elifantz, H.; Nevin, Kelly P.

2010-02-01

Nutrient limitation is an environmental stress that may reduce the effectiveness of bioremediation strategies, especially when the contaminants are organic compounds or when organic compounds are added to promote microbial activities such as metal reduction. Genes indicative of phosphate-limitation were identified via microarray analysis of chemostat cultures of Geobacter sulfureducens. This analysis revealed that genes in the pst-pho operon, which is associated with a high affinity phosphate uptake system in other microorganisms, had significantly higher transcript abundance under phosphate-limiting conditions, with the genes pstB and phoU the most up-regulated. Quantitative PCR analysis of pstB and phoU transcript levels in G.more » sulfurreducens grown in chemostats demonstrated that the expression of these genes increased when phosphate was removed from the culture medium. Transcripts of pstB and phoU within the subsurface Geobacter species predominating during an in situ uranium bioremediation field experiment were more abundant than in chemostat cultures of G. sulfurreducens that were not limited for phosphate. Addition of phosphate to incubations of subsurface sediments did not stimulate dissimilatory metal reduction. The added phosphate was rapidly adsorbed onto the sediments. The results demonstrate that Geobacter species can effectively reduce U(VI) even when experiencing suboptimal phosphate concentrations and that increasing phosphate availability with phosphate additions is difficult to achieve due to the high reactivity of this compound. This transcript-based approach developed for diagnosing phosphate limitation should be applicable to assessing the potential need for additional phosphate in other bioremediation processes.« less

Application of Water Quality Model of Jordan River to Evaluate Climate Change Effects on Eutrophication

NASA Astrophysics Data System (ADS)

Van Grouw, B.

2016-12-01

The Jordan River is a 51 mile long freshwater stream in Utah that provides drinking water to more than 50% of Utah's population. The various point and nonpoint sources introduce an excess of nutrients into the river. This excess induces eutrophication that results in an inhabitable environment for aquatic life is expected to be exacerbated due to climate change. Adaptive measures must be evaluated based on predictions of climate variation impacts on eutrophication and ecosystem processes in the Jordan River. A Water Quality Assessment Simulation Program (WASP) model was created to analyze the data results acquired from a Total Maximum Daily Load (TMDL) study conducted on the Jordan River. Eutrophication is modeled based on levels of phosphates and nitrates from point and nonpoint sources, temperature, and solar radiation. It will simulate the growth of phytoplankton and periphyton in the river. This model will be applied to assess how water quality in the Jordan River is affected by variations in timing and intensity of spring snowmelt and runoff during drought in the valley and the resulting effects on eutrophication in the river.

Effect of strain on actomyosin kinetics in isometric muscle fibers.

PubMed

Siththanandan, V B; Donnelly, J L; Ferenczi, M A

2006-05-15

Investigations were conducted into the biochemical and mechanical states of cross-bridges during isometric muscle contraction. Rapid length steps (3 or 6 nm hs(-1)) were applied to rabbit psoas fibers, permeabilized and isometric, at either 12 degrees C or 20 degrees C. Fibers were activated by photolysis of P(3)-1-(2-nitrophenyl)-ethyl ester of ATP infused into rigor fibers at saturating Ca(2+). Sarcomere length, tension, and phosphate release were recorded-the latter using the MDCC-PBP fluorescent probe. A reduction in strain, induced by a rapid release step, produced a short-lived acceleration of phosphate release. Rates of the phosphate transient and that of phases 3 and 4 of tension recovery were unaffected by step size but were elevated at higher temperatures. In contrast the amplitude of the phosphate transient was smaller at 20 degrees C than 12 degrees C. The presence of 0.5 or 1.0 mM added ADP during a release step reduced both the rate of tension recovery and the poststep isometric tension. A kinetic scheme is presented to simulate the observed data and to precisely determine the rate constants for the elementary steps of the ATPase cycle.

Potentiostatic pulse-deposition of calcium phosphate on magnesium alloy for temporary implant applications--an in vitro corrosion study.

PubMed

Kannan, M Bobby; Wallipa, O

2013-03-01

In this study, a magnesium alloy (AZ91) was coated with calcium phosphate using potentiostatic pulse-potential and constant-potential methods and the in vitro corrosion behaviour of the coated samples was compared with the bare metal. In vitro corrosion studies were carried out using electrochemical impedance spectroscopy and potentiodynamic polarization in simulated body fluid (SBF) at 37 °C. Calcium phosphate coatings enhanced the corrosion resistance of the alloy, however, the pulse-potential coating performed better than the constant-potential coating. The pulse-potential coating exhibited ~3 times higher polarization resistance than that of the constant-potential coating. The corrosion current density obtained from the potentiodynamic polarization curves was significantly less (~60%) for the pulse-deposition coating as compared to the constant-potential coating. Post-corrosion analysis revealed only slight corrosion on the pulse-potential coating, whereas the constant-potential coating exhibited a large number of corrosion particles attached to the coating. The better in vitro corrosion performance of the pulse-potential coating can be attributed to the closely packed calcium phosphate particles. Copyright © 2012 Elsevier B.V. All rights reserved.

SU-E-T-494: Influence of Proton Track-Cell Nucleus Incidence Angle On Relative Biological Effectiveness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pater, P; Backstrom, G; Enger, S

2015-06-15

Purpose: To explain a Monte Carlo (MC) simulation artifact whereby differences in relative biological effectiveness (RBE) in the induction of initial double strand breaks are observed as a function of the proton track incidence angles in a geometric cell nucleus model. Secondly, to offer an alternative isotropic irradiation procedure to mitigate this effect. Methods: MC tracks of 1 MeV protons were generated in an event-by-event mode. They were overlaid on a cylindrical model of a cell nucleus containing 6×109 nucleotide base pairs. The tracks incidence angle θ with respect to the cell nucleus’s axis was varied in 10 degrees intervals,more » each time generating one hundred fractions of ∼2 Gy. Strand breaks were scored in the modeled DNA sugar-phosphate groups and further sub-classified into single or double strand breaks (ssbs or dsbs). For each angle, an RBE for the induction of initial dsbs with reference to Co-60 was calculated. Results: Our results show significant angular dependencies of RBE, with maximum values for incidence angles parallel to the nucleus central axis. Further examination shows that the higher cross-sections for the creation of dsbs is due to the preferential alignment of tracks with geometrical sub-parts of the cell nucleus model, especially the nucleosomes containing the sugar-phosphate groups. To alleviate the impact of this simulation artifact, an average RBE was calculated with a procedure based on a weighted sampling of the angular data. Conclusion: This work demonstrates a possible numerical artifact in estimated RBE if the influence of the particle incidence angle is not correctly taken into account. A correction procedure is presented to better conform the simulations to real-life experimental conditions. We would like to acknowledge support from the Fonds de recherche du Quebec Sante (FRQS), from the CREATE Medical Physics Research Training Network grant (number 432290) of NSERC, support from NSERC under grants RGPIN 397711-11 and RGPIN-2014-06475 and support from the CIHR under grants MOP-114910, MOP-136774 and MOP-102550.« less

Network-level fossil of a phosphate-free biosphere

NASA Astrophysics Data System (ADS)

Goldford, J.; Hartman, H.; Smith, T. F.; Segre, D.

2017-12-01

The emergence of a metabolism capable of sustaining cellular life on early Earth is a major unresolved enigma. Such a transition from prebiotic chemistry to an organized biochemical network seemingly required the concurrent availability of multiple molecular components. One of these components, phosphate, carries several essential functions in present-day metabolism, most notably energy transduction through ATP. However, the ubiquity of phosphate in living systems today stands in sharp contrast with its poor geochemical availability, prompting previous efforts to search for plausible prebiotic sources. The alternative, intriguing possibility is that primitive life did not require phosphate. Here we explore this possibility by determining the feasibility and functional potential of a phosphate-independent metabolism amongst the set of all known biochemical reactions in the biosphere. Surprisingly, we identified a cryptic phosphate-independent core metabolism that can be generated from simple sets of compounds thought to be available on early Earth. This network can support the biosynthesis of a broad category of key biomolecules. The enzymes contained in this network display a striking enrichment for dependence on iron-sulfur and transition metal coenzymes, a fundamental cornerstone of early biochemistry. We furthermore show that phosphate-independent precursors of present-day cofactors could have helped overcome thermodynamic energy barriers, enabling the production of a rich set of biomolecules, including 15 out of the 20 amino acids, vitamins, pentoses and nucleobases. Altogether, our results suggest that present-day biochemical networks may contain vestiges of a very ancient past, and that a complex thioester-based metabolism could have predated the incorporation of phosphate and an RNA-based genetic system.

Scale-up of phosphate remobilization from sewage sludge in a microbial fuel cell.

PubMed

Happe, Manuel; Sugnaux, Marc; Cachelin, Christian Pierre; Stauffer, Marc; Zufferey, Géraldine; Kahoun, Thomas; Salamin, Paul-André; Egli, Thomas; Comninellis, Christos; Grogg, Alain-François; Fischer, Fabian

2016-01-01

Phosphate remobilization from digested sewage sludge containing iron phosphate was scaled-up in a microbial fuel cell (MFC). A 3litre triple chambered MFC was constructed. This reactor was operated as a microbial fuel cell and later as a microbial electrolysis cell to accelerate cathodic phosphate remobilization. Applying an additional voltage and exceeding native MFC power accelerated chemical base formation and the related phosphate remobilization rate. The electrolysis approach was extended using a platinum-RVC cathode. The pH rose to 12.6 and phosphate was recovered by 67% in 26h. This was significantly faster than using microbial fuel cell conditions. Shrinking core modelling particle fluid kinetics showed that the reaction resistance has to move inside the sewage sludge particle for considerable rate enhancement. Remobilized phosphate was subsequently precipitated as struvite and inductively coupled plasma mass spectrometry indicated low levels of cadmium, lead, and other metals as required by law for recycling fertilizers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Combination of struvite pyrolysate recycling with mixed-base technology for removing ammonium from fertilizer wastewater.

PubMed

Yu, Rongtai; Geng, Jinju; Ren, Hongqiang; Wang, Yanru; Xu, Ke

2012-11-01

Removal of ammonium from wastewater via struvite (MAP) pyrolysate recycling combined with a mixed-base NaOH/Mg(OH)(2) technology was investigated, and the phosphate and magnesium concentration in the supernatant were measured. The optimal parameters for acidolysis were a pH of 1; temperature of 120°C and time of 2h. The presence of derivatives of amorphous magnesium hydrogen phosphate (MgHPO(4)), namely magnesium phosphate (Mg(3)(PO(4))(2)) and magnesium pyrophosphate (Mg(2)P(2)O(7)) were verified by experiment. The ammonium removal ratio in this combined mixed-base technology was 96.8% in the first cycle, 80.6% in the second, and 81.0% after acidolysis. The phosphate and magnesium ions concentration in the supernatant were about 1mg/L and 40 mg/L, respectively. The grain size of MAP was 1.52 nm without seeding and 1.79 nm with seeding, and the growth rate of MAP was 17.6%. Copyright © 2012 Elsevier Ltd. All rights reserved.

A construction of novel iron-foam-based calcium phosphate/chitosan coating biodegradable scaffold material.

PubMed

Wen, Zhaohui; Zhang, Liming; Chen, Chao; Liu, Yibo; Wu, Changjun; Dai, Changsong

2013-04-01

Slow corrosion rate and poor bioactivity restrict iron-based implants in biomedical application. In this study, we design a new iron-foam-based calcium phosphate/chitosan coating biodegradable composites offering a priority mechanical and bioactive property for bone tissue engineering through electrophoretic deposition (EPD) followed by a conversion process into a phosphate buffer solution (PBS). Tensile test results showed that the mechanical property of iron foam could be regulated through altering the construction of polyurethane foam. The priority coatings were deposited from 40% nano hydroxyapatite (nHA)/ethanol suspension mixed with 60% nHA/chitosan-acetic acid aqueous solution. In vitro immersion test showed that oxidation-iron foam as the matrix decreased the amount of iron implanted and had not influence on the bioactivity of this implant, obviously. So, this method could also be a promising method for the preparation of a new calcium phosphate/chitosan coating on foam construction. Copyright © 2012. Published by Elsevier B.V.

GDP Release Preferentially Occurs on the Phosphate Side in Heterotrimeric G-proteins

PubMed Central

Louet, Maxime; Martinez, Jean; Floquet, Nicolas

2012-01-01

After extra-cellular stimulation of G-Protein Coupled Receptors (GPCRs), GDP/GTP exchange appears as the key, rate limiting step of the intracellular activation cycle of heterotrimeric G-proteins. Despite the availability of a large number of X-ray structures, the mechanism of GDP release out of heterotrimeric G-proteins still remains unknown at the molecular level. Starting from the available X-ray structure, extensive unconstrained/constrained molecular dynamics simulations were performed on the complete membrane-anchored Gi heterotrimer complexed to GDP, for a total simulation time overcoming 500 ns. By combining Targeted Molecular Dynamics (TMD) and free energy profiles reconstruction by umbrella sampling, our data suggest that the release of GDP was much more favored on its phosphate side. Interestingly, upon the forced extraction of GDP on this side, the whole protein encountered large, collective motions in perfect agreement with those we described previously including a domain to domain motion between the two ras-like and helical sub-domains of Gα. PMID:22829757

Rapid simulated gastric fluid digestion of in-seed/grain proteins expressed in genetically engineered crops.

PubMed

Schafer, Barry W; Embrey, Shawna K; Herman, Rod A

2016-11-01

The speed of simulated gastric digestion of proteins expressed in genetically engineered (GE) crops is commonly used to inform the allergenicity risk assessment. However, persistence of purified proteins in simulated gastric fluid (SGF) is poorly correlated with the allergenic status of proteins. It has been proposed that the plant or food matrix may affect the digestion of proteins and should be considered in interpreting digestion results. Here the SGF digestion of several GE proteins both as purified preparations and in soybean, corn, and cotton seed/grain extracts (in-matrix) are compared. Cry1F, Cry1Ac, phosphinothricin acetyltransferase (PAT), aryloxyalkanoate dioxygenase-1 (AAD-1), aryloxyalkanoate dioxygenase-12 (AAD-12), and double mutant 5-enol pyruvylshikimate-3-phosphate synthase (2mEPSPS) were all found to rapidly digest both as purified protein preparations and in seed/grain extracts from GE crops expressing these proteins. Based on these results, purified protein from microbial sources is a suitable surrogate for proteins in-matrix when conducting SGF digestion studies. Copyright © 2016 Elsevier Inc. All rights reserved.

Improved model of hydrated calcium ion for molecular dynamics simulations using classical biomolecular force fields.

PubMed

Yoo, Jejoong; Wilson, James; Aksimentiev, Aleksei

2016-10-01

Calcium ions (Ca(2+) ) play key roles in various fundamental biological processes such as cell signaling and brain function. Molecular dynamics (MD) simulations have been used to study such interactions, however, the accuracy of the Ca(2+) models provided by the standard MD force fields has not been rigorously tested. Here, we assess the performance of the Ca(2+) models from the most popular classical force fields AMBER and CHARMM by computing the osmotic pressure of model compounds and the free energy of DNA-DNA interactions. In the simulations performed using the two standard models, Ca(2+) ions are seen to form artificial clusters with chloride, acetate, and phosphate species; the osmotic pressure of CaAc2 and CaCl2 solutions is a small fraction of the experimental values for both force fields. Using the standard parameterization of Ca(2+) ions in the simulations of Ca(2+) -mediated DNA-DNA interactions leads to qualitatively wrong outcomes: both AMBER and CHARMM simulations suggest strong inter-DNA attraction whereas, in experiment, DNA molecules repel one another. The artificial attraction of Ca(2+) to DNA phosphate is strong enough to affect the direction of the electric field-driven translocation of DNA through a solid-state nanopore. To address these shortcomings of the standard Ca(2+) model, we introduce a custom model of a hydrated Ca(2+) ion and show that using our model brings the results of the above MD simulations in quantitative agreement with experiment. Our improved model of Ca(2+) can be readily applied to MD simulations of various biomolecular systems, including nucleic acids, proteins and lipid bilayer membranes. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 752-763, 2016. © 2016 Wiley Periodicals, Inc.

An unexpected phosphate binding site in Glyceraldehyde 3-Phosphate Dehydrogenase: Crystal structures of apo, holo and ternary complex of Cryptosporidium parvum enzyme

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, William J; Senkovich, Olga; Chattopadhyay, Debasish

2009-06-08

The structure, function and reaction mechanism of glyceraldehyde 3-phosphate dehydrogenase (GAPDH) have been extensively studied. Based on these studies, three anion binding sites have been identified, one 'Ps' site (for binding the C-3 phosphate of the substrate) and two sites, 'Pi' and 'new Pi', for inorganic phosphate. According to the original flip-flop model, the substrate phosphate group switches from the 'Pi' to the 'Ps' site during the multistep reaction. In light of the discovery of the 'new Pi' site, a modified flip-flop mechanism, in which the C-3 phosphate of the substrate binds to the 'new Pi' site and flips tomore » the 'Ps' site before the hydride transfer, was proposed. An alternative model based on a number of structures of B. stearothermophilus GAPDH ternary complexes (non-covalent and thioacyl intermediate) proposes that in the ternary Michaelis complex the C-3 phosphate binds to the 'Ps' site and flips from the 'Ps' to the 'new Pi' site during or after the redox step. We determined the crystal structure of Cryptosporidium parvum GAPDH in the apo and holo (enzyme + NAD) state and the structure of the ternary enzyme-cofactor-substrate complex using an active site mutant enzyme. The C. parvum GAPDH complex was prepared by pre-incubating the enzyme with substrate and cofactor, thereby allowing free movement of the protein structure and substrate molecules during their initial encounter. Sulfate and phosphate ions were excluded from purification and crystallization steps. The quality of the electron density map at 2{angstrom} resolution allowed unambiguous positioning of the substrate. In three subunits of the homotetramer the C-3 phosphate group of the non-covalently bound substrate is in the 'new Pi' site. A concomitant movement of the phosphate binding loop is observed in these three subunits. In the fourth subunit the C-3 phosphate occupies an unexpected site not seen before and the phosphate binding loop remains in the substrate-free conformation. Orientation of the substrate with respect to the active site histidine and serine (in the mutant enzyme) also varies in different subunits. The structures of the C. parvum GAPDH ternary complex and other GAPDH complexes demonstrate the plasticity of the substrate binding site. We propose that the active site of GAPDH can accommodate the substrate in multiple conformations at multiple locations during the initial encounter. However, the C-3 phosphate group clearly prefers the 'new Pi' site for initial binding in the active site.« less

Plasma-Sprayed Hydroxylapatite-Based Coatings: Chemical, Mechanical, Microstructural, and Biomedical Properties

NASA Astrophysics Data System (ADS)

Heimann, Robert B.

2016-06-01

This contribution discusses salient properties and functions of hydroxylapatite (HA)-based plasma-sprayed coatings, including the effect on biomedical efficacy of coating thickness, phase composition and distribution, amorphicity and crystallinity, porosity and surface roughness, cohesion and adhesion, micro- and nano-structured surface morphology, and residual coating stresses. In addition, it will provide details of the thermal alteration that HA particles undergo in the extremely hot plasma jet that leads to dehydroxylated phases such as oxyhydroxylapatite (OHA) and oxyapatite (OA) as well as thermal decomposition products such as tri-(TCP) and tetracalcium phosphates (TTCP), and quenched phases such as amorphous calcium phosphate (ACP). The contribution will further explain the role of ACP during the in vitro interaction of the as-deposited coatings with simulated body fluid resembling the composition of extracellular fluid (ECF) as well as the in vivo responses of coatings to the ECF and the host tissue, respectively. Finally, it will briefly describe performance profiles required to fulfill biological functions of osteoconductive bioceramic coatings designed to improve osseointegration of hip endoprostheses and dental root implants. In large parts, the content of this contribution is a targeted review of work done by the author and his students and coworkers over the last two decades. In addition, it is considered a stepping stone toward a standard operation procedure aimed at depositing plasma-sprayed bioceramic implant coatings with optimum properties.

A time-based potential step analysis of electrochemical impedance incorporating a constant phase element: a study of commercially pure titanium in phosphate buffered saline.

PubMed

Ehrensberger, Mark T; Gilbert, Jeremy L

2010-05-01

The measurement of electrochemical impedance is a valuable tool to assess the electrochemical environment that exists at the surface of metallic biomaterials. This article describes the development and validation of a new technique, potential step impedance analysis (PSIA), to assess the electrochemical impedance of materials whose interface with solution can be modeled as a simplified Randles circuit that is modified with a constant phase element. PSIA is based upon applying a step change in voltage to a working electrode and analyzing the subsequent current transient response in a combined time and frequency domain technique. The solution resistance, polarization resistance, and interfacial capacitance are found directly in the time domain. The experimental current transient is numerically transformed to the frequency domain to determine the constant phase exponent, alpha. This combined time and frequency approach was tested using current transients generated from computer simulations, from resistor-capacitor breadboard circuits, and from commercially pure titanium samples immersed in phosphate buffered saline and polarized at -800 mV or +1000 mV versus Ag/AgCl. It was shown that PSIA calculates equivalent admittance and impedance behavior over this range of potentials when compared to standard electrochemical impedance spectroscopy. This current transient approach characterizes the frequency response of the system without the need for expensive frequency response analyzers or software. Copyright 2009 Wiley Periodicals, Inc.

Data Fusion Analysis for Range Test Validation System

DTIC Science & Technology

2010-07-14

simulants were released during the RTVS ’08 test series: triethyl phosphate (TEP), methyl salicylate (MeS), and acetic acid (AA). A total of 29 release...the combination of a grid of point sensors at ground level and a standoff FTIR system monitoring above ground areas proved effective in detecting the...presence of simulants over the test grid. A Dempster-Shafer approach for data fusion was selected as the most effective strategy for RTVS data fusion

Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution

DOE PAGES

Munasinghe, P. Sumudu; Elwood Madden, Megan E.; Brooks, Scott C.; ...

2015-04-17

We report that natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Thus, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, we carried out batch experiments with goethite and mica at pHmore » 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations.« less

Mesocarbon Microbead Carbon-Supported Magnesium Hydroxide Nanoparticles: Turning Spent Li-ion Battery Anode into a Highly Efficient Phosphate Adsorbent for Wastewater Treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yan; Guo, Xingming; Wu, Feng

Phosphorus in water eutrophication has become a serious problem threatening the environment. However, the development of efficient adsorbents for phosphate removal from water is lagging. In this work, we recovered the waste material, graphitized carbon, from spent lithium ion batteries and modified it with nanostructured Mg(OH)2 on the surface to treat excess phosphate. This phosphate adsorbent shows one of the highest phosphate adsorption capacities to date, 588.4 mg/g (1 order of magnitude higher than previously reported carbon-based adsorbents), and exhibits decent stability. A heterogeneous multilayer adsorption mechanism was proposed on the basis of multiple adsorption results. This highly efficient adsorbentmore » from spent Li-ion batteries displays great potential to be utilized in industry, and the mechanism study paved a way for further design of the adsorbent for phosphate adsorption.« less

Double differential cross sections for proton induced electron emission from molecular analogues of DNA constituents for energies in the Bragg peak region

NASA Astrophysics Data System (ADS)

Rudek, Benedikt; Bennett, Daniel; Bug, Marion U.; Wang, Mingjie; Baek, Woon Yong; Buhr, Ticia; Hilgers, Gerhard; Champion, Christophe; Rabus, Hans

2016-09-01

For track structure simulations in the Bragg peak region, measured electron emission cross sections of DNA constituents are required as input for developing parameterized model functions representing the scattering probabilities. In the present work, double differential cross sections were measured for the electron emission from vapor-phase pyrimidine, tetrahydrofuran, and trimethyl phosphate that are structural analogues to the base, the sugar, and the phosphate residue of the DNA, respectively. The range of proton energies was from 75 keV to 135 keV, the angles ranged from 15° to 135°, and the electron energies were measured from 10 eV to 200 eV. Single differential and total electron emission cross sections are derived by integration over angle and electron energy and compared to the semi-empirical Hansen-Kocbach-Stolterfoht (HKS) model and a quantum mechanical calculation employing the first Born approximation with corrected boundary conditions (CB1). The CB1 provides the best prediction of double and single differential cross section, while total cross sections can be fitted with semi-empirical models. The cross sections of the three samples are proportional to their total number of valence electrons.

Ac-conductivity and dielectric response of new zinc-phosphate glass/metal composites

NASA Astrophysics Data System (ADS)

Maaroufi, A.; Oabi, O.; Lucas, B.

2016-07-01

The ac-conductivity and dielectric response of new composites based on zinc-phosphate glass with composition 45 mol%ZnO-55 mol%P2O5, filled with metallic powder of nickel (ZP/Ni) were investigated by impedance spectroscopy in the frequency range from 100 Hz to 1 MHz at room temperature. A high percolating jump of seven times has been observed in the conductivity behavior from low volume fraction of filler to the higher fractions, indicating an insulator - semiconductor phase transition. The measured conductivity at higher filler volume fraction is about 10-1 S/cm and is frequency independent, while, the obtained conductivity for low filler volume fraction is around 10-8 S/cm and is frequency dependent. Moreover, the elaborated composites are characterized by high dielectric constants in the range of 105 for conductive composites at low frequencies (100 Hz). In addition, the distribution of the relaxation processes was also evaluated. The Debye, Cole-Cole, Davidson-Cole and Havriliak-Negami models in electric modulus formalism were used to model the observed relaxation phenomena in ZP/Ni composites. The observed relaxation phenomena are fairly simulated by Davidson-Cole model, and an account of the interpretation of results is given.

Elucidation of new condition-dependent roles for fructose-1,6-bisphosphatase linked to cofactor balances

PubMed Central

Kilian, Stephanus G.; du Preez, James C.

2017-01-01

The cofactor balances in metabolism is of paramount importance in the design of a metabolic engineering strategy and understanding the regulation of metabolism in general. ATP, NAD+ and NADP+ balances are central players linking the various fluxes in central metabolism as well as biomass formation. NADP+ is especially important in the metabolic engineering of yeasts for xylose fermentation, since NADPH is required by most yeasts in the initial step of xylose utilisation, including the fast-growing Kluyveromyces marxianus. In this simulation study of yeast metabolism, the complex interplay between these cofactors was investigated; in particular, how they may affect the possible roles of fructose-1,6-bisphosphatase, the pentose phosphate pathway, glycerol production and the pyruvate dehydrogenase bypass. Using flux balance analysis, it was found that the potential role of fructose-1,6-bisphosphatase was highly dependent on the cofactor specificity of the oxidative pentose phosphate pathway and on the carbon source. Additionally, the excessive production of ATP under certain conditions might be involved in some of the phenomena observed, which may have been overlooked to date. Based on these findings, a strategy is proposed for the metabolic engineering of a future xylose-fermenting yeast for biofuel production. PMID:28542187

Pentose phosphates in nucleoside interconversion and catabolism.

PubMed

Tozzi, Maria G; Camici, Marcella; Mascia, Laura; Sgarrella, Francesco; Ipata, Piero L

2006-03-01

Ribose phosphates are either synthesized through the oxidative branch of the pentose phosphate pathway, or are supplied by nucleoside phosphorylases. The two main pentose phosphates, ribose-5-phosphate and ribose-1-phosphate, are readily interconverted by the action of phosphopentomutase. Ribose-5-phosphate is the direct precursor of 5-phosphoribosyl-1-pyrophosphate, for both de novo and 'salvage' synthesis of nucleotides. Phosphorolysis of deoxyribonucleosides is the main source of deoxyribose phosphates, which are interconvertible, through the action of phosphopentomutase. The pentose moiety of all nucleosides can serve as a carbon and energy source. During the past decade, extensive advances have been made in elucidating the pathways by which the pentose phosphates, arising from nucleoside phosphorolysis, are either recycled, without opening of their furanosidic ring, or catabolized as a carbon and energy source. We review herein the experimental knowledge on the molecular mechanisms by which (a) ribose-1-phosphate, produced by purine nucleoside phosphorylase acting catabolically, is either anabolized for pyrimidine salvage and 5-fluorouracil activation, with uridine phosphorylase acting anabolically, or recycled for nucleoside and base interconversion; (b) the nucleosides can be regarded, both in bacteria and in eukaryotic cells, as carriers of sugars, that are made available though the action of nucleoside phosphorylases. In bacteria, catabolism of nucleosides, when suitable carbon and energy sources are not available, is accomplished by a battery of nucleoside transporters and of inducible catabolic enzymes for purine and pyrimidine nucleosides and for pentose phosphates. In eukaryotic cells, the modulation of pentose phosphate production by nucleoside catabolism seems to be affected by developmental and physiological factors on enzyme levels.

Molecular analysis of phosphate limitation in Geobacteraceae during the bioremediation of a uranium-contaminated aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

N'Guessan, A. Lucie; Elifantz, H.; Nevin, Kelly P.

2010-01-10

Nutrient limitation is an environmental stress that may reduce the effectiveness of bioremediation strategies, especially when the contaminants are organic compounds or when organic compounds are added to promote microbial activities such as metal reduction. Genes indicative of phosphatelimitation were identified by microarray analysis of chemostat cultures of Geobacter sulfureducens. This analysis revealed that genes in the pst-pho operon, which is associated with a high-affinity phosphate uptake system in other microorganisms, had significantly higher transcript abundance under phosphate-limiting conditions, with the genes pstB and phoU upregulated the most. Quantitative PCR analysis of pstB and phoU transcript levels in G. sulfurreducensmore » grown in chemostats demonstrated that the expression of these genes increased when phosphate was removed from the culture medium. Transcripts of pstB and phoU within the subsurface Geobacter species predominating during an in situ uranium-bioremediation field experiment were more abundant than in chemostat cultures of G. sulfurreducens that were not limited for phosphate. Addition of phosphate to incubations of subsurface sediments did not stimulate dissimilatory metal reduction. The added phosphate was rapidly adsorbed onto the sediments. The results demonstrate that Geobacter species can effectively reduce U(VI) even when experiencing suboptimal phosphate concentrations and that increasing phosphate availability with phosphate additions is difficult to achieve because of the high reactivity of this compound. This transcript-based approach developed for diagnosing phosphate limitation should be applicable to assessing the potential need for additional phosphate in other bioremediation processes.« less

The sodium phosphate cotransporter family and nicotinamide phosphoribosyltransferase contribute to the daily oscillation of plasma inorganic phosphate concentration.

PubMed

Miyagawa, Atsumi; Tatsumi, Sawako; Takahama, Wako; Fujii, Osamu; Nagamoto, Kenta; Kinoshita, Emi; Nomura, Kengo; Ikuta, Kayo; Fujii, Toru; Hanazaki, Ai; Kaneko, Ichiro; Segawa, Hiroko; Miyamoto, Ken-Ichi

2018-05-01

Circulating inorganic phosphate exhibits a remarkable daily oscillation based on food intake. In humans and rodents, the daily oscillation in response to food intake may be coordinated to control the intestinal absorption, renal excretion, cellular shifts, and extracellular concentration of inorganic phosphate. However, mechanisms regulating the resulting oscillation are unknown. Here we investigated the roles of the sodium phosphate cotransporter SLC34 (Npt2) family and nicotinamide phosphoribosyltransferase (Nampt) in the daily oscillation of plasma inorganic phosphate levels. First, it is roughly linked to urinary inorganic phosphate excretion. Second, expression of renal Npt2a and Npt2c, and intestinal Npt2b proteins also exhibit a dynamic daily oscillation. Analyses of Npt2a, Npt2b, and Npt2c knockout mice revealed the importance of renal inorganic phosphate reabsorption and cellular inorganic phosphate shifts in the daily oscillation. Third, experiments in which nicotinamide and a specific Nampt inhibitor (FK866) were administered in the active and rest phases revealed that the Nampt/NAD + system is involved in renal inorganic phosphate excretion. Additionally, for cellular shifts, liver-specific Nampt deletion disturbed the daily oscillation of plasma phosphate during the rest but not the active phase. In systemic Nampt +/- mice, NAD levels were significantly reduced in the liver, kidney, and intestine, and the daily oscillation (active and rest phases) of the plasma phosphate concentration was attenuated. Thus, the Nampt/NAD + system for Npt2 regulation and cellular shifts to tissues such as the liver play an important role in generating daily oscillation of plasma inorganic phosphate levels. Copyright © 2017 International Society of Nephrology. Published by Elsevier Inc. All rights reserved.

Study of phosphate release from Bogor botanical gardens’ sediment into pore water using diffusive gradient in thin film (DGT)

NASA Astrophysics Data System (ADS)

Tirta, A. P.; Saefumillah, A.; Foliatini

2017-04-01

Eutrophication is one of the environmental problems caused by the excessive nutrients in aquatic ecosystems. In most lakes, phosphate is a limiting nutrient for algae photosynthesis. Even though the concentration of phosphate from external loading into the water body has been reduced, eutrophication could still be occured due to internal mobilization of phosphate from the sediment pore water into the overlying water. Therefore, the released phosphate from sediments and their interaction in the pore water must be included in the monitoring of phosphate concentration in aquatic system. The released phosphate from sediment into pore water has been studied by DGT device with ferrihydrite as binding gel and N-N‧-methylenebisacrylamide as crosslinker. The results showed that DGT with 15% acrylamide; 0.1 % N-N‧-methylenebisacrylamide and ferrihydrite as binding gel was suitable for the measurement of the released phosphate from sediment into pore water. The result of the deployed DGT in oxic and anoxic conditions in seven days incubation showed the released phosphate process from the sediment into pore water was affected by incubation time and the existence of oxygen in the environment. The released phosphate from the sediment into pore water in anoxic condition has a higher value than oxic condition. The experimental results of the deployed DGT in natural sediment core at a depth of 1 to 15 cm from the surface of the water for 7 days showed that the sediment has a different phosphate mass profile based on depth. The concentration of phosphate tends to be increased with depth. The maximum CDGT of phosphate released in oxic and anoxic conditions at 7th day period of incubation are 29.23 μg/L at 14 cm depth and 30.19 μg/L at 8 cm depth, respectively.

Physicochemical and osteoplastic characteristics of 3D printed bone grafts based on synthetic calcium phosphates and natural polymers

NASA Astrophysics Data System (ADS)

Nezhurina, E. K.; Karalkin, P. A.; Komlev, V. S.; Sviridova, I. K.; Kirsanova, V. A.; Akhmedova, S. A.; Shanskiy, Ya D.; Fedotov, A. Yu; Barinov, S. M.; Sergeeva, N. S.

2018-04-01

A creation of personalized implants for regeneration of bone tissue seems to be a very promising biomedical technological approach. We have studied the physicochemical characteristics, cyto- and biocompatibility of three-dimensional constructs based on sodium alginate and gelatin in combination with 2 types of calcium phosphate (tricalcium phosphate or octacalcium phosphate) obtained by inkjet 3D printing. In our experiments, we have studied the physical and chemical properties of the constructs – their porosity, chemical composition, microarchitecture of the surface and mechanical elasticity. The cytocompatibility of 3D constructs and matrix-for-cell properties were investigated in vitro on a model of human osteosarcoma MG-63 cell line by means of MTT assay. The biocompatibility of 3D constructs was studied on the model of subcutaneous implantation in mice up to 12 weeks. All types of 3D constructs were cytocompatible in vitro, demonstrated good matrix-for-cells properties, and had supported cell proliferation for 2 weeks. In results of subcutaneous in vivo test all constructs demonstrated biocompatibility with slow bioresorption of organic and inorganic components. Osteogenesis proceeded more actively in rat tibia model defects (marginal excision), substituted by 3D printed 3-component implants based on alginate, gelatin and octacalcium phosphate.

Analysis of genomic responses in a rat lung model treated with a humidifier sterilizer containing polyhexamethyleneguanidine phosphate.

PubMed

Kim, Min-Seok; Jeong, Seok Won; Choi, Seong-Jin; Han, Jin-Young; Kim, Sung-Hwan; Yoon, Seokjoo; Oh, Jung-Hwa; Lee, Kyuhong

2017-02-15

The antimicrobial biocide polyhexamethyleneguanidine (PHMG) phosphate is the main ingredient in the commercially available humidifier disinfectant. PHMG phosphate-based humidifier disinfectants can cause pulmonary fibrosis and induce inflammatory and fibrotic responses both in vivo and in vitro. However, toxicological mechanisms including genomic alterations induced by inhalation exposure to PHMG phosphate have not been elucidated. Therefore, this study evaluated the toxicological effects of the PHMG phosphate-containing humidifier disinfectant. We used DNA microarray to identify global gene expression changes in rats treated with PHMG phosphate-containing humidifier disinfectant for 4 weeks and 10 weeks. Functional significance of differentially expressed genes (DEGs) was estimated by gene ontology (GO) analysis. Four weeks post-exposure, 320 and 392 DEGs were identified in female and male rats, respectively (>2-fold, p<0.05). Ten weeks post-exposure, 1290 and 995 DEGs were identified in females and males, respectively. Of these, 119 and 556 genes overlapped between females and males at 4 weeks and 10 weeks, respectively, post-PHMG phosphate exposure. In addition, 21 genes were upregulated and 4 genes were downregulated in response to PHMG phosphate in a time-dependent manner. Thus, we predict that changes in genomic responses could be a significant molecular mechanism underlying PHMG phosphate toxicity. Further studies are required to determine the detailed mechanism of PHMG phosphate-induced pulmonary toxicity. Copyright © 2016. Published by Elsevier B.V.

Improved treatment of nucleosides and nucleotides in the OPLS-AA force field

NASA Astrophysics Data System (ADS)

Robertson, Michael J.; Tirado-Rives, Julian; Jorgensen, William L.

2017-09-01

DFT calculations have been used to develop improved descriptions of the torsional energetics for nucleosides and nucleotides in the OPLS-AA force field. Scans of nucleotide dihedral angles (γ, χ, and β) and methyl phosphates provided the bases for the new torsional parameters. In addition, the angle-bending parameters of phosphodiesters and ribose were updated, and adjustments were made to existing carbohydrate torsions to better capture the sugar puckering landscape of ribose. MD simulations of nucleosides with the new parameters demonstrate a significant improvement in the ribose sugar puckering and χ angle distributions. Additionally, energy-minimization of protein-nucleotide crystal structures with the new parameters produced accurate poses.

Hydroxyapatite Growth Inhibition Effect of Pellicle Statherin Peptides.

PubMed

Xiao, Y; Karttunen, M; Jalkanen, J; Mussi, M C M; Liao, Y; Grohe, B; Lagugné-Labarthet, F; Siqueira, W L

2015-08-01

In our recent studies, we have shown that in vivo-acquired enamel pellicle is a sophisticated biological structure containing a significant portion of naturally occurring salivary peptides. From a functional aspect, the identification of peptides in the acquired enamel pellicle is of interest because many salivary proteins exhibit functional domains that maintain the activities of the native protein. Among the in vivo-acquired enamel pellicle peptides that have been newly identified, 5 peptides are derived from statherin. Here, we assessed the ability of these statherin pellicle peptides to inhibit hydroxyapatite crystal growth. In addition, atomistic molecular dynamics (MD) simulations were performed to better understand the underlying physical mechanisms of hydroxyapatite growth inhibition. A microplate colorimetric assay was used to quantify hydroxyapatite growth. Statherin protein, 5 statherin-derived peptides, and a peptide lacking phosphate at residues 2 and 3 were analyzed. Statherin peptide phosphorylated on residues 2 and 3 indicated a significant inhibitory effect when compared with the 5 other peptides (P < 0.05). MD simulations showed a strong affinity and fast adsorption to hydroxyapatite for phosphopeptides, whereas unphosphorylated peptides interacted weakly with the hydroxyapatite. Our data suggest that the presence of a covalently linked phosphate group (at residues 2 and 3) in statherin peptides modulates the effect of hydroxyapatite growth inhibition. This study provides a mechanism to account for the composition and function of acquired enamel pellicle statherin peptides that will contribute as a base for the development of biologically stable and functional synthetic peptides for therapeutic use against dental caries and/or periodontal disease. © International & American Associations for Dental Research 2015.

Toward a Rational Design of Bioactive Glasses with Optimal Structural Features: Composition–Structure Correlations Unveiled by Solid-State NMR and MD Simulations

PubMed Central

2013-01-01

The physiological responses of silicate-based bioactive glasses (BGs) are known to depend critically on both the P content (nP) of the glass and its silicate network connectivity (N̅BOSi). However, while the bioactivity generally displays a nonmonotonic dependence on nP itself, recent work suggest that it is merely the net orthophosphate content that directly links to the bioactivity. We exploit molecular dynamics (MD) simulations combined with 31P and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy to explore the quantitative relationships between N̅BOSi, nP, and the silicate and phosphate speciations in a series of Na2O–CaO–SiO2–P2O5 glasses spanning 2.1 ≤ N̅BOSi ≤ 2.9 and variable P2O5 contents up to 6.0 mol %. The fractional population of the orthophosphate groups remains independent of nP at a fixed N̅BOSi-value, but is reduced slightly as N̅BOSi increases. Nevertheless, P remains predominantly as readily released orthophosphate ions, whose content may be altered essentially independently of the network connectivity, thereby offering a route to optimize the glass bioactivity. We discuss the observed composition-structure links in relation to known composition-bioactivity correlations, and define how Na2O–CaO–SiO2–P2O5 compositions exhibiting an optimal bioactivity can be designed by simultaneously altering three key parameters: the silicate network connectivity, the (ortho)phosphate content, and the nNa/nCa molar ratio. PMID:24364818

A Chemist’s Perspective on the Role of Phosphorus at the Origins of Life

PubMed Central

Fernández-García, Christian; Coggins, Adam J.

2017-01-01

The central role that phosphates play in biological systems, suggests they also played an important role in the emergence of life on Earth. In recent years, numerous important advances have been made towards understanding the influence that phosphates may have had on prebiotic chemistry, and here, we highlight two important aspects of prebiotic phosphate chemistry. Firstly, we discuss prebiotic phosphorylation reactions; we specifically contrast aqueous electrophilic phosphorylation, and aqueous nucleophilic phosphorylation strategies, with dry-state phosphorylations that are mediated by dissociative phosphoryl-transfer. Secondly, we discuss the non-structural roles that phosphates can play in prebiotic chemistry. Here, we focus on the mechanisms by which phosphate has guided prebiotic reactivity through catalysis or buffering effects, to facilitating selective transformations in neutral water. Several prebiotic routes towards the synthesis of nucleotides, amino acids, and core metabolites, that have been facilitated or controlled by phosphate acting as a general acid–base catalyst, pH buffer, or a chemical buffer, are outlined. These facile and subtle mechanisms for incorporation and exploitation of phosphates to orchestrate selective, robust prebiotic chemistry, coupled with the central and universally conserved roles of phosphates in biochemistry, provide an increasingly clear message that understanding phosphate chemistry will be a key element in elucidating the origins of life on Earth. PMID:28703763

Ferrous ion as a reducing agent in the generation of antibiofilm nitric oxide from a copper-based catalytic system.

PubMed

Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

2018-05-01

The work found that the electron-donating properties of ferrous ions (Fe 2+ ) can be used for the conversion of nitrite (NO 2 - ) into the biofilm-dispersing signal nitric oxide (NO) by a copper(II) complex (CuDTTCT) catalyst, a potentially applicable biofilm control technology for the water industries. The availability of Fe 2+ varied depending on the characteristics of the aqueous systems (phosphate- and carbonate-containing nitrifying bacteria growth medium, NBGM and phosphate buffered saline, PBS at pH 6 to 8, to simulate conditions typically present in the water industries) and was found to affect the production of NO from nitrite by CuDTTCT (casted into PVC). Greater amounts of NO were generated from the CuDTTCT-nitrite-Fe 2+ systems in PBS compared to those in NBGM, which was associated with the reduced extent of Fe 2+ -to-Fe 3+ autoxidation by the iron-precipitating moieties phosphates and carbonate in the former system. Further, acidic conditions at pH 6.0 were found to favor NO production from the catalytic system in both PBS and NBGM compared to neutral or basic pH (pH 7.0 or 8.0). Lower pH was shown to stabilize Fe 2+ and reduce its autoxidation to Fe 3+ . These findings will be beneficial for the potential implementation of the NO-generating catalytic technology and indeed, a 'non-killing' biofilm dispersal activity of CuDTTCT-nitrite-Fe 2+ was observed on nitrifying bacteria biofilms in PBS at pH 6. Copyright © 2018 Elsevier Inc. All rights reserved.

Indirect estimation of emission factors for phosphate surface mining using air dispersion modeling.

PubMed

Tartakovsky, Dmitry; Stern, Eli; Broday, David M

2016-06-15

To date, phosphate surface mining suffers from lack of reliable emission factors. Due to complete absence of data to derive emissions factors, we developed a methodology for estimating them indirectly by studying a range of possible emission factors for surface phosphate mining operations and comparing AERMOD calculated concentrations to concentrations measured around the mine. We applied this approach for the Khneifiss phosphate mine, Syria, and the Al-Hassa and Al-Abyad phosphate mines, Jordan. The work accounts for numerous model unknowns and parameter uncertainties by applying prudent assumptions concerning the parameter values. Our results suggest that the net mining operations (bulldozing, grading and dragline) contribute rather little to ambient TSP concentrations in comparison to phosphate processing and transport. Based on our results, the common practice of deriving the emission rates for phosphate mining operations from the US EPA emission factors for surface coal mining or from the default emission factor of the EEA seems to be reasonable. Yet, since multiple factors affect dispersion from surface phosphate mines, a range of emission factors, rather than only a single value, was found to satisfy the model performance. Copyright © 2016 Elsevier B.V. All rights reserved.

Salt bridge dynamics control substrate-induced conformational change in the membrane transporter GlpT

PubMed Central

Law, Christopher J.; Almqvist, Jonas; Bernstein, Adam; Goetz, Regina M.; Huang, Yafei; Soudant, Celine; Laaksonen, Aatto; Hovmöller, Sven; Wang, Da-Neng

2008-01-01

Summary Active transport of substrates across cytoplasmic membranes is of great physiological, medical and pharmaceutical importance. The glycerol-3-phosphate (G3P) transporter (GlpT) of the E. coli inner membrane is a secondary active antiporter from the ubiquitous major facilitator superfamily that couples the import of G3P to the efflux of inorganic phosphate (Pi) down its concentration gradient. Integrating information from a novel combination of structural, molecular dynamics simulations and biochemical studies, we identify the residues involved directly in binding of substrate to the inward-facing conformation of GlpT, thus defining the structural basis for the substrate-specificity of this transporter. The substrate binding mechanism involves protonation of a histidine residue at the binding site. Furthermore, our data suggest that the formation and breaking of inter- and intradomain salt bridges control the conformational change of the transporter that accompanies substrate translocation across the membrane. The mechanism we propose may be a paradigm for organophosphate/phosphate antiporters. PMID:18395745

[Apatite-forming ability of pure titanium implant after micro-arc oxidation treatment].

PubMed

Tian, Zhihui; Zhang, Yu; Wang, Lichao; Nan, Kaihui

2013-10-01

To investigate the apatite forming ability of pure titanium implant after micro-arc oxidation treatment in simulated body fluid (SBF) and obtain implants with calcium phosphate (Ca-P) layers. The implants were immersed in (SBF) after micro-arc oxidation treatment for different time lengths, and their apatite forming ability and the morphology and constituents of the Ca-P layers formed on the sample surface were analyzed using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive electron probe. After immersion in SBF, large quantities of Ca-P layers were induced on the surface of the samples. The Ca-P layers were composed of octacalcium phosphate and carbonated hydroxyapatite, and the crystals showed a plate-like morphology with an oriented growth. The implants with micro-arc oxidation treatment show good apatite forming ability on the surface with rich calcium and phosphorus elements. The formed layers are composed of bone-like apatite including octacalcium phosphate and carbonated hydroxyapatite.

Prevention of bone mineral changes induced by bed rest: Modification by static compression simulating weight bearing, combined supplementation of oral calcium and phosphate, calcitonin injections, oscillating compression, the oral diophosphonatedisodium etidronate, and lower body negative pressure

NASA Technical Reports Server (NTRS)

Schneider, V. S.; Hulley, S. B.; Donaldson, C. L.; Vogel, J. M.; Rosen, S. N.; Hantman, D. A.; Lockwood, D. R.; Seid, D.; Hyatt, K. H.; Jacobson, L. B.

1974-01-01

The phenomenon of calcium loss during bed rest was found to be analogous to the loss of bone material which occurs in the hypogravic environment of space flight. Ways of preventing this occurrence are investigated. A group of healthy adult males underwent 24-30 weeks of continuous bed rest. Some of them were given an exercise program designed to resemble normal ambulatory activity; another subgroup was fed supplemental potassium phosphate. The results from a 12-week period of treatment were compared with those untreated bed rest periods. The potassium phosphate supplements prevented the hypercalciuria of bed rest, but fecal calcium tended to increase. The exercise program did not diminish the negative calcium balance. Neither treatment affected the heavy loss of mineral from the calcaneus. Several additional studies are developed to examine the problem further.

Paracrystalline Disorder from Phosphate Ion Orientation and Substitution in Synthetic Bone Mineral.

PubMed

Marisa, Mary E; Zhou, Shiliang; Melot, Brent C; Peaslee, Graham F; Neilson, James R

2016-12-05

Hydroxyapatite is an inorganic mineral closely resembling the mineral phase in bone. However, as a biological mineral, it is highly disordered, and its composition and atomistic structure remain poorly understood. Here, synchrotron X-ray total scattering and pair distribution function analysis methods provide insight into the nature of atomistic disorder in a synthetic bone mineral analogue, chemically substituted hydroxyapatite. By varying the effective hydrolysis rate and/or carbonate concentration during growth of the mineral, compounds with varied degrees of paracrystallinity are prepared. From advanced simulations constrained by the experimental pair distribution function and density functional theory, the paracrystalline disorder prevalent in these materials appears to result from accommodation of carbonate in the lattice through random displacement of the phosphate groups. Though many substitution modalities are likely to occur in concert, the most predominant substitution places carbonate into the mirror plane of an ideal phosphate site. Understanding the mineralogical imperfections of a biologically analogous hydroxyapatite is important not only to potential bone grafting applications but also to biological mineralization processes themselves.

The carbon cycle in the Australian Community Climate and Earth System Simulator (ACCESS-ESM1) - Part 1: Model description and pre-industrial simulation

NASA Astrophysics Data System (ADS)

Law, Rachel M.; Ziehn, Tilo; Matear, Richard J.; Lenton, Andrew; Chamberlain, Matthew A.; Stevens, Lauren E.; Wang, Ying-Ping; Srbinovsky, Jhan; Bi, Daohua; Yan, Hailin; Vohralik, Peter F.

2017-07-01

Earth system models (ESMs) that incorporate carbon-climate feedbacks represent the present state of the art in climate modelling. Here, we describe the Australian Community Climate and Earth System Simulator (ACCESS)-ESM1, which comprises atmosphere (UM7.3), land (CABLE), ocean (MOM4p1), and sea-ice (CICE4.1) components with OASIS-MCT coupling, to which ocean and land carbon modules have been added. The land carbon model (as part of CABLE) can optionally include both nitrogen and phosphorous limitation on the land carbon uptake. The ocean carbon model (WOMBAT, added to MOM) simulates the evolution of phosphate, oxygen, dissolved inorganic carbon, alkalinity and iron with one class of phytoplankton and zooplankton. We perform multi-centennial pre-industrial simulations with a fixed atmospheric CO2 concentration and different land carbon model configurations (prescribed or prognostic leaf area index). We evaluate the equilibration of the carbon cycle and present the spatial and temporal variability in key carbon exchanges. Simulating leaf area index results in a slight warming of the atmosphere relative to the prescribed leaf area index case. Seasonal and interannual variations in land carbon exchange are sensitive to whether leaf area index is simulated, with interannual variations driven by variability in precipitation and temperature. We find that the response of the ocean carbon cycle shows reasonable agreement with observations. While our model overestimates surface phosphate values, the global primary productivity agrees well with observations. Our analysis highlights some deficiencies inherent in the carbon models and where the carbon simulation is negatively impacted by known biases in the underlying physical model and consequent limits on the applicability of this model version. We conclude the study with a brief discussion of key developments required to further improve the realism of our model simulation.

Studies on the electrochemical behavior of thiazolidine and its applications using a flow-through chronoamperometric sensor based on a gold electrode.

PubMed

Wang, Lai-Hao; Li, Wen-Jie

2011-09-06

The electrochemical behaviors of thiazolidine (tetrahydrothiazole) on gold and platinum electrodes were investigated in a Britton-Robinson buffer (pH 2.77-11.61), acetate buffer (pH 4.31), phosphate buffer solutions (pH 2.11 and 6.38) and methanol or acetonitrile containing various supporting electrolytes. Detection was based on a gold wire electrochemical signal obtained with a supporting electrolyte containing 20% methanol-1.0 mM of phosphate buffer (pH 6.87, potassium dihydrogen phosphate and dipotassium hydrogen phosphate) as the mobile phase. Comparison with results obtained with a commercial amperometric detector shows good agreement. Using the chronoamperometric sensor with the current at a constant potential, and measurements with suitable experimental parameters, a linear concentration from 0.05 to 16 mg L-1 was found. The limit of quantification (LOQ) of the method for thiazolidine was found to be 1 ng.

Changes in serum phosphate and potassium and their effects on mortality in malnourished African HIV-infected adults starting antiretroviral therapy and given vitamins and minerals in lipid-based nutritional supplements: secondary analysis from the Nutritional Support for African Adults Starting Antiretroviral Therapy (NUSTART) trial.

PubMed

Rehman, Andrea Mary; Woodd, Susannah Louise; Heimburger, Douglas Corbett; Koethe, John Robert; Friis, Henrik; PrayGod, George; Kasonka, Lackson; Kelly, Paul; Filteau, Suzanne

2017-03-01

Malnourished HIV-infected patients starting antiretroviral therapy (ART) are at high risk of early mortality, some of which may be attributed to altered electrolyte metabolism. We used data from a randomised controlled trial of electrolyte-enriched lipid-based nutritional supplements to assess the association of baseline and time-varying serum phosphate and K concentrations with mortality within the first 12 weeks after starting ART. Baseline phosphate results were available from 1764 patients and there were 9096 subsequent serum phosphate measurements, a median of 6 per patient. For serum K there were 1701 baseline and 8773 subsequent measures, a median of 6 per patient. Abnormally high or low serum phosphate was more common than high or low serum K. Controlling for other factors found to affect mortality in this cohort, low phosphate which had not changed from the previous time interval was associated with increased mortality; the same was not true for high phosphate or for high or low K. Both increases and decreases in serum electrolytes from the previous time interval were generally associated with increased mortality, particularly in the electrolyte-supplemented group. The results suggest that changes in serum electrolytes, largely irrespective of the starting point and the direction of change, were more strongly associated with mortality than were absolute electrolyte levels. Although K and phosphate are required for tissue deposition during recovery from malnutrition, further studies are needed to determine whether specific supplements exacerbate physiologically adverse shifts in electrolyte levels during nutritional rehabilitation of ill malnourished HIV patients.

Structural Basis for Substrate Specificity in Phosphate Binding (beta/alpha)8-Barrels: D-Allulose 6-Phosphate 3-Epimerase from Escherichia coli K-12

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chan,K.; Fedorov, A.; Almo, S.

2008-01-01

Enzymes that share the ({beta}/{alpha})8-barrel fold catalyze a diverse range of reactions. Many utilize phosphorylated substrates and share a conserved C-terminal ({beta}/a)2-quarter barrel subdomain that provides a binding motif for the dianionic phosphate group. We recently reported functional and structural studies of d-ribulose 5-phosphate 3-epimerase (RPE) from Streptococcus pyogenes that catalyzes the equilibration of the pentulose 5-phosphates d-ribulose 5-phosphate and d-xylulose 5-phosphate in the pentose phosphate pathway [J. Akana, A. A. Fedorov, E. Fedorov, W. R. P. Novack, P. C. Babbitt, S. C. Almo, and J. A. Gerlt (2006) Biochemistry 45, 2493-2503]. We now report functional and structural studies ofmore » d-allulose 6-phosphate 3-epimerase (ALSE) from Escherichia coli K-12 that catalyzes the equilibration of the hexulose 6-phosphates d-allulose 6-phosphate and d-fructose 6-phosphate in a catabolic pathway for d-allose. ALSE and RPE prefer their physiological substrates but are promiscuous for each other's substrate. The active sites (RPE complexed with d-xylitol 5-phosphate and ALSE complexed with d-glucitol 6-phosphate) are superimposable (as expected from their 39% sequence identity), with the exception of the phosphate binding motif. The loop following the eighth {beta}-strand in ALSE is one residue longer than the homologous loop in RPE, so the binding site for the hexulose 6-phosphate substrate/product in ALSE is elongated relative to that for the pentulose 5-phosphate substrate/product in RPE. We constructed three single-residue deletion mutants of the loop in ALSE, ?T196, ?S197 and ?G198, to investigate the structural bases for the differing substrate specificities; for each, the promiscuity is altered so that d-ribulose 5-phosphate is the preferred substrate. The changes in kcat/Km are dominated by changes in kcat, suggesting that substrate discrimination results from differential transition state stabilization. In both ALSE and RPE, the phosphate group hydrogen bonds not only with the conserved motif but also with an active site loop following the sixth {beta}-strand, providing a potential structural mechanism for coupling substrate binding with catalysis.« less

Protein-adsorption and Ca-phosphate formation on chitosan-bioactive glass composite coatings

NASA Astrophysics Data System (ADS)

Wagener, V.; Boccaccini, A. R.; Virtanen, S.

2017-09-01

In the last years, chitosan-bioactive glass (BG) composites have been developed and investigated as bioactive coatings for orthopedic applications. The increase of bioactivity occurs due to the stimulation of calcium-phosphate/hydroxyapatite formation on the surface while the coating is degrading. In the present work, protein adsorption and its influence on calcium-phosphate precipitation was studied for the first time on such composite coatings. The experiments involved coating of 316L stainless steel substrates with chitosan (Ch) and chitosan-bioactive glass (Ch-BG) and immersion of the coated samples in two different bovine serum albumin (BSA) containing solutions, namely DI H2O (with pH adjusted to about 7.2 with diluted NaOH) and simulated body fluid (SBF). In order to investigate the influence of protein adsorption on calcium-phosphate precipitation, samples were also immersed in DI H2O and in SBF without BSA. Samples were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Surface analysis revealed that adsorption of BSA takes place on all studied samples and that protein adsorption is influenced by the presence of Ca2+ and PO43- ions. Bioactivity in the form of hydroxyapatite pre-stage formation is significantly increased on Ch-BG composite coating as compared with bare stainless steel surface. However, calcium-phosphate precipitation in SBF is reduced by the presence of BSA.

High temperature insulation for ceramic matrix composites

DOEpatents

Merrill, Gary B.; Morrison, Jay Alan

2001-01-01

A ceramic composition is provided to insulate ceramic matrix composites under high temperature, high heat flux environments. The composition comprises a plurality of hollow oxide-based spheres of various dimensions, a phosphate binder, and at least one oxide filler powder, whereby the phosphate binder partially fills gaps between the spheres and the filler powders. The spheres are situated in the phosphate binder and the filler powders such that each sphere is in contact with at least one other sphere. The spheres may be any combination of Mullite spheres, Alumina spheres, or stabilized Zirconia spheres. The filler powder may be any combination of Alumina, Mullite, Ceria, or Hafnia. Preferably, the phosphate binder is Aluminum Ortho-Phosphate. A method of manufacturing the ceramic insulating composition and its application to CMC substrates are also provided.

High temperature insulation for ceramic matrix composites

DOEpatents

Merrill, Gary B.; Morrison, Jay Alan

2000-01-01

A ceramic composition is provided to insulate ceramic matrix composites under high temperature, high heat flux environments. The composite comprises a plurality of hollow oxide-based spheres of varios dimentions, a phosphate binder, and at least one oxide filler powder, whereby the phosphate binder partially fills gaps between the spheres and the filler powders. The spheres are situated in the phosphate binder and the filler powders such that each sphere is in contact with at least one other sphere. The spheres may be any combination of Mullite spheres, Alumina spheres, or stabilized Zirconia spheres. The filler powder may be any combination of Alumina, Mullite, Ceria, or Hafnia. Preferably, the phosphate binder is Aluminum Ortho-Phosphate. A method of manufacturing the ceramic insulating composition and its application to CMC substates are also provided.

High temperature insulation for ceramic matrix composites

DOEpatents

Merrill, Gary B.; Morrison, Jay Alan

2004-01-13

A ceramic composition is provided to insulate ceramic matrix composites under high temperature, high heat flux environments. The composition comprises a plurality of hollow oxide-based spheres of various dimensions, a phosphate binder, and at least one oxide filler powder, whereby the phosphate binder partially fills gaps between the spheres and the filler powders. The spheres are situated in the phosphate binder and the filler powders such that each sphere is in contact with at least one other sphere. The spheres may be any combination of Mullite spheres, Alumina spheres, or stabilized Zirconia spheres. The filler powder may be any combination of Alumina, Mullite, Ceria, or Hafnia. Preferably, the phosphate binder is Aluminum Ortho-Phosphate. A method of manufacturing the ceramic insulating composition and its application to CMC substrates are also provided.

Conformation-dependent DNA attraction

NASA Astrophysics Data System (ADS)

Li, Weifeng; Nordenskiöld, Lars; Zhou, Ruhong; Mu, Yuguang

2014-05-01

Understanding how DNA molecules interact with other biomolecules is related to how they utilize their functions and is therefore critical for understanding their structure-function relationships. For a long time, the existence of Z-form DNA (a left-handed double helical version of DNA, instead of the common right-handed B-form) has puzzled the scientists, and the definitive biological significance of Z-DNA has not yet been clarified. In this study, the effects of DNA conformation in DNA-DNA interactions are explored by molecular dynamics simulations. Using umbrella sampling, we find that for both B- and Z-form DNA, surrounding Mg2+ ions always exert themselves to screen the Coulomb repulsion between DNA phosphates, resulting in very weak attractive force. On the contrary, a tight and stable bound state is discovered for Z-DNA in the presence of Mg2+ or Na+, benefiting from their hydrophobic nature. Based on the contact surface and a dewetting process analysis, a two-stage binding process of Z-DNA is outlined: two Z-DNA first attract each other through charge screening and Mg2+ bridges to phosphate groups in the same way as that of B-DNA, after which hydrophobic contacts of the deoxyribose groups are formed via a dewetting effect, resulting in stable attraction between two Z-DNA molecules. The highlighted hydrophobic nature of Z-DNA interaction from the current study may help to understand the biological functions of Z-DNA in gene transcription.Understanding how DNA molecules interact with other biomolecules is related to how they utilize their functions and is therefore critical for understanding their structure-function relationships. For a long time, the existence of Z-form DNA (a left-handed double helical version of DNA, instead of the common right-handed B-form) has puzzled the scientists, and the definitive biological significance of Z-DNA has not yet been clarified. In this study, the effects of DNA conformation in DNA-DNA interactions are explored by molecular dynamics simulations. Using umbrella sampling, we find that for both B- and Z-form DNA, surrounding Mg2+ ions always exert themselves to screen the Coulomb repulsion between DNA phosphates, resulting in very weak attractive force. On the contrary, a tight and stable bound state is discovered for Z-DNA in the presence of Mg2+ or Na+, benefiting from their hydrophobic nature. Based on the contact surface and a dewetting process analysis, a two-stage binding process of Z-DNA is outlined: two Z-DNA first attract each other through charge screening and Mg2+ bridges to phosphate groups in the same way as that of B-DNA, after which hydrophobic contacts of the deoxyribose groups are formed via a dewetting effect, resulting in stable attraction between two Z-DNA molecules. The highlighted hydrophobic nature of Z-DNA interaction from the current study may help to understand the biological functions of Z-DNA in gene transcription. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03235c

Event Record for the Joint Chemical Agent Detector (JCAD) Increment 2 Chamber Upgrades

DTIC Science & Technology

2009-05-27

trials began. The simulants [ methyl salicylate (MeS) and dimethyl methyl phosphate (DMMP)] were chosen for their similarity to CWA evaporation...rate and the measured con- centration. 2. The temperature in the evaporation zone was controlled at 150ºC. Figure 2. Methyl Salicylate (MeS

Raman imaging using fixed bandpass filter

NASA Astrophysics Data System (ADS)

Landström, L.; Kullander, F.; Lundén, H.; Wästerby, P.

2017-05-01

By using fixed narrow band pass optical filtering and scanning the laser excitation wavelength, hyperspectral Raman imaging could be achieved. Experimental, proof-of-principle results from the Chemical Warfare Agent (CWA) tabun (GA) as well as the common CWA simulant tributyl phosphate (TBP) on different surfaces/substrates are presented and discussed.

High-efficiency frequency doubling of continuous-wave laser light.

PubMed

Ast, Stefan; Nia, Ramon Moghadas; Schönbeck, Axel; Lastzka, Nico; Steinlechner, Jessica; Eberle, Tobias; Mehmet, Moritz; Steinlechner, Sebastian; Schnabel, Roman

2011-09-01

We report on the observation of high-efficiency frequency doubling of 1550 nm continuous-wave laser light in a nonlinear cavity containing a periodically poled potassium titanyl phosphate crystal (PPKTP). The fundamental field had a power of 1.10 W and was converted into 1.05 W at 775 nm, yielding a total external conversion efficiency of 95±1%. The latter value is based on the measured depletion of the fundamental field being consistent with the absolute values derived from numerical simulations. According to our model, the conversion efficiency achieved was limited by the nonperfect mode matching into the nonlinear cavity and by the nonperfect impedance matching for the maximum input power available. Our result shows that cavity-assisted frequency conversion based on PPKTP is well suited for low-decoherence frequency conversion of quantum states of light.

Managing oral phosphate binder medication expenditures within the Medicare bundled end-stage renal disease prospective payment system: economic implications for large U.S. dialysis organizations.

PubMed

Park, Haesuk; Rascati, Karen L; Keith, Michael S

2015-06-01

From January 2016, payment for oral-only renal medications (including phosphate binders and cinacalcet) was expected to be included in the new Medicare bundled end-stage renal disease (ESRD) prospective payment system (PPS). The implementation of the ESRD PPS has generated concern within the nephrology community because of the potential for inadequate funding and the impact on patient quality of care. To estimate the potential economic impact of the new Medicare bundled ESRD PPS reimbursement from the perspective of a large dialysis organization in the United States. We developed an interactive budget impact model to evaluate the potential economic implications of Medicare payment changes to large dialysis organizations treating patients with ESRD who are receiving phosphate binders. In this analysis, we focused on the budget impact of the intended 2016 integration of oral renal drugs, specifically oral phosphate binders, into the PPS. We also utilized the model to explore the budgetary impact of a variety of potential shifts in phosphate binder market shares under the bundled PPS from 2013 to 2016. The base model predicts that phosphate binder costs will increase to $34.48 per dialysis session in 2016, with estimated U.S. total costs for phosphate binders of over $682 million. Based on these estimates, a projected Medicare PPS $33.44 reimbursement rate for coverage of all oral-only renal medications (i.e., phosphate binders and cinacalcet) would be insufficient to cover these costs. A potential renal drugs and services budget shortfall for large dialysis organizations of almost $346 million was projected. Our findings suggest that large dialysis organizations will be challenged to manage phosphate binder expenditures within the planned Medicare bundled rate structure. As a result, large dialysis organizations may have to make treatment choices in light of potential inadequate funding, which could have important implications for the quality of care for patients with ESRD.

Structural features of phosphate accumulations in the Gantour basin - Morocco : Application of GIS

NASA Astrophysics Data System (ADS)

Mohamed, Laadraoui; El Hassane, Boumaggard; Essaid, Jourani

2010-05-01

The Moroccan Atlantic margin raises a lot of interest because of its potential resources in phosphates. It also holds in its Mesetien part one of the largest phosphatic deposit in the world. The authors present the results of their researches on structural environments of the phosphatic sedimentary sequences in the Gantour deposit in western Morocco. These investigations are mainly based on field data, data recorded from work done by the OCP (Office Chérifien des Phosphates) group, the interpretation of industrial seismic profiles and the application of GIS. Our aim are devoted to the apprehension of the geometry and the cinematic of these basins which are contemporaneous to the Central Atlantic Rifting, as well as the determination of the list of factors liable to the genesis of these phosphatic basins. Other data of field observations (cartography, study of structural features,...) permit to identify the general structure of the prospect. Sedimentation of phosphated deposits is strained by the presence of two wrench faulting systems oriented N20¬40E, N80¬120E and N140¬160E.

Radiological impact of natural radioactivity in Egyptian phosphate rocks, phosphogypsum and phosphate fertilizers.

PubMed

El-Bahi, S M; Sroor, A; Mohamed, Gehan Y; El-Gendy, N S

2017-05-01

In this study, the activity concentrations of the natural radionuclides in phosphate rocks and its products were measured using a high- purity germanium detector (HPGe). The obtained activity results show remarkable wide variation in the radioactive contents for the different phosphate samples. The average activity concentration of 235 U, 238 U, 226 Ra, 232 Th and 40 K was found as (45, 1031, 786, 85 and 765Bq/kg) for phosphate rocks, (28, 1234, 457, 123 and 819Bq/kg) for phosphate fertilizers, (47, 663, 550, 79 and 870Bq/kg) for phosphogypsum and (25, 543, 409, 54 and 897Bq/kg) for single super phosphate respectively. Based on the measured activities, the radiological parameters (activity concentration index, absorbed gamma dose rate in outdoor and indoor and the corresponding annual effective dose rates and total excess lifetime cancer risk) were estimated to assess the radiological hazards. The total excess lifetime cancer risk (ELCR) has been calculated and found to be high in all samples, which related to high radioactivity, representing radiological risk for the health of the population. Copyright © 2017 Elsevier Ltd. All rights reserved.

Environmental and Water Quality Operational Studies. Supplemental Limnological Studies at Richard B. Russell and Clarks Hill Lakes, 1983-1985

DTIC Science & Technology

1987-04-01

Simulation Division (ERSD), Environmental Laboratory (EL), WES. Dr. Thomas L. Hart was Chief, APEG; Mr. Donald L. Robey was Chief, ERSD; and Dr. John...a technical committee to outline potential problems at the project site. b. Simulation of the Hartwell-Russell-Clarks Hill Lake system using physical...Heath (1979) reported the release of phosphate from two different classes of dissolved organic compounds. One of these classes had a high molecular

Analysis of l-glutamic acid fermentation by using a dynamic metabolic simulation model of Escherichia coli

PubMed Central

2013-01-01

Background Understanding the process of amino acid fermentation as a comprehensive system is a challenging task. Previously, we developed a literature-based dynamic simulation model, which included transcriptional regulation, transcription, translation, and enzymatic reactions related to glycolysis, the pentose phosphate pathway, the tricarboxylic acid (TCA) cycle, and the anaplerotic pathway of Escherichia coli. During simulation, cell growth was defined such as to reproduce the experimental cell growth profile of fed-batch cultivation in jar fermenters. However, to confirm the biological appropriateness of our model, sensitivity analysis and experimental validation were required. Results We constructed an l-glutamic acid fermentation simulation model by removing sucAB, a gene encoding α-ketoglutarate dehydrogenase. We then performed systematic sensitivity analysis for l-glutamic acid production; the results of this process corresponded with previous experimental data regarding l-glutamic acid fermentation. Furthermore, it allowed us to predicted the possibility that accumulation of 3-phosphoglycerate in the cell would regulate the carbon flux into the TCA cycle and lead to an increase in the yield of l-glutamic acid via fermentation. We validated this hypothesis through a fermentation experiment involving a model l-glutamic acid-production strain, E. coli MG1655 ΔsucA in which the phosphoglycerate kinase gene had been amplified to cause accumulation of 3-phosphoglycerate. The observed increase in l-glutamic acid production verified the biologically meaningful predictive power of our dynamic metabolic simulation model. Conclusions In this study, dynamic simulation using a literature-based model was shown to be useful for elucidating the precise mechanisms involved in fermentation processes inside the cell. Further exhaustive sensitivity analysis will facilitate identification of novel factors involved in the metabolic regulation of amino acid fermentation. PMID:24053676

Analysis of L-glutamic acid fermentation by using a dynamic metabolic simulation model of Escherichia coli.

PubMed

Nishio, Yousuke; Ogishima, Soichi; Ichikawa, Masao; Yamada, Yohei; Usuda, Yoshihiro; Masuda, Tadashi; Tanaka, Hiroshi

2013-09-22

Understanding the process of amino acid fermentation as a comprehensive system is a challenging task. Previously, we developed a literature-based dynamic simulation model, which included transcriptional regulation, transcription, translation, and enzymatic reactions related to glycolysis, the pentose phosphate pathway, the tricarboxylic acid (TCA) cycle, and the anaplerotic pathway of Escherichia coli. During simulation, cell growth was defined such as to reproduce the experimental cell growth profile of fed-batch cultivation in jar fermenters. However, to confirm the biological appropriateness of our model, sensitivity analysis and experimental validation were required. We constructed an L-glutamic acid fermentation simulation model by removing sucAB, a gene encoding α-ketoglutarate dehydrogenase. We then performed systematic sensitivity analysis for L-glutamic acid production; the results of this process corresponded with previous experimental data regarding L-glutamic acid fermentation. Furthermore, it allowed us to predicted the possibility that accumulation of 3-phosphoglycerate in the cell would regulate the carbon flux into the TCA cycle and lead to an increase in the yield of L-glutamic acid via fermentation. We validated this hypothesis through a fermentation experiment involving a model L-glutamic acid-production strain, E. coli MG1655 ΔsucA in which the phosphoglycerate kinase gene had been amplified to cause accumulation of 3-phosphoglycerate. The observed increase in L-glutamic acid production verified the biologically meaningful predictive power of our dynamic metabolic simulation model. In this study, dynamic simulation using a literature-based model was shown to be useful for elucidating the precise mechanisms involved in fermentation processes inside the cell. Further exhaustive sensitivity analysis will facilitate identification of novel factors involved in the metabolic regulation of amino acid fermentation.

Effective adsorption of phosphate from wastewaters by big composite pellets made of reduced steel slag and iron ore concentrate.

PubMed

Wang, Hongjuan; Shen, Shaobo; Liu, Longhui; Ji, Yilong; Wang, Fuming

2015-01-01

In order to remove phosphate from wastewater, a large plastic adsorption column filled with big phosphate-adsorbing pellets with diameters of 10 mm, heated by electromagnetic induction coils, was conceived. It was found that the prepared big pellets, which were made of reduced steel slag and iron ore concentrate, contain magnetic Fe and Fe3O4. The thermodynamics and kinetics of adsorption of phosphate from synthetic wastewaters on the pellets were studied in this work. The phosphate adsorption on the pellets followed three models of Freundlich, Langmuir and Dubinin-Kaganer-Radushkevick. The maximum phosphate adsorption capacity Qmax of the pellets were 2.46, 2.74 and 2.77 mg/g for the three temperatures of 20°C, 30°C and 40°C, respectively, based on the Langmuir model. The apparent adsorption energies were -12.9 kJ/mol for the three temperatures. It implied that ion exchange was the main mechanism involved in the adsorption processes. The adsorbed phosphate existed on the pellet surface mainly in the form of Fe3(PO4)2. A reduction pre-treatment of the pellet precursor with H2 greatly enhanced pellet adsorption for phosphate. The adsorption kinetics is better represented by a pseudo-first-order model. The adsorbed phosphate amounts were similar for both real and synthetic wastewaters under similar adsorption conditions. The percentage of adsorbed phosphate for a real wastewater increased with increasing pellet concentration and reached 99.2% at a pellet concentration of 64 (g/L). Some specific phosphate adsorption mechanisms for the pellets were revealed and the pellets showed the potential to efficiently adsorb phosphate from a huge amount of real wastewaters in an industrial scale.

Structure-composition trends in multicomponent borosilicate-based glasses deduced from molecular dynamics simulations with improved B-O and P-O force fields.

PubMed

Stevensson, Baltzar; Yu, Yang; Edén, Mattias

2018-03-28

We present a comprehensive molecular dynamics (MD) simulation study of composition-structure trends in a set of 25 glasses of widely spanning compositions from the following four systems of increasing complexity: Na 2 O-B 2 O 3 , Na 2 O-B 2 O 3 -SiO 2 , Na 2 O-CaO-SiO 2 -P 2 O 5 , and Na 2 O-CaO-B 2 O 3 -SiO 2 -P 2 O 5 . The simulations involved new B-O and P-O potential parameters developed within the polarizable shell-model framework, thereby combining the beneficial features of an overall high accuracy and excellent transferability among different glass systems and compositions: this was confirmed by the good accordance with experimental data on the relative BO 3 /BO 4 populations in borate and boro(phospho)silicate networks, as well as with the orthophosphate fractions in bioactive (boro)phosphosilicate glasses, which is believed to strongly influence their bone-bonding properties. The bearing of the simulated melt-cooling rate on the borate/phosphate speciations is discussed. Each local {BO 3 , BO 4 , SiO 4 , PO 4 } coordination environment remained independent of the precise set of co-existing network formers, while all trends observed in bond-lengths/angles mainly reflected the glass-network polymerization, i.e., the relative amounts of bridging oxygen (BO) and non-bridging oxygen (NBO) species. The structural roles of the Na + /Ca 2+ cations were also probed, targeting their local coordination environments and their relative preferences to associate with the various borate, silicate, and phosphate moieties. We evaluate and discuss the common classification of alkali/alkaline-earth metal ions as charge-compensators of either BO 4 tetrahedra or NBO anions in borosilicate glasses, also encompassing the less explored NBO-rich regime: the Na + /Ca 2+ cations mainly associate with BO/NBO species of SiO 4 /BO 3 groups, with significant relative Na-BO 4 contacts only observed in B-rich glass networks devoid of NBO species, whereas NBO-rich glass networks also reveal substantial amounts of NBO-bearing BO 4 tetrahedra.

Model-Based Design of Biochemical Microreactors

PubMed Central

Elbinger, Tobias; Gahn, Markus; Neuss-Radu, Maria; Hante, Falk M.; Voll, Lars M.; Leugering, Günter; Knabner, Peter

2016-01-01

Mathematical modeling of biochemical pathways is an important resource in Synthetic Biology, as the predictive power of simulating synthetic pathways represents an important step in the design of synthetic metabolons. In this paper, we are concerned with the mathematical modeling, simulation, and optimization of metabolic processes in biochemical microreactors able to carry out enzymatic reactions and to exchange metabolites with their surrounding medium. The results of the reported modeling approach are incorporated in the design of the first microreactor prototypes that are under construction. These microreactors consist of compartments separated by membranes carrying specific transporters for the input of substrates and export of products. Inside the compartments of the reactor multienzyme complexes assembled on nano-beads by peptide adapters are used to carry out metabolic reactions. The spatially resolved mathematical model describing the ongoing processes consists of a system of diffusion equations together with boundary and initial conditions. The boundary conditions model the exchange of metabolites with the neighboring compartments and the reactions at the surface of the nano-beads carrying the multienzyme complexes. Efficient and accurate approaches for numerical simulation of the mathematical model and for optimal design of the microreactor are developed. As a proof-of-concept scenario, a synthetic pathway for the conversion of sucrose to glucose-6-phosphate (G6P) was chosen. In this context, the mathematical model is employed to compute the spatio-temporal distributions of the metabolite concentrations, as well as application relevant quantities like the outflow rate of G6P. These computations are performed for different scenarios, where the number of beads as well as their loading capacity are varied. The computed metabolite distributions show spatial patterns, which differ for different experimental arrangements. Furthermore, the total output of G6P increases for scenarios where microcompartimentation of enzymes occurs. These results show that spatially resolved models are needed in the description of the conversion processes. Finally, the enzyme stoichiometry on the nano-beads is determined, which maximizes the production of glucose-6-phosphate. PMID:26913283

Oxygen isotopes of phosphatic compounds - Application for marine particulate matter, sediments and soils

USGS Publications Warehouse

McLaughlin, K.; Paytan, A.; Kendall, C.; Silva, S.

2006-01-01

The phosphate oxygen isotopic composition in naturally occurring particulate phosphatic compounds (??18Op) can be used as a tracer for phosphate sources and to evaluate the cycling of phosphorus (P) in the environment. However, phosphatic compounds must be converted to silver phosphate prior to isotopic analysis, a process that involves digestion of particulate matter in acid. This digestion will hydrolyze some of the phosphatic compounds such that oxygen from the acid solution will be incorporated into the sample as these phosphatic compounds are converted to orthophosphate (PO 43-). To determine the extent of incorporation of reagent oxygen into the sample, we digested various phosphatic compounds in both acid amended with H218O (spiked) and unspiked acid and then converted the samples to silver phosphate for ??18Op analysis. Our results indicate that there is no isotopic fractionation associated with acid digestion at 50??C. Furthermore, we found that reagent oxygen incorporation is a function of the oxygen to phosphorus ratio (O:P) of the digested compound whereby the percentage of reagent oxygen incorporated into the sample is the same as that which is required to convert all of the P-compounds into orthophosphate. Based on these results, we developed a correction for reagent oxygen incorporation using simple mass balance, a procedure that allows for the determination of the ??18O p of samples containing a mixture of phosphatic compounds. We analyzed a variety of environmental samples for ??18O p to demonstrate the utility of this approach for understanding sources and cycling of P. ?? 2005 Elsevier B.V. All rights reserved.

Direct deposited porous scaffolds of calcium phosphate cement with alginate for drug delivery and bone tissue engineering.

PubMed

Lee, Gil-Su; Park, Jeong-Hui; Shin, Ueon Sang; Kim, Hae-Won

2011-08-01

This study reports the preparation of novel porous scaffolds of calcium phosphate cement (CPC) combined with alginate, and their potential usefulness as a three-dimensional (3-D) matrix for drug delivery and tissue engineering of bone. An α-tricalcium phosphate-based powder was mixed with sodium alginate solution and then directly injected into a fibrous structure in a Ca-containing bath. A rapid hardening reaction of the alginate with Ca(2+) helps to shape the composite into a fibrous form with diameters of hundreds of micrometers, and subsequent pressing in a mold allows the formation of 3-D porous scaffolds with different porosity levels. After transformation of the CPC into a calcium-deficient hydroxyapatite phase in simulated biological fluid the scaffold was shown to retain its mechanical stability. During the process biological proteins, such as bovine serum albumin and lysozyme, used as model proteins, were observed to be effectively loaded onto and released from the scaffolds for up to more than a month, proving the efficacy of the scaffolds as a drug delivering matrix. Mesenchymal stem cells (MSCs) were isolated from rat bone marrow and then cultured on the CPC-alginate porous scaffolds to investigate the ability to support proliferation of cells and their subsequent differentiation along the osteogenic lineage. It was shown that MSCs increasingly actively populated and also permeated into the porous network with time of culture. In particular, cells cultured within a scaffold with a relatively high porosity level showed favorable proliferation and osteogenic differentiation. An in vivo pilot study of the CPC-alginate porous scaffolds after implantation into the rat calvarium for 6 weeks revealed the formation of new bone tissue within the scaffold, closing the defect almost completely. Based on these results, the newly developed CPC-alginate porous scaffolds could be potentially useful as a 3-D matrix for drug delivery and tissue engineering of bone. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Three-step preparation and purification of phosphorus-33-labeled creatine phosphate of high specific activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savabi, F.; Geiger, P.J.; Bessman, S.P.

1984-03-01

Rabbit heart mitochondria were used as a source of enzymes for the synthesis of phosphorus-labeled creatine phosphate. This method is based on the coupled reaction between mitochondrial oxidative phosphorylation and mitochondrial-bound creatine kinase. It is possible to convert more than 90% of the inorganic phosphate (P/sub i/) to creatine phosphate. The method used only small amounts of adenine nucleotides which led to a product with only slight nucleotide contamination. This could be removed by activated charcoal extraction. For further purification, a method for the removal of residual P/sub i/ is described. 20 references.

Effects of surface treatments and bonding types on the interfacial behavior of fiber metal laminate based on magnesium alloy

NASA Astrophysics Data System (ADS)

Zhang, Xi; Ma, Quanyang; Dai, Yu; Hu, Faping; Liu, Gang; Xu, Zouyuan; Wei, Guobing; Xu, Tiancai; Zeng, Qingwen; Xie, Weidong

2018-01-01

Fiber metal laminates based on magnesium alloys (MgFML) with different surface treatments and different bonding types were tested and analyzed. By using dynamic contact angle measurement and scanning electron microscopy (SEM), it was found that phosphating treatment can significantly improve the surface energy and wettability of magnesium alloy, and the surface energy of phosphated magnesium alloy was approximately 50% higher than that of abraded-only magnesium alloy. The single cantilever beam (SCB) test showed that the interfacial fracture energies of directly bonded MgFMLs based on abraded-only magnesium and abraded + phosphated magnesium were 650 J/m2 and 1030 J/m2, respectively, whereas the interfacial fracture energies of indirectly bonded MgFMLs were 1650 J/m2 and 2260 J/m2, respectively. Phosphating treatment and modified polypropylene interleaf were observed to improve the tensile strength and interfacial fracture toughness of MgFML. In addition, the rougher surface was more conducive to enhance the bonding strength and interfacial fracture toughness of MgFML.

Analysis of organophosphate hydraulic fluids in U.S. Air force base soils

PubMed

David; Seiber

1999-04-01

Tri-aryl and tri-alkyl organophosphates (TAPs) have been used extensively as flame-retardant hydraulic fluids and fluid additives in commercial and military aircraft. Up to 80% of the consumption of these fluids has been estimated to be lost to unrecovered leakage. Tri-aryl phosphate components of these fluids are resistant to volatilization and solubilization in water, thus, their primary environmental fate pathway is sorption to soils. Environmental audits of military air bases generally do not include quantification of these compounds in soils. We have determined the presence and extent of TAP contamination in soil samples from several U.S. Air Force bases. Soils were collected, extracted, and analyzed using GC/FPD and GC/MS. Tricresyl phosphate was the most frequently found TAP in soil, ranging from 0.02 to 130 ppm. Other TAPs in soils included triphenyl phosphate and isopropylated triphenyl phosphate. Observations are made regarding the distribution, typical concentrations, persistence, and need for further testing of TAPs in soils at military installations. Additionally, GC and mass spectral data for these TAPs are presented, along with methods for their extraction, sample clean-up, and quantification.

Efficacy of tooth whitening with different calcium phosphate-based formulations.

PubMed

Jin, Jian; Xu, Xiaohui; Lai, Guangyun; Kunzelmann, Karl-Heinz

2013-08-01

The aim of this in-vitro study was to evaluate the efficacy of tooth whitening using different calcium phosphate-based formulations. Teeth were treated with three different hydroxyapatite preparations at different concentrations and with two control preparations; each tooth was treated a total of three times. After application of the last material, hydrodynamic shear force was applied to mimic mechanical loading. After each treatment, tooth color was measured using a dental spectrophotometer, and the mean changes in L*a*b* values between different measurements were expressed as ∆E. The results indicated significant differences between the materials, but neither dose- nor time-dependent associations were found. The suspension containing tricalcium phosphate (10 wt%) showed the most obvious color change (∆E = 2.20 ± 0.90), while the suspension containing zinc-carbonate-apatite (20 wt%) showed the least obvious color change (∆E = 0.91 ± 0.50). Calcium phosphate-based formulations that can adhere to the enamel surface and contribute to tooth whitening have promising tooth-whitening potential. © 2013 Eur J Oral Sci.

Molybdate transport in a chemically complex aquifer: Field measurements compared with solute-transport model predictions

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1998-01-01

A natural-gradient tracer test was conducted in an unconfined sand and gravel aquifer on Cape Cod, Massachusetts. Molybdate was included in the injectate to study the effects of variable groundwater chemistry on its aqueous distribution and to evaluate the reliability of laboratory experiments for identifying and quantifying reactions that control the transport of reactive solutes in groundwater. Transport of molybdate in this aquifer was controlled by adsorption. The amount adsorbed varied with aqueous chemistry that changed with depth as freshwater recharge mixed with a plume of sewage-contaminated groundwater. Molybdate adsorption was strongest near the water table where pH (5.7) and the concentration of the competing solutes phosphate (2.3 micromolar) and sulfate (86 micromolar) were low. Adsorption of molybdate decreased with depth as pH increased to 6.5, phosphate increased to 40 micromolar, and sulfate increased to 340 micromolar. A one-site diffuse-layer surface-complexation model and a two-site diffuse-layer surface-complexation model were used to simulate adsorption. Reactions and equilibrium constants for both models were determined in laboratory experiments and used in the reactive-transport model PHAST to simulate the two-dimensional transport of molybdate during the tracer test. No geochemical parameters were adjusted in the simulation to improve the fit between model and field data. Both models simulated the travel distance of the molybdate cloud to within 10% during the 2-year tracer test; however, the two-site diffuse-layer model more accurately simulated the molybdate concentration distribution within the cloud.

Crystallization of dicalcium phosphate dihydrate with presence of glutamic acid and arginine at 37 °C.

PubMed

Li, Chengfeng; Ge, Xiaolu; Li, Guochang; Bai, Jiahai; Ding, Rui

2014-08-01

The formations of non-metabolic stones, bones and teeth were seriously related to the morphology, size and surface reactivity of dicalcium phosphate dihydrate (DCPD). Herein, a facile biomimetic mineralization method with presence of glutamic acid and arginine was employed to fabricate DCPD with well-defined morphology and adjustable crystallite size. In reaction solution containing more arginine, crystallization of DCPD occurred with faster rate of nucleation and higher density of stacked layers due to the generation of more OH(-) ions after hydrolysis of arginine at 37 °C. With addition of fluorescein or acetone, the consumption of OH(-) ions or desolvation reaction of Ca(2+) ions was modulated, which resulted in the fabrication of DCPD with adjustable crystallite sizes and densities of stacked layers. In comparison with fluorescein-loading DCPD, dicalcium phosphate anhydrate was prepared with enhanced photoluminescence properties due to the reduction of self-quenching effect and regular arrangement of encapsulated fluorescein molecules. With addition of more acetone, DCPD was prepared with smaller crystallite size via antisolvent crystallization. The simulated process with addition of amino acids under 37 °C would shed light on the dynamic process of biomineralization for calcium phosphate compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

Are mixed explicit/implicit solvation models reliable for studying phosphate hydrolysis? A comparative study of continuum, explicit and mixed solvation models.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kamerlin, Shina C. L.; Haranczyk, Maciej; Warshel, Arieh

2009-05-01

Phosphate hydrolysis is ubiquitous in biology. However, despite intensive research on this class of reactions, the precise nature of the reaction mechanism remains controversial. In this work, we have examined the hydrolysis of three homologous phosphate diesters. The solvation free energy was simulated by means of either an implicit solvation model (COSMO), hybrid quantum mechanical / molecular mechanical free energy perturbation (QM/MM-FEP) or a mixed solvation model in which N water molecules were explicitly included in the ab initio description of the reacting system (where N=1-3), with the remainder of the solvent being implicitly modelled as a continuum. Here, bothmore » COSMO and QM/MM-FEP reproduce Delta Gobs within an error of about 2kcal/mol. However, we demonstrate that in order to obtain any form of reliable results from a mixed model, it is essential to carefully select the explicit water molecules from short QM/MM runs that act as a model for the true infinite system. Additionally, the mixed models tend to be increasingly inaccurate the more explicit water molecules are placed into the system. Thus, our analysis indicates that this approach provides an unreliable way for modelling phosphate hydrolysis in solution.« less

Changes in soil toxicity by phosphate-aided soil washing: effect of soil characteristics, chemical forms of arsenic, and cations in washing solutions.

PubMed

Jho, Eun Hea; Im, Jinwoo; Yang, Kyung; Kim, Young-Jin; Nam, Kyoungphile

2015-01-01

This study was set to investigate the changes in the toxicity of arsenic (As)-contaminated soils after washing with phosphate solutions. The soil samples collected from two locations (A: rice paddy and B: forest land) of a former smelter site were contaminated with a similar level of As. Soil washing (0.5 M phosphate solution for 2 h) removed 24.5% As, on average, in soil from both locations. Regardless of soil washing, Location A soil toxicities, determined using Microtox, were greater than that of Location B and this could be largely attributed to different soil particle size distribution. With soils from both locations, the changes in As chemical forms resulted in either similar or greater toxicities after washing. This emphasizes the importance of considering ecotoxicological aspects, which are likely to differ depending on soil particle size distribution and changes in As chemical forms, in addition to the total concentration based remedial goals, in producing ecotoxicologically-sound soils for reuse. In addition, calcium phosphate used as the washing solution seemed to contribute more on the toxic effects of the washed soils than potassium phosphate and ammonium phosphate. Therefore, it would be more appropriate to use potassium or ammonium phosphate than calcium phosphate for phosphate-aided soil washing of the As-contaminated soils. Copyright © 2014 Elsevier Ltd. All rights reserved.

Gondolellid conodonts and depositional setting of the Phosphoria Formation

USGS Publications Warehouse

Wardlaw, Bruce R.

2015-01-01

The Phosphoria Formation and related rocks were deposited over an 8.9 m.y. interval beginning approximately 274.0Ma and ending approximately 265.1Ma. The Meade Peak Phosphatic Shale Member was deposited in southeastern Idaho and adjacent Wyoming over 5.4 m.y. from approximately 273.2 to 268.6 Ma. The Retort Phosphatic Shale Member was deposited in southwestern Montana and west-central Wyoming over 1.3 m.y. from approximately 267.4 to 266.1Ma. The base of the Roadian Stage of the Middle Permian occurs within the lower phosphate zone of the Meade Peak. The base of the Wordian Stage occurs within the upper phosphate zone of the Meade Peak. The presence of a cool-water brachiopod fauna, cool-water conodont faunas, and the absence of fusulinids throughout the Phosphoria basin indicate the presence of pervasive cool, upwelling waters. Acritarchs are intimately associated with phosphorites and phosphatic shales and may have been the primary organic producer to help drive phosphate production. The gondolellid conodont fauna of the Phosphoria Formation links a geographic cline of Jinogondolella nankingensis from the Delaware basin, West Texas, to the Sverdrup basin, Canadian Arctic, and shows distinct differentiation in species distribution, as do other conodont groups, within the Phosphoria basin. Ten species and two subspecies of gondolellid conodonts are recognized from the Phosphoria Formation and related rocks that belong to Mesogondolella and Jinogondolella.

Phosphate-Modified Nucleotides for Monitoring Enzyme Activity.

PubMed

Ermert, Susanne; Marx, Andreas; Hacker, Stephan M

2017-04-01

Nucleotides modified at the terminal phosphate position have been proven to be interesting entities to study the activity of a variety of different protein classes. In this chapter, we present various types of modifications that were attached as reporter molecules to the phosphate chain of nucleotides and briefly describe the chemical reactions that are frequently used to synthesize them. Furthermore, we discuss a variety of applications of these molecules. Kinase activity, for instance, was studied by transfer of a phosphate modified with a reporter group to the target proteins. This allows not only studying the activity of kinases, but also identifying their target proteins. Moreover, kinases can also be directly labeled with a reporter at a conserved lysine using acyl-phosphate probes. Another important application for phosphate-modified nucleotides is the study of RNA and DNA polymerases. In this context, single-molecule sequencing is made possible using detection in zero-mode waveguides, nanopores or by a Förster resonance energy transfer (FRET)-based mechanism between the polymerase and a fluorophore-labeled nucleotide. Additionally, fluorogenic nucleotides that utilize an intramolecular interaction between a fluorophore and the nucleobase or an intramolecular FRET effect have been successfully developed to study a variety of different enzymes. Finally, also some novel techniques applying electron paramagnetic resonance (EPR)-based detection of nucleotide cleavage or the detection of the cleavage of fluorophosphates are discussed. Taken together, nucleotides modified at the terminal phosphate position have been applied to study the activity of a large diversity of proteins and are valuable tools to enhance the knowledge of biological systems.

Modulating protein behaviors on responsive surface by external electric fields: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Xie, Yun; Pan, Yufang; Zhang, Rong; Liang, Ying; Li, Zhanchao

2015-01-01

Molecular dynamics simulations were employed to investigate the modulation of protein behaviors on the electrically responsive zwitterionic phosphorylcholine self-assembled monolayers (PC-SAMs). Results show that PC-SAMs could sensitively respond to the applied electric fields and exhibit three states with different charge distributions, namely both the negatively charged phosphate groups and the positively charged choline groups are exposed to the solution in the absence of electric fields (state 1), phosphate groups exposed in the presence of positive electric fields (state 2), and choline groups exposed in the presence of negative electric fields (state 3). Under state 1, the adsorption of Cyt c on the PC-SAM is reversible and the orientations of Cyt c are randomly distributed. Under state 2, the adsorption of Cyt c is enhanced due to the electrostatic attractions between the exposed phosphate groups and the positively charged protein; when adsorbed on the PC-SAMs, Cyt c tends to adopt the orientation with the heme plane perpendicular to the surface plane, and the percentage of this orientation increases as the field strength rises up. Under state 3, the adsorption of Cyt c is retarded because of the electrostatic repulsions between the exposed choline groups and the protein; however, if the gaps between PC chains are large enough, Cyt c could insert into the PC-SAM and access the phosphate groups after overcoming a slight energy barrier. Under three states, the basic backbone structures of Cyt c are well kept within the simulation time since the conformation of Cyt c is mainly affected by the surface-generated electric fields, whose strengths are modulated by the external electric fields and are not strong enough to deform protein. The results indicate the possibility of regulating protein behaviors, including promoting or retarding protein adsorption and regulating protein orientations, on responsive surfaces by applying electric fields on the surfaces without worrying protein deformation, which may be helpful in the applications of protein separation and controlled drug delivery.

Analysis of alkyl phosphates in petroleum samples by comprehensive two-dimensional gas chromatography with nitrogen phosphorus detection and post-column Deans switching.

PubMed

Nizio, Katie D; Harynuk, James J

2012-08-24

Alkyl phosphate based gellants used as viscosity builders for fracturing fluids used in the process of hydraulic fracturing have been implicated in numerous refinery-fouling incidents in North America. In response, industry developed an inductively coupled plasma optical emission spectroscopy (ICP-OES) based method for the analysis of total volatile phosphorus in distillate fractions of crude oil; however, this method is plagued by poor precision and a high limit of detection (0.5±1μg phosphorus mL(-1)). Furthermore this method cannot provide speciation information, which is critical for developing an understanding of the challenge of alkyl phosphates at a molecular level. An approach using comprehensive two-dimensional gas chromatography with nitrogen phosphorus detection (GC×GC-NPD) and post-column Deans switching is presented. This method provides qualitative and quantitative profiles of alkyl phosphates in industrial petroleum samples with increased precision and at levels comparable to or below those achievable by ICP-OES. A recovery study in a fracturing fluid sample and a profiling study of alkyl phosphates in four recovered fracturing fluid/crude oil mixtures (flowback) are also presented. Copyright © 2012 Elsevier B.V. All rights reserved.

Approach to hypophosphataemia in intensive care units - a nationwide survey.

PubMed

Geerse, D A; Bindels, A J; Kuiper, M A; Roos, A N; Spronk, P E; Schultz, M J

2012-11-01

Evidence-based guidelines for monitoring of serum phosphate levels and for the treatment of hypophosphataemia in critically ill patients are lacking. The aim of this survey was to evaluate current practice with respect to diagnosis and treatment of hypophosphataemia in critically ill patients among intensive care unit (ICU) physicians in the Netherlands. A survey was conducted among all hospitals with an ICU in the Netherlands. Paediatric ICUs were excluded from participation. A questionnaire was sent, with questions on practice regarding serum phosphate monitoring and treatment of hypophosphataemia. Respondents returned the questionnaire either by mail or through a web-based survey. A response was received from 67÷89 ICUs (75%). Respondents mentioned renal replacement therapy, sepsis and malnutrition, as well as surgery involving cardiopulmonary bypass as the most important causes of hypophosphataemia in intensive care unit patients. Of all respondents, 46% reported to measure serum phosphate levels on a daily basis, whereas in 12% serum phosphate levels were measured only on clinical indication. Less than half of the respondents had some sort of guideline for correction of hypophosphataemia. In a vast majority (79%), correction of hypophosphataemia was reported to start with serum phosphate levels.

Phosphate recovery from wastewater using engineered superparamagnetic particles modified with layered double hydroxide ion exchangers.

PubMed

Drenkova-Tuhtan, Asya; Mandel, Karl; Paulus, Anja; Meyer, Carsten; Hutter, Frank; Gellermann, Carsten; Sextl, Gerhard; Franzreb, Matthias; Steinmetz, Heidrun

2013-10-01

An innovative nanocomposite material is proposed for phosphate recovery from wastewater using magnetic assistance. Superparamagnetic microparticles modified with layered double hydroxide (LDH) ion exchangers of various compositions act as phosphate adsorbers. Magnetic separation and chemical regeneration of the particles allows their reuse, leading to the successful recovery of phosphate. Based upon the preliminary screening of different LDH ion exchanger modifications for phosphate selectivity and uptake capacity, MgFe-Zr LDH coated magnetic particles were chosen for further characterization and application. The adsorption kinetics of phosphate from municipal wastewater was studied in dependence with particle concentration, contact time and pH. Adsorption isotherms were then determined for the selected particle system. Recovery of phosphate and regeneration of the particles was examined via testing a variety of desorption solutions. Reusability of the particles was demonstrated for 15 adsorption/desorption cycles. Adsorption in the range of 75-97% was achieved in each cycle after 1 h contact time. Phosphate recovery and enrichment was possible through repetitive application of the desorption solution. Finally, a pilot scale experiment was carried out by treating 125 L of wastewater with the particles in five subsequent 25 L batches. Solid-liquid separation on this scale was carried out with a high-gradient magnetic filter (HGMF). Copyright © 2013 Elsevier Ltd. All rights reserved.

TPhP exposure disturbs carbohydrate metabolism, lipid metabolism, and the DNA damage repair system in zebrafish liver

NASA Astrophysics Data System (ADS)

Du, Zhongkun; Zhang, Yan; Wang, Guowei; Peng, Jianbiao; Wang, Zunyao; Gao, Shixiang

2016-02-01

Triphenyl phosphate is a high production volume organophosphate flame retardant that has been detected in multiple environmental media at increasing concentrations. The environmental and health risks of triphenyl phosphate have drawn attention because of the multiplex toxicity of this chemical compound. However, few studies have paid close attention to the impacts of triphenyl phosphate on liver metabolism. We investigated hepatic histopathological, metabolomic and transcriptomic responses of zebrafish after exposure to 0.050 mg/L and 0.300 mg/L triphenyl phosphate for 7 days. Metabolomic analysis revealed significant changes in the contents of glucose, UDP-glucose, lactate, succinate, fumarate, choline, acetylcarnitine, and several fatty acids. Transcriptomic analysis revealed that related pathways, such as the glycosphingolipid biosynthesis, PPAR signaling pathway and fatty acid elongation, were significantly affected. These results suggest that triphenyl phosphate exposure markedly disturbs hepatic carbohydrate and lipid metabolism in zebrafish. Moreover, DNA replication, the cell cycle, and non-homologous end-joining and base excision repair were strongly affected, thus indicating that triphenyl phosphate hinders the DNA damage repair system in zebrafish liver cells. The present study provides a systematic analysis of the triphenyl phosphate-induced toxic effects in zebrafish liver and demonstrates that low concentrations of triphenyl phosphate affect normal metabolism and cell cycle.

TPhP exposure disturbs carbohydrate metabolism, lipid metabolism, and the DNA damage repair system in zebrafish liver

PubMed Central

Du, Zhongkun; Zhang, Yan; Wang, Guowei; Peng, Jianbiao; Wang, Zunyao; Gao, Shixiang

2016-01-01

Triphenyl phosphate is a high production volume organophosphate flame retardant that has been detected in multiple environmental media at increasing concentrations. The environmental and health risks of triphenyl phosphate have drawn attention because of the multiplex toxicity of this chemical compound. However, few studies have paid close attention to the impacts of triphenyl phosphate on liver metabolism. We investigated hepatic histopathological, metabolomic and transcriptomic responses of zebrafish after exposure to 0.050 mg/L and 0.300 mg/L triphenyl phosphate for 7 days. Metabolomic analysis revealed significant changes in the contents of glucose, UDP-glucose, lactate, succinate, fumarate, choline, acetylcarnitine, and several fatty acids. Transcriptomic analysis revealed that related pathways, such as the glycosphingolipid biosynthesis, PPAR signaling pathway and fatty acid elongation, were significantly affected. These results suggest that triphenyl phosphate exposure markedly disturbs hepatic carbohydrate and lipid metabolism in zebrafish. Moreover, DNA replication, the cell cycle, and non-homologous end-joining and base excision repair were strongly affected, thus indicating that triphenyl phosphate hinders the DNA damage repair system in zebrafish liver cells. The present study provides a systematic analysis of the triphenyl phosphate-induced toxic effects in zebrafish liver and demonstrates that low concentrations of triphenyl phosphate affect normal metabolism and cell cycle. PMID:26898711

Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios.

PubMed

Li, Ronghua; Wang, Jim J; Zhou, Baoyue; Awasthi, Mukesh Kumar; Ali, Amjad; Zhang, Zengqiang; Gaston, Lewis A; Lahori, Altaf Hussain; Mahar, Amanullah

2016-07-15

Mg/Al ratio plays a significant role for anion adsorption by Mg/Al-layered double hydroxides (Mg/Al-LDHs) modified biochar. In this study, Mg/Al-LDHs biochar with different Mg/Al ratios (2, 3, 4) were prepared by co-precipitation for phosphate removal from aqueous solution. Factors on phosphate adsorption including Mg/Al ratio, pH, and the presence of other inorganic anions were investigated through batch experiments. Increasing Mg/Al ratio in the Mg/Al-LDHs biochar composites generally enhanced phosphate adsorption with Langmuir adsorption maximum calculated at 81.83mg phosphorous (P) per gram of 4:1Mg/Al-LDHs biochar at pH3.0. The adsorption process was best described by the pseudo-second-order kinetic model. Solution pH had greater effects on the phosphate adsorption by Mg/Al LDHs biochar composites with lower Mg/Al ratios. The presence of other inorganic anions decreased the phosphate adsorption efficiency in the order of F(-) > SO4(2-) > NO2(-) >Cl(-). Phosphate adsorption mechanism involves ion exchange, electrostatic attraction and surface inner-sphere complex formation. Overall, Mg/Al-LDHs biochar composites offer a potential alternative of carbon-based adsorbent for phosphate removal from aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Simulations Meet Experiment to Reveal New Insights into DNA Intrinsic Mechanics

PubMed Central

Ben Imeddourene, Akli; Elbahnsi, Ahmad; Guéroult, Marc; Oguey, Christophe; Foloppe, Nicolas; Hartmann, Brigitte

2015-01-01

The accurate prediction of the structure and dynamics of DNA remains a major challenge in computational biology due to the dearth of precise experimental information on DNA free in solution and limitations in the DNA force-fields underpinning the simulations. A new generation of force-fields has been developed to better represent the sequence-dependent B-DNA intrinsic mechanics, in particular with respect to the BI ↔ BII backbone equilibrium, which is essential to understand the B-DNA properties. Here, the performance of MD simulations with the newly updated force-fields Parmbsc0εζOLI and CHARMM36 was tested against a large ensemble of recent NMR data collected on four DNA dodecamers involved in nucleosome positioning. We find impressive progress towards a coherent, realistic representation of B-DNA in solution, despite residual shortcomings. This improved representation allows new and deeper interpretation of the experimental observables, including regarding the behavior of facing phosphate groups in complementary dinucleotides, and their modulation by the sequence. It also provides the opportunity to extensively revisit and refine the coupling between backbone states and inter base pair parameters, which emerges as a common theme across all the complementary dinucleotides. In sum, the global agreement between simulations and experiment reveals new aspects of intrinsic DNA mechanics, a key component of DNA-protein recognition. PMID:26657165

Phosphate Remediation and Recovery using Iron Oxide-based Adsorbents

EPA Science Inventory

E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese and nanoparticles. Characterization was done by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-...

DECREASING LEAD BIOAVAILABILITY OF MINE WASTES: TWO PHOSPHATE FIELD STUDIES

EPA Science Inventory

Findings from two evaluation studies of phosphate-based in situ treatment of soils for reducing lead (Pb) bioavailability at two lead mining and lead refining Superfund sites will be presented and discussed. These assessments correlated physicochemical data with results obtained...

Incident-response monitoring technologies for aircraft cabin air quality

NASA Astrophysics Data System (ADS)

Magoha, Paul W.

Poor air quality in commercial aircraft cabins can be caused by volatile organophosphorus (OP) compounds emitted from the jet engine bleed air system during smoke/fume incidents. Tri-cresyl phosphate (TCP), a common anti-wear additive in turbine engine oils, is an important component in today's global aircraft operations. However, exposure to TCP increases risks of certain adverse health effects. This research analyzed used aircraft cabin air filters for jet engine oil contaminants and designed a jet engine bleed air simulator (BAS) to replicate smoke/fume incidents caused by pyrolysis of jet engine oil. Field emission scanning electron microscopy (FESEM) with X-ray energy dispersive spectroscopy (EDS) and neutron activation analysis (NAA) were used for elemental analysis of filters, and gas chromatography interfaced with mass spectrometry (GC/MS) was used to analyze used filters to determine TCP isomers. The filter analysis study involved 110 used and 90 incident filters. Clean air filter samples exposed to different bleed air conditions simulating cabin air contamination incidents were also analyzed by FESEM/EDS, NAA, and GC/MS. Experiments were conducted on a BAS at various bleed air conditions typical of an operating jet engine so that the effects of temperature and pressure variations on jet engine oil aerosol formation could be determined. The GC/MS analysis of both used and incident filters characterized tri- m-cresyl phosphate (TmCP) and tri-p-cresyl phosphate (TpCP) by a base peak of an m/z = 368, with corresponding retention times of 21.9 and 23.4 minutes. The hydrocarbons in jet oil were characterized in the filters by a base peak pattern of an m/z = 85, 113. Using retention times and hydrocarbon thermal conductivity peak (TCP) pattern obtained from jet engine oil standards, five out of 110 used filters tested had oil markers. Meanwhile 22 out of 77 incident filters tested positive for oil fingerprints. Probit analysis of jet engine oil aerosols obtained from BAS tests by optical particle counter (OPC) revealed lognormal distributions with the mean (range) of geometric mass mean diameter (GMMD) = 0.41 (0.39, 0.45) microm and geometric standard deviation (GSD), sigma g = 1.92 (1.87, 1.98). FESEM/EDS and NAA techniques found a wide range of elements on filters, and further investigations of used filters are recommended using these techniques. The protocols for air and filter sampling and GC/MS analysis used in this study will increase the options available for detecting jet engine oil on cabin air filters. Such criteria could support policy development for compliance with cabin air quality standards during incidents.

Serum Phosphate and Retinal Microvascular Changes: The Multi-Ethnic Study of Atherosclerosis and the Beaver Dam Eye Study.

PubMed

Mehta, Rupal; Hodakowski, Alexander; Cai, Xuan; Lee, Kris E; Kestenbaum, Bryan R; de Boer, Ian H; Fawzi, Amani; Wong, Tien Yin; Ix, Joachim; Klein, Barbara; Klein, Ronald; Isakova, Tamara

2017-12-01

Higher levels of serum phosphate are strongly linked to increased risk of cardiovascular disease and therapies aimed to lower serum phosphate are employed in the management of patients with chronic kidney disease (CKD). Data are limited, however, on serum phosphate as a risk factor for microvascular disease in community-based populations. It is important to determine the impact of novel risk factors, such as phosphate, on the microvasculature. We conducted a prospective study of 3919 individuals in the Multi-Ethnic Study of Atherosclerosis (MESA) and 3544 individuals in the Beaver Dam Eye Study (BDES) to test the associations of serum phosphate with retinopathy and retinal vessel caliber, and change in retinopathy severity and change in retinal vessel caliber. Mean (standard deviation) serum phosphate was 3.66 (0.52) mg/dl in the MESA and 3.77 (0.55) mg/dl in the BDES. In multivariable adjusted models, phosphate was significantly associated with prevalent retinopathy in the MESA (Odds Ratio [OR] per 1 mg/dl increase in phosphate, 1.22; Confidence Interval [CI] 1.02-1.47) and the BDES (OR 1.06; CI 1.01-1.11). In stratified analyses, these relationships were even stronger and only seen in individuals with diabetes in both the MESA (OR 1.81; CI 1.30-2.53) and the BDES (OR 1.16; CI 1.05-1.29). Phosphate was not associated with incident or change in retinopathy severity, nor any retinal caliber outcome. Among community-living individuals with low prevalence of CKD, higher serum phosphate was associated with prevalent retinopathy in individuals with diabetes. Further longitudinal assessments in patients with diabetes necessitate further investigation.

Combining Experiments and Simulations of Extraction Kinetics and Thermodynamics in Advanced Separation Processes for Used Nuclear Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nilsson, Mikael

This 3-year project was a collaboration between University of California Irvine (UC Irvine), Pacific Northwest National Laboratory (PNNL), Idaho National Laboratory (INL), Argonne National Laboratory (ANL) and with an international collaborator at ForschungZentrum Jülich (FZJ). The project was led from UC Irvine under the direction of Profs. Mikael Nilsson and Hung Nguyen. The leads at PNNL, INL, ANL and FZJ were Dr. Liem Dang, Dr. Peter Zalupski, Dr. Nathaniel Hoyt and Dr. Giuseppe Modolo, respectively. Involved in this project at UC Irvine were three full time PhD graduate students, Tro Babikian, Ted Yoo, and Quynh Vo, and one MS student,more » Alba Font Bosch. The overall objective of this project was to study how the kinetics and thermodynamics of metal ion extraction can be described by molecular dynamic (MD) simulations and how the simulations can be validated by experimental data. Furthermore, the project includes the applied separation by testing the extraction systems in a single stage annular centrifugal contactor and coupling the experimental data with computational fluid dynamic (CFD) simulations. Specific objectives of the proposed research were: Study and establish a rigorous connection between MD simulations based on polarizable force fields and extraction thermodynamic and kinetic data. Compare and validate CFD simulations of extraction processes for An/Ln separation using different sizes (and types) of annular centrifugal contactors. Provide a theoretical/simulation and experimental base for scale-up of batch-wise extraction to continuous contactors. We approached objective 1 and 2 in parallel. For objective 1 we started by studying a well established extraction system with a relatively simple extraction mechanism, namely tributyl phosphate. What we found was that well optimized simulations can inform experiments and new information on TBP behavior was presented in this project, as well be discussed below. The second objective proved a larger challenge and most of the efforts were devoted to experimental studies.« less

Study of a hydraulic dicalcium phosphate dihydrate/calcium oxide-based cement for dental applications.

PubMed

el-Briak, Hasna; Durand, Denis; Nurit, Josiane; Munier, Sylvie; Pauvert, Bernard; Boudeville, Phillipe

2002-01-01

By mixing CaHPO(4) x 2H(2)O (DCPD) and CaO with water or sodium phosphate buffers as liquid phase, a calcium phosphate cement was obtained. Its physical and mechanical properties, such as compressive strength, initial and final setting times, cohesion time, dough time, swelling time, dimensional and thermal behavior, and injectability were investigated by varying different parameters such as liquid to powder (L/P) ratio (0.35-0.7 ml g(-1)), molar calcium to phosphate (Ca/P) ratio (1.67-2.5) and the pH (4, 7, and 9) and the concentration (0-1 M) of the sodium phosphate buffer. The best results were obtained with the pH 7 sodium phosphate buffer at the concentration of 0.75 M. With this liquid phase, physical and mechanical properties depended on the Ca/P and L/P ratios, varying from 3 to 11 MPa (compressive strength), 6 to 10 min (initial setting time), 11 to 15 min (final setting time), 15 to 30 min (swelling time), 7 to 20 min (time of 100% injectability). The dough or working time was over 16 min. This cement expanded during its setting (1.2-5 % according to Ca/P and L/P ratios); this would allow a tight filling. Given the mechanical and rheological properties of this new DCPD/CaO-based cement, its use as root canal sealing material can be considered as classical calcium hydroxide or ZnO/eugenol-based pastes, without or with a gutta-percha point. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 447-453, 2002

EFFECTS OF TREATMENTS ON SOIL-LEAD BIOAVAILABILITY: IMPLICATIONS OF IN-VITRO EXTRACTION TESTING

EPA Science Inventory

A field-scale study on the use of phosphate amendments to reduce lead bioavailabity from soil is being conducted at the Joplin site. One of the tools used to evaluate whether lead bioavailability is being reduced is an in vitro extraction test. The in vitro test simulates the gas...

Structure and short time degradation studies of sodium zirconium phosphate ceramics loaded with simulated fast breeder (FBR) waste

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Ambashta, R. D.; Sudarsan, V.; Ajithkumar, T.; Sen, D.; Mazumder, S.; Wattal, P. K.

2017-04-01

Sodium zirconium phosphate (NZP) ceramics have been prepared using conventional sintering and hot isostatic pressing (HIP) routes. The structure of NZP ceramics, prepared using the HIP route, has been compared with conventionally sintered NZP using a combination of X-ray diffraction (XRD) and (31P and 23Na) nuclear magnetic resonance (NMR) spectroscopy techniques. It is observed that NZP with no waste loading is aggressive toward the steel HIP-can during hot isostatic compaction and significant fraction of cations from the steel enter the ceramic material. Waste loaded NZP samples (10 wt% simulated FBR waste) show significantly low can-interaction and primary NZP phase is evident in this material. Upon exposure of can-interacted and waste loaded NZP to boiling water and steam, 31P NMR does not detect any major modifications in the network structure. However, the 23Na NMR spectra indicate migration of Na+ ions from the surface and possible re-crystallization. This is corroborated by Small-Angle Neutron Scattering (SANS) data and Scanning Electron Microscopy (SEM) measurements carried out on these samples.

Chemical immobilization of Pb, Cu, and Cd by phosphate materials and calcium carbonate in contaminated soils.

PubMed

Huang, Guoyong; Su, Xiaojuan; Rizwan, Muhammad Shahid; Zhu, Yifei; Hu, Hongqing

2016-08-01

Soil contamination with toxic metals has increasingly become a global concern over the past few decades. Phosphate and carbonate compounds are good passivation materials for Pb immobilization, while the effect of phosphate and carbonate on the immobilization of multiple heavy metals (Pb, Cu, and Cd) in contaminated soils was seldom investigated. In this study, bone meal (BM), phosphate rock (PR), oxalic acid-activated phosphate rock (APR), super phosphate (SP), and calcium carbonate (CC) were added to the contaminated soils to evaluate the effect of phosphate materials and calcium carbonate on the immobilization of Pb, Cu, and Cd. The results showed that the pH of the treated soils increased 1.3-2.7, except SP which decreased 0.5 at most. Compared to the control treatment, all phosphates and calcium carbonate added to the polluted soils increased the fraction of residual metals, and the application of APR, PR, BM, and CC significantly reduced exchangeable and carbonate-bound fraction metals. PR and APR were the most effective for the immobilization of Pb, Cu, and Cd in the soils among these materials. Moreover, the concentrations of all metals in the toxicity characteristic leaching procedure (TCLP) leachate decreased with increasing amounts of amendments, and the concentrations of Pb in the TCLP leachate for soils treated with PR and APR were below the nonhazardous regulatory limit of 5 mg L(-1) (US Environmental Protection Agency). Based on our results, phosphate rock and oxalic acid-activated phosphate rock are effective in the immobilization of multiple metals by reducing their mobility in the co-contaminated soils.

Phosphatization Associated Features of Ferromanganese Crusts at Lemkein Seamount, Marshall Islands

NASA Astrophysics Data System (ADS)

Choi, J.; Lee, I.; Park, B. K.; Kim, J.

2014-12-01

Old layers of ferromanganese crusts, especially in the Pacific Ocean, have been affected by phosphatization. Ferromanganese crusts on Lemkein seamount in Marshall Islands also are phosphatized (3.3 to 4.2 wt % of P concentration). Furthermore, they have characteristic features that are different from other ferromanganese crusts. These features occur near the phosphorite, which were thought to fill the pore spaces of ferromanganese crusts. Inside the features, ferromanganese crusts are botryoidally precipitated from the round-boundary. The features of the phosphatized lower crusts of Lemkein seamount are observed using microscope and SEM. Elemental compositions of the selected samples were analyzed by SEM-EDS. Based on the observation and analysis of samples, three characteristic structures are identified: (1) phosphate-filled circles, (2) tongue-shaped framboidal crust, and (3) massive framboidal crust. The phosphate-filled circles are mostly composed of phosphorite, and they include trace fossils such as foraminifera. Phosphatized ferromanganese crusts exist at the boundary of this structure. The tongue-shaped crust is connected with the lips downward, and ferromanganese crusts inside the tongue show distinct growth rim. The massive framboidal crust is located below the tongue. Ferromanganese crusts in the massive framboidal crust are enveloped by phosphate, and some of the crusts are phosphatized. Around the structures, Mn oxide phase is concentrated as a shape of corona on BSE image. All of the structures are in the phosphatized crusts that show columnar growth of ferromanganese crusts and have sub-parallel lamination. These observation and chemical analysis of the ferromanganese crusts can provide a clue of diagenetic processes during the formation of ferromanganese crusts.

Phosphate homeostasis in CKD: report of a scientific symposium sponsored by the National Kidney Foundation.

PubMed

Block, Geoffrey A; Ix, Joachim H; Ketteler, Markus; Martin, Kevin J; Thadhani, Ravi I; Tonelli, Marcello; Wolf, Myles; Jüppner, Harald; Hruska, Keith; Wheeler, David C

2013-09-01

Chronic kidney disease (CKD)-mineral and bone disorder is associated with diverse metabolic and endocrine disturbances that ultimately may contribute to further loss of kidney function, bone demineralization, and fatal or nonfatal cardiovascular events. Recent insights into the pathophysiology of the events that unfold during the development of this disorder suggest that disturbances in phosphate metabolism are pivotal. The consequences of abnormal phosphate homeostasis are evident at estimated glomerular filtration rates <70 mL/min/1.73 m(2), long before serum phosphate levels increase. Healthy individuals with blood phosphate levels in the top quartile of the normal range have an increased risk of developing CKD, reaching end-stage renal disease, and experiencing cardiovascular events. Substantial public health consequences may be related to increased dietary phosphorus exposure from additives that contain phosphate in the food supply and from modest increases in serum phosphate levels; however, it remains to be established whether interventions aimed at these targets can impact on the development of adverse clinical outcomes. Current approaches involving dietary intervention and intestinal phosphate binders are based on principles and assumptions that need to be examined more rigorously. Compelling animal, observational, and clinical data indicate that interventions directed at lowering phosphate exposure and serum phosphate levels should be subject to rigorous clinical trials that use appropriate placebo comparators and focus on key clinical outcomes, such as cardiovascular events, progression of CKD, fractures, quality of life, and mortality. Copyright © 2013 National Kidney Foundation, Inc. Published by Elsevier Inc. All rights reserved.

Characterization of phosphate rock and phosphogypsum from Gabes phosphate fertilizer factories (SE Tunisia): high mining potential and implications for environmental protection.

PubMed

El Zrelli, Radhouan; Rabaoui, Lotfi; Daghbouj, Nabil; Abda, Heithem; Castet, Sylvie; Josse, Claudie; van Beek, Pieter; Souhaut, Marc; Michel, Sylvain; Bejaoui, Nejla; Courjault-Radé, Pierre

2018-05-01

Since the establishment of the coastal industrial complex in Gabes city (Gulf of Gabes, SE Tunisia), hundred million tons of untreated phosphogypsum have been discharged in the open sea causing serious environmental problems. To better understand the dynamic and behavior of phosphate/phosphogypsum contaminants from raw ores to marine environment, a chemical, organic, mineralogical, and morphological characterization of phosphate rock and phosphogypsum was conducted using several sophisticated techniques. The chemical analysis showed that phosphate and phosphogypsum contain high loads of trace elements and that the transfer factors of pollutants varied from 5.83% (U) to 140% (Hg). Estimated annual flows of phosphogypsum contaminants into the marine environment ranged between 0.05 (Re) and 87,249.60 (F) tons. The phosphate rock was found to be formed by carbonate fluorapatite, calcite, dolomite, natural gypsum, quartz, calcite-Mg, apatite, pyrite, fluorite, and sphalerite-Cd and phosphogypsum by synthetic gypsum and sphalerite-Cd. The phosphate was found to be richer in organic compounds compared to phosphogypsum. Based on this work, the Tunisian phosphogypsum has a high mining potential and encourages the development of an economically beneficial and environmentally friendly phosphogypsum-treating industry.

Metal sites in 3,4-dihydroxy-2-butanone 4-phosphate synthase from Methanococcus jannaschii in complex with the substrate ribulose 5-phosphate.

PubMed

Steinbacher, Stefan; Schiffmann, Susanne; Bacher, Adelbert; Fischer, Markus

2004-07-01

The crystal structure of Methanococcus jannaschii 3,4-dihydroxy-2-butanone 4-phosphate synthase in complex with the substrate ribulose 5-phosphate at a dimetal centre has recently been determined at 1.7 A resolution. The enzyme converts ribulose 5-phosphate into 3,4-dihydroxy-2-butanone 4-phosphate, while its C4 atom is released as formate. The resulting four-carbon body supplies all eight C atoms for the xylene moiety of riboflavin. Three of the four hydroxyl groups of ribulose 5-phosphate were coordinated by the metal ions. Based on crystallographic refinement, the metals were assigned as zinc and calcium, which were present in the crystallization buffer. Neither metal supports the enzymatic reaction. In the present study, the correctness of this assignment is assessed using anomalous diffraction data collected at the high-energy side of the zinc absorption edge (lambda = 1.2823 A). Only the three tentative zinc ions give strong peaks in an anomalous difference Fourier map (>20sigma), whereas the four tentative calcium ions do not show anomalous signals above the noise level. These results confirm the initial assignment. In addition, the resolution was improved to 1.55 A.

Synthesis of cellulose functionalized with polyallylamine and its application to on-line collection/concentration and determination of phosphate by ICP/AES.

PubMed

Sumida, Takashi; Yamashita, Minoru; Okazaki, Yuka; Kawakita, Hirohisa; Fukutomi, Takashi

2012-01-01

A novel cellulose-based resin functionalized with polyallylamine was synthesized. It was applied to the collection of phosphate in environmental water samples, followed by concentration determination using an inductively coupled plasma-atomic emission spectrometer (ICP/AES). The synthesized resin, cellulose-glycidylmethacrylate-polyallylamine (CGP), showed good adsorption behavior toward trace amounts of phosphate over a wide pH range. The adsorbed-analyte can be easily eluted using 0.5 M hydrochloric acid; its recoveries was found to be 80 - 100%. The CGP resin synthesized was packed in a mini-column, which was then installed in a computer-controlled auto-pretreatment system for on-line collection/concentration and determination of trace phosphate by ICP/AES. The limit of detection for phosphate was found to be 0.6 µg P l(-1). The sample volumes were only 5 ml and the total analysis time was about 4 min. The developed method with CGP resin was successfully applied to the determination of phosphate in river water and tap water samples with satisfactory results. The recovery test showed that common matrices that may exist in environmental waters did not interfere with the determination of phosphate.

Optimal use of phosphate binders in chronic kidney disease.

PubMed

Sonikian, Makrouhi; Papachristou, Evangelos; Goumenos, Dimitrios S

2013-12-01

Hyperphosphatemia is one of the major factors associated with the development of vascular calcification in patients with chronic kidney disease (CKD). Since phosphate is retained in such patients, pharmacological treatment and other measures are necessary to control hyperphosphatemia. Several phosphate binders (calcium salts, magnesium salts, non-calcium-based binders and aluminium) are available for the treatment of hyperphosphatemia. Nevertheless, none of the above mentioned agents has shown an overall superiority over others, while potency and side effects are quite variable among them creating difficulties in choosing the optimal drug for each patient. The authors discuss the disturbed phosphate metabolism, the available phosphate binders, as well as the general therapeutic principles of treating hyperphosphatemia in CKD patients. The literature used for this review had been retrieved from PubMed and covers a large number of original and retrospective studies as well as prospective cohort studies, meta-analyses and international clinical guidelines. Lowering serum phosphate levels in CKD patients may potentially have a positive impact on cardiovascular morbidity and mortality. Factors that should be taken into consideration when selecting a specific drug include CKD stage, cardiovascular disease, severity of secondary hyperparathyroidism, concomitant medications, life expectancy and patient compliance. Therefore, when selecting a specific phosphate binder, individualisation is mandatory.

Research on the material removal in the polishing of potassium dihydrogen phosphate crystals based on deliquescent action.

PubMed

Guo, Shaolong; Zhang, Feihu; Zhang, Yong; Luan, Dianrong

2014-01-01

Through the polishing experiments of potassium dihydrogen phosphate (KDP) crystals based on deliquescent action, the effect of several major factors, including crystal's initial surface state, polishing time, and revolution of polishing plate, on material removal was researched. Under certain experimental conditions, the rules of material removal were reached, and experimental results are discussed, which lays the foundation for popularization and application of polishing technology for KDP crystals based on deliquescent action.

Phosphate Remediation and Recovery from Lake Water using Modified Iron Oxide-based Adsorbents - abstract

EPA Science Inventory

As a limiting nutrient in most aquatic ecosystems, increased phosphate (PO43-) concentrations can accelerate eutrophication resulting in the proliferation of potentially toxic harmful algal blooms. In addition to environmental impacts of PO43- pollution, overall reserves of this ...

Occurrence and risk assessment of organophosphorus and brominated flame retardants in the River Aire (UK).

PubMed

Cristale, Joyce; Katsoyiannis, Athanasios; Sweetman, Andrew J; Jones, Kevin C; Lacorte, Silvia

2013-08-01

This study presents the occurrence and risk of PBDEs, new brominated and organophosphorus flame retardants along a river affected by urban and industrial pressures (River Aire, UK). Tris(2-choroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris[2-chloro-1-(chloromethyl)ethyl] phosphate (TDCP) and triphenyl phosphate (TPhP) were detected in all samples, with TCPP present at the highest concentrations, ranging from 113 to 26,050 ng L⁻¹. BDE-209 was detected in most of the sampled sites, ranging from 17 to 295 ng L⁻¹, while hexabromobenzene (HBB) and pentabromoethyl benzene (PBEB) were seldom detected. A risk quotients based on predicted no effect concentrations (PNEC) and flame retardants water concentration proved significant risk for adverse effects for algae, Daphnia and fish in sites close to industrial and urban sewage discharges. This study provides a protocol for the risk estimation of priority and new generation flame retardants based on river concentrations and toxicological values. Copyright © 2013 Elsevier Ltd. All rights reserved.

Piezoelectric sensor for sensitive determination of metal ions based on the phosphate-modified dendrimer

NASA Astrophysics Data System (ADS)

Wang, S. H.; Shen, C. Y.; Lin, Y. M.; Du, J. C.

2016-08-01

Heavy metal ions arising from human activities are retained strongly in water; therefore public water supplies must be monitored regularly to ensure the timely detection of potential problems. A phosphate-modified dendrimer film was investigated on a quartz crystal microbalance (QCM) for sensing metal ions in water at room temperature in this study. The chemical structures and sensing properties were characterized by Fourier transform infrared spectroscopy and QCM measurement, respectively. This phosphate-modified dendrimer sensor can directly detect metal ions in aqueous solutions. This novel sensor was evaluated for its capacity to sense various metal ions. The sensor exhibited a higher sensitivity level and shorter response time to copper(II) ions than other sensors. The linear detection range of the prepared QCM based on the phosphate-modified dendrimer was 0.0001 ∼ 1 μM Cu(II) ions (R2 = 0.98). The detection properties, including sensitivity, response time, selectivity, reusability, maximum adsorption capacity, and adsorption equilibrium constants, were also investigated.

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

The genomic response of the mouse kidney to low-phosphate diet is altered in X-linked hypophosphatemia.

PubMed

Meyer, Martha H; Dulde, Emily; Meyer, Ralph A

2004-06-17

The mechanism for the renal adaptation to low-phosphate diets is not well understood. Whether the Hyp mutation of the Phex gene blocks this adaptation is also not clear. To gain further insight into this, 5-wk-old normal and Hyp mice were fed a control (1.0% P) or low-phosphate diet (0.03% P) for 3-5 days. Renal RNA was hybridized to Affymetrix U74Av2 microarrays (5 arrays/group). Of the 5,719 detectable genes on each array, 290 responded significantly (P < 0.01) to low-phosphate diet in normal mice. This was reduced significantly (P < 0.001) to 7 in the Hyp mice. This suggested that the adaptations of the normal kidney to a low-phosphate environment were blocked by the Hyp mutation. The Npt2 phosphate transporter, vitamin D 1alpha- and 24-hydroxylases, and calbindins D9K and D28K responded in the expected fashion. Genes with significant (P < 0.05) diet-by-genotype interaction were analyzed by GenMAPP and MAPPFinder. This revealed a cluster of differentially expressed genes associated with microtubule-based processes. Most alpha- and beta-tubulins and most kinesins had responses to low-phosphate diet in normal mice which were abolished or reversed in Hyp mice. In summary, renal adaptation to low-phosphate diet involved changes in the mRNA expression of specific genes. Disruption of these responses in Hyp mice may contribute to their abnormal phosphate homeostasis.

Trace organic chemical attenuation during managed aquifer recharge: Insights from a variably saturated 2D tank experiment

NASA Astrophysics Data System (ADS)

Regnery, Julia; Lee, Jonghyun; Drumheller, Zachary W.; Drewes, Jörg E.; Illangasekare, Tissa H.; Kitanidis, Peter K.; McCray, John E.; Smits, Kathleen M.

2017-05-01

Meaningful model-based predictions of water quality and quantity are imperative for the designed footprint of managed aquifer recharge installations. A two-dimensional (2D) synthetic MAR system equipped with automated sensors (temperature, water pressure, conductivity, soil moisture, oxidation-reduction potential) and embedded water sampling ports was used to test and model fundamental subsurface processes during surface spreading managed aquifer recharge operations under controlled flow and redox conditions at the meso-scale. The fate and transport of contaminants in the variably saturated synthetic aquifer were simulated using the finite element analysis model, FEFLOW. In general, the model concurred with travel times derived from contaminant breakthrough curves at individual sensor locations throughout the 2D tank. However, discrepancies between measured and simulated trace organic chemical concentrations (i.e., carbamazepine, sulfamethoxazole, tris (2-chloroethyl) phosphate, trimethoprim) were observed. While the FEFLOW simulation of breakthrough curves captured overall shapes of trace organic chemical concentrations well, the model struggled with matching individual data points, although compound-specific attenuation parameters were used. Interestingly, despite steady-state operation, oxidation-reduction potential measurements indicated temporal disturbances in hydraulic properties in the saturated zone of the 2D tank that affected water quality.

Contribution to the modelling and analysis of logistics system performance by Petri nets and simulation models: Application in a supply chain

NASA Astrophysics Data System (ADS)

Azougagh, Yassine; Benhida, Khalid; Elfezazi, Said

2016-02-01

In this paper, the focus is on studying the performance of complex systems in a supply chain context by developing a structured modelling approach based on the methodology ASDI (Analysis, Specification, Design and Implementation) by combining the modelling by Petri nets and simulation using ARENA. The linear approach typically followed in conducting of this kind of problems has to cope with a difficulty of modelling due to the complexity and the number of parameters of concern. Therefore, the approach used in this work is able to structure modelling a way to cover all aspects of the performance study. The modelling structured approach is first introduced before being applied to the case of an industrial system in the field of phosphate. Results of the performance indicators obtained from the models developed, permitted to test the behaviour and fluctuations of this system and to develop improved models of the current situation. In addition, in this paper, it was shown how Arena software can be adopted to simulate complex systems effectively. The method in this research can be applied to investigate various improvements scenarios and their consequences before implementing them in reality.

Structure and electrical properties of DNA nanotubes embedded in lipid bilayer membranes

PubMed Central

Maiti, Prabal K

2018-01-01

Abstract Engineering the synthetic nanopores through lipid bilayer membrane to access the interior of a cell is a long persisting challenge in biotechnology. Here, we demonstrate the stability and dynamics of a tile-based 6-helix DNA nanotube (DNT) embedded in POPC lipid bilayer using the analysis of 0.2 μs long equilibrium MD simulation trajectories. We observe that the head groups of the lipid molecules close to the lumen cooperatively tilt towards the hydrophilic sugar-phosphate backbone of DNA and form a toroidal structure around the patch of DNT protruding in the membrane. Further, we explore the effect of ionic concentrations to the in-solution structure and stability of the lipid-DNT complex. Transmembrane ionic current measurements for the constant electric field MD simulation provide the I-V characteristics of the water filled DNT lumen in lipid membrane. With increasing salt concentrations, the measured values of transmembrane ionic conductance of the porous DNT lumen vary from 4.3 to 20.6 nS. Simulations of the DNTs with ssDNA and dsDNA overhangs at the mouth of the pore show gating effect with remarkable difference in the transmembrane ionic conductivities for open and close state nanopores. PMID:29136243

Optimization for Reduced-Fat / Low-NaCl Meat Emulsion Systems with Sea Mustard (Undaria pinnatifida) and Phosphate

PubMed Central

Kim, Cheon-Jei; Hwang, Ko-Eun; Song, Dong-Heon; Jeong, Tae-Jun; Kim, Hyun-Wook

2015-01-01

The effects of reducing fat levels from 30% to 20% and salt concentrations from 1.5% to 1.0% by partially substituting incorporated phosphate and sea mustard were investigated based on physicochemical properties of reduced-fat / low-NaCl meat emulsion systems. Cooking loss and emulsion stability, hardness, springiness, and cohesiveness for reduced-fat / low-NaCl meat emulsion systems with 20% pork back fat and 1.2% sodium chloride samples with incorporation of phosphate and sea mustard were similar to the control with 30% pork back fat and 1.5% sodium chloride. Results showed that reduced-fat / low-NaCl meat emulsion system samples containing phosphate and sea mustard had higher apparent viscosity. The results of this study show that the incorporation of phosphate and sea mustard in the formulation will successfully reduce fat and salt in the final meat products. PMID:26761874

Chewability testing in the development of a chewable tablet for hyperphosphatemia.

PubMed

Lanz, Michael; Baldischweiler, Jan; Kriwet, Burkhard; Schill, Jutta; Stafford, John; Imanidis, Georgios

2014-12-01

The official Pharmacopeia does not include a test procedure for the in vitro estimation of the chewability of tablets and publications in the scientific literature on this subject are rare. The purpose of this study was to evaluate a number of different test procedures for assessing chewability, starting from standard breaking force and strength testing and progressing to develop new procedures that simulate the actual chewing action on tablets. A further goal was to apply these test procedures to characterize the chewability of the novel phosphate binder PA21 in comparison with a commercially available phosphate binder chewable tablet product based on lanthanum (Fosrenol®) and a chewable tablet product containing calcium (Calcimagon®) - the latter being used as a standard for its very good chewability. For this purpose, a number of development formulations (different batches of PA21) were tested. The radial or diametrical tablet breaking force offers a poor means of assessing chewability while the axial breaking force was concluded to better reflect the effect of chewing on the tablet. Measurement of tablet behavior upon repeated loading afforded the best simulation of the actual chewing action and was found to have a good discriminating power with respect to chewability of the tested tablets, especially when the tablet was moistened with artificial saliva. The developed tests are shown to be more suitable for evaluating chewing properties of tablets than currently used Pharmacopeial tests. Following ICHQ6, which calls for specification of hardness for chewable tablets, these test procedures enabled the optimal chewability features of PA21 tablets in development to be confirmed whilst still maintaining capabilities for robust production and transportation processes.

Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers

NASA Technical Reports Server (NTRS)

Kanavarioti, A.; Rosenbach, M. T.

1991-01-01

Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 < or = pH < or = 8.6. This degradation is been attributed to (i) nucleophilic substitution of the imidazolide and (ii) catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

Novel mode of inhibition by D-tagatose 6-phosphate through a Heyns rearrangement in the active site of transaldolase B variants.

PubMed

Stellmacher, Lena; Sandalova, Tatyana; Schneider, Sarah; Schneider, Gunter; Sprenger, Georg A; Samland, Anne K

2016-04-01

Transaldolase B (TalB) and D-fructose-6-phosphate aldolase A (FSAA) from Escherichia coli are C-C bond-forming enzymes. Using kinetic inhibition studies and mass spectrometry, it is shown that enzyme variants of FSAA and TalB that exhibit D-fructose-6-phosphate aldolase activity are inhibited covalently and irreversibly by D-tagatose 6-phosphate (D-T6P), whereas no inhibition was observed for wild-type transaldolase B from E. coli. The crystal structure of the variant TalB(F178Y) with bound sugar phosphate was solved to a resolution of 1.46 Å and revealed a novel mode of covalent inhibition. The sugar is bound covalently via its C2 atom to the ℇ-NH2 group of the active-site residue Lys132. It is neither bound in the open-chain form nor as the closed-ring form of D-T6P, but has been converted to β-D-galactofuranose 6-phosphate (D-G6P), a five-membered ring structure. The furanose ring of the covalent adduct is formed via a Heyns rearrangement and subsequent hemiacetal formation. This reaction is facilitated by Tyr178, which is proposed to act as acid-base catalyst. The crystal structure of the inhibitor complex is compared with the structure of the Schiff-base intermediate of TalB(E96Q) formed with the substrate D-fructose 6-phosphate determined to a resolution of 2.20 Å. This comparison highlights the differences in stereochemistry at the C4 atom of the ligand as an essential determinant for the formation of the inhibitor adduct in the active site of the enzyme.

Supramolecular structure of the casein micelle.

PubMed

McMahon, D J; Oommen, B S

2008-05-01

The supramolecular structure of colloidal casein micelles in milk was investigated by using a sample preparation protocol based on adsorption of proteins onto a poly-l-lysine and parlodion-coated copper grid, staining of proteins and calcium phosphate by uranyl oxalate, instantaneous freezing, and drying under a high vacuum. High-resolution transmission electron microscopy stereo-images were obtained showing the interior structure of casein micelles. On the basis of our interpretation of these images, an interlocked lattice model was developed in which both casein-calcium phosphate aggregates and casein polymer chains act together to maintain casein micelle integrity. The caseins form linear and branched chains (2 to 5 proteins long) interlocked by the casein-stabilized calcium phosphate nanoclusters. This model suggests that stabilization of calcium phosphate nanoclusters by phosphoserine domains of alpha(s1)-, alpha(s2)-, or beta-casein, or their combination, would orient their hydrophobic domains outward, allowing interaction and binding to other casein molecules. Other interactions between the caseins, such as calcium bridging, could also occur and further stabilize the supramolecule. The combination of having an interlocked lattice structure and multiple interactions results in an open, sponge-like colloidal supramolecule that is resistant to spatial changes and disintegration. Hydrophobic interactions between caseins surrounding a calcium phosphate nanocluster would prevent complete dissociation of casein micelles when the calcium phosphate nanoclusters are solubilized. Likewise, calcium bridging and other electrostatic interactions between caseins would prevent dissociation of the casein micelles into casein-calcium phosphate nanocluster aggregates when milk is cooled or urea is added to milk, and hydrophobic interactions are reduced. The appearance of both polymer chains and small aggregate particles during milk synthesis would also be expected based on this interlocked lattice model of casein micelles, and its supramolecule structure thus exhibits the principles of self-aggregation, interdependence, and diversity observed in nature.

Determination of organophosphate diesters in urine samples by a high-sensitivity method based on ultra high pressure liquid chromatography-triple quadrupole-mass spectrometry.

PubMed

Su, Guanyong; Letcher, Robert J; Yu, Hongxia

2015-12-24

Organophosphate (OP) diesters in urine samples have potential use as biomarkers of organism exposure to environmentally relevant OP triester precursors and in particular OP triester flame retardants. This present study developed a quantitatively sensitive ultra high pressure liquid chromatography (UHPLC-MS) based method for urine and the determination of OP diesters (i.e. diphenyl phosphate (DPHP), bis(2-chloroethyl) phosphate (BCEP), bis(2-chloroisopropyl) phosphate (BDCIPP), di-n-butyl phosphate (DNBP), di(2-ethylhexyl) phosphate (DEHP), bis(1-chloro-2-propyl) phosphate (BCIPP), and bis(2-butoxyethyl) phosphate (BBOEP)). Fortified with the 7 OP diesters, 1mL of human urine sample was cleaned up using weak anion exchange solid phase extraction and eluted with high ionic strength ammonium acetate buffer. Subsequently, 4 non-chlorinated OP diesters were directly determined using UHPLC-electrospray(-)-triple quadrupole-MS (UHPLC-ESI(-)-QqQ-MS), and UHPLC-ESI(+)-QqQ-MS was used for determination of 3 chlorinated OP diesters after methylation using diazomethane. Recovery efficiencies of OP diesters ranged from 88 to 160% at three spiking levels (0.4, 2 and 10ng/mL urine). Matrix effects (MEs) and method limits of quantification (MLOQs) were 15-134% and 0.10-0.32ng/mL urine, respectively. Concentrations of OP diesters in n=12 urine samples (from 4 Canadian residents, 2014) varied as follows, nd-<0.28 (DNBP), nd-1.29 (DPHP), nd-<0.28 (DEHP), <0.16-12.33 (BCEP), nd-1.17 (BCDIPP) and nd-0.68ng/mL (BCIPP). Copyright © 2015. Published by Elsevier B.V.

Short-term implantation effects of a DCPD-based calcium phosphate cement.

PubMed

Frayssinet, P; Gineste, L; Conte, P; Fages, J; Rouquet, N

1998-06-01

Calcium phosphate cements can be handled in paste form and set in a wet medium after precipitation of calcium phosphate crystals in the implantation site. Depending on the products entering into the chemical reaction leading to the precipitation of calcium phosphates, different phases can be obtained with different mechanical properties, setting times and injectability. We tested a cement composed of a powder, containing beta-tricalcium phosphate (beta-TCP) and sodium pyrophosphate mixed with a solution of phosphoric and sulphuric acids. The cement set under a dicalcium phosphate dihydrate (DCPD)-based matrix containing beta-TCP particles. This was injected with a syringe into a defect drilled in rabbit condyles, the control being an identical defect left empty in the opposite condyle. The condyles were analysed histologically 2, 6 and 18 weeks after implantation. After injection into the bone defect the cement set and formed a porous calcium phosphate structure. Two different calcium phosphate phases with different solubility rates could be identified by scanning electron microscopy (SEM) observation. The less-soluble fragments could be degraded by cell phagocytosis in cell compartments of low pH or integrated in the newly formed bone matrix. The degradation rate of the material was relatively high but compatible with the ingrowth of bone trabeculae within the resorbing material. The ossification process was different from the creeping substitution occurring at the ceramic contact. Bone did not form directly at the cement surface following the differentiation of osteoblasts at the material surface. The trabeculae came to the material surface from the edges of the implantation site. Bone formation in the implantation site was significantly higher than in the control region during the first week of implantation. In conclusion, this material set in situ was well tolerated, inducing a mild foreign-body reaction, which did not impair its replacement by newly formed bone within a few weeks.

Use of alternative assays to identify and prioritize organophosphorus flame retardants for potential developmental and neurotoxicity.

PubMed

Behl, Mamta; Hsieh, Jui-Hua; Shafer, Timothy J; Mundy, William R; Rice, Julie R; Boyd, Windy A; Freedman, Jonathan H; Hunter, E Sidney; Jarema, Kimberly A; Padilla, Stephanie; Tice, Raymond R

2015-01-01

Due to their toxicity and persistence in the environment, brominated flame retardants (BFRs) are being phased out of commercial use, leading to the increased use of alternative chemicals such as the organophosphorus flame retardants (OPFRs). There is, however, limited information on the potential health effects of OPFRs. Due to the structural similarity of the OPFRs to organophosphorus insecticides, there is concern regarding developmental toxicity and neurotoxicity. In response, we evaluated a set of OPFRs (triphenyl phosphate [TPHP]), isopropylated phenyl phosphate [IPP], 2-ethylhexyl diphenyl phosphate [EHDP], tert-butylated phenyl diphenyl phosphate [BPDP], trimethyl phenyl phosphate [TMPP], isodecyl diphenyl phosphate [IDDP], (tris(1,3-dichloroisopropyl) phosphate [TDCIPP], and tris(2-chloroethyl)phosphate [TCEP]) in a battery of cell-based in vitro assays and alternative model organisms and compared the results to those obtained for two classical BFRs (3,3',5,5'-tetrabromobisphenol A [TBBPA] and 2,2'4,4'-brominated diphenyl ether [BDE-47]). The assays used evaluated the effects of chemicals on the differentiation of mouse embryonic stem cells, the proliferation and growth of human neural stem cells, rat neuronal growth and network activity, and development of nematode (Caenorhabditis elegans) and zebrafish (Danio rerio). All assays were performed in a concentration-response format, allowing for the determination of the point of departure (POD: the lowest concentration where a chemically-induced response exceeds background noise). The majority of OPFRs (8/9) were active in multiple assays in the range of 1-10 μM, most of which had comparable activity to the BFRs TBBPA and BDE-47. TCEP was negative in all assays. The results indicate that the replacement OPFRs, with the exception of TCEP, showed comparable activity to the two BFRs in the assays tested. Based on these results, more comprehensive studies are warranted to further characterize the potential hazard of some of these OPFR compounds. Published by Elsevier Inc.

Dietary and genetic evidence for phosphate toxicity accelerating mammalian aging

PubMed Central

Ohnishi, Mutsuko; Razzaque, M. Shawkat

2010-01-01

Identifying factors that accelerate the aging process can provide important therapeutic targets for slowing down this process. Misregulation of phosphate homeostasis has been noted in various skeletal, cardiac, and renal diseases, but the exact role of phosphate toxicity in mammalian aging is not clearly defined. Phosphate is widely distributed in the body and is involved in cell signaling, energy metabolism, nucleic acid synthesis, and the maintenance of acid-base balance by urinary buffering. In this study, we used an in vivo genetic approach to determine the role of phosphate toxicity in mammalian aging. Klotho-knockout mice (klotho−/−) have a short life span and show numerous physical, biochemical, and morphological features consistent with premature aging, including kyphosis, uncoordinated movement, hypogonadism, infertility, severe skeletal muscle wasting, emphysema, and osteopenia, as well as generalized atrophy of the skin, intestine, thymus, and spleen. Molecular and biochemical analyses suggest that increased renal activity of sodium-phosphate cotransporters (NaPi2a) leads to severe hyperphosphatemia in klotho−/− mice. Genetically reducing serum phosphate levels in klotho−/− mice by generating a NaPi2a and klotho double-knockout (NaPi2a−/−/klotho−/−) strain resulted in amelioration of premature aging-like features. The NaPi2a−/−/klotho−/− double-knockout mice regained reproductive ability, recovered their body weight, reduced their organ atrophy, and suppressed ectopic calcifications, with the resulting effect being prolonged survival. More important, when hyperphosphatemia was induced in NaPi2a−/−/klotho−/− mice by feeding with a high-phosphate diet, premature aging-like features reappeared, clearly suggesting that phosphate toxicity is the main cause of premature aging in klotho−/− mice. The results of our dietary and genetic manipulation studies provide in vivo evidence for phosphate toxicity accelerating the aging process and suggest a novel role for phosphate in mammalian aging.—Ohnishi, M., Razzaque, M. S. Dietary and genetic evidence for phosphate toxicity accelerating mammalian aging. PMID:20418498

Single- and multiple-dose pharmacokinetics and absolute bioavailability of tedizolid.

PubMed

Flanagan, Shawn; Fang, Edward; Muñoz, Kelly A; Minassian, Sonia L; Prokocimer, Philippe G

2014-09-01

Tedizolid phosphate is a novel antibacterial under investigation for the treatment of gram-positive infections. This study was conducted to assess the pharmacokinetics, safety, and tolerability of intravenous tedizolid phosphate as well as the oral bioavailability of tedizolid phosphate. Double-blind, single-ascending dose, multiple-dose pharmacokinetics study, as well as tolerability and open-label crossover studies. Single center in the United States (Covance Clinical Research Unit, Madison, WI) between September 2009 and January 2010. Ninety healthy volunteers. Single intravenous (IV) doses of tedizolid phosphate 50 mg (lead-in) and 100-400 mg. Single oral and IV dose of tedizolid phosphate 200 mg in crossover fashion. Multiple IV doses of tedizolid phosphate 200 and 300 mg for up to 7 days. A dose-dependent increase was observed in the maximum plasma concentration (1.2-5.1 μg/ml) and the area under the concentration-time curve (17.4-58.7 μg × hr/ml) of tedizolid (the microbiologically active moiety of tedizolid phosphate) after single IV doses of tedizolid phosphate 100-400 mg. Administration of IV tedizolid phosphate 200 mg once/day for 7 days resulted in minimal (28%) tedizolid accumulation. The absolute oral bioavailability of tedizolid after a single 200-mg dose of tedizolid phosphate was 91%; pharmacokinetic parameters of tedizolid were similar with oral and IV administration. Treatment-related adverse events occurred in 41% of subjects. Most adverse events were related to infusion site and became more frequent with multiple dosing. In an additional 3-day tolerability study, IV tedizolid phosphate 200 mg and placebo were similarly tolerated, based on visual infusion phlebitis scores. These results from a population of healthy volunteers support once/day dosing of tedizolid phosphate 200 mg with both the oral and IV formulations, without the need for dose adjustment when switching administration routes. © 2014 Cubist Pharmaceuticals. Pharmacotherapy published by Wiley Periodicals, Inc. on behalf of Pharmacotherapy Publications, Inc.

Cone calorimeter evaluation of two flame retardant cotton fabrics

USDA-ARS?s Scientific Manuscript database

Unbleached (grey) cotton needle punched nonwoven (NW) fabrics with 12.5% polypropylene scrim were treated with two phosphate-nitrogen based fire-retardant (FR) formulations, SRRC-1 and SRRC-2. The SRRC-1 formulation contains diammonium phosphate as the flame retardant chemical along with urea and d...

ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS. II. ACID AND GENERAL BASE CATALYZED HYDROLYSIS

EPA Science Inventory

SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate acid and neutral hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition states of a ...

Enhanced phosphate removal from wastewater by using in situ generated fresh trivalent Fe composition through the interaction of Fe(II) on CaCO3.

PubMed

Li, Yujie; He, Xiaoman; Hu, Huimin; Zhang, Tingting; Qu, Jun; Zhang, Qiwu

2018-05-21

Excessive existences of nutrients such as phosphate in the aqueous environment remain as a heavy concern although many researches have been reported for dealing with their removal. Based on the understanding toward the interactions of Fe compounds with phosphate and carbonate from many available researches, we designed a very simple and efficient approach for phosphate removal by using in situ generated fresh trivalent Fe composition through the interaction of Fe(II) as FeSO 4 on CaCO 3 . Addition and agitation of Fe(II) and CaCO 3 simultaneously to phosphate solution allowed an amorphous Fe(III)-P or Ca-Fe(III)-P precipitation, with a phosphate removal rate close to 100%, to reduce the residual phosphorus concentration less than 0.03 mg/L from 100 mg/L, reaching the discharge limit, even with the addition amounts of CaCO 3 as low as a stoichiometric ratio of CaCO 3 /PO 4 3- at 0.9 and ratio of Fe(II)/PO 4 3- at 1.5, and the percent of P 2 O 5 in the precipitate was as high as 19.4% enough as phosphate source for fertilizer production. Different from the alkaline process with enough OH - group, the slow hydrolysis of CaCO 3 resulting in low concentration of OH - group for the formation of Fe(OH) 2 , which was oxidized soon by air into trivalent Fe, achieved a continuous generation of fresh ferric composition for phosphate precipitation and could avoid its rapid formation and subsequent transformation into stable FeOOH of large particle size to lose the activity. These results based on the synergistic effect of using CaCO 3 and Fe(II) together may have applications in the treatment of eutrophic wastewater through a process with many advantages of easy operation and low-cost besides the high removal efficiency with phosphate percentage inside the precipitate high enough to serve for fertilizer production. Copyright © 2018 Elsevier Ltd. All rights reserved.

Dynamics of metals in backfill of a phosphate mine of guiyang, China using a three-step sequential extraction technique.

PubMed

Shi, Ying; Gan, Lei; Li, Xibing; He, Suya; Sun, Cheng; Gao, Li

2018-02-01

Phosphate rock in Guiyang (Southwest of China) is used for the phosphate production, and hence generating a by-product phosphogypsum (PG). From 2007, part of the PG was used as main raw material for cemented backfill. The main objective of this paper is to investigate the geochemical evolution of metals before and after the PG inclusion into the backfill matrix. A sequential extraction procedure was selected to determine the chemical speciation of metals in phosphate rock, PG, binder and field backfill samples. Dynamics of metals going from phosphate rock and PG to backfill have been evaluated. The results showed that almost all the metals in the PG and binder had been effectively transferred to the backfill. Furthermore, compared to metals taken out along with phosphate rock exploitation, PG-based cemented backfill might bring some metals back but with only little metals in mobile fraction. Additionally, in order to determine the long-term behavior of metals in PG-based cemented backfill, the field samples which were backfilled from 2007 to 2016 were collected and analyzed. The results showed that total amounts of metals in backfill were all within similar range, indicating that the cemented PG backfill could be an effective method to solidify/stabilize metals in PG. Nevertheless, Due to the high water-soluble fractions detected, the concentrations of As, Mn and Zn should be continuously monitored. Copyright © 2017. Published by Elsevier Ltd.

Structure-based prediction and identification of 4-epimerization activity of phosphate sugars in class II aldolases.

PubMed

Lee, Seon-Hwa; Hong, Seung-Hye; An, Jung-Ung; Kim, Kyoung-Rok; Kim, Dong-Eun; Kang, Lin-Woo; Oh, Deok-Kun

2017-05-16

Sugar 4-epimerization reactions are important for the production of rare sugars and their derivatives, which have various potential industrial applications. For example, the production of tagatose, a functional sweetener, from fructose by sugar 4-epimerization is currently constrained because a fructose 4-epimerase does not exist in nature. We found that class II D-fructose-1,6-bisphosphate aldolase (FbaA) catalyzed the 4-epimerization of D-fructose-6-phosphate (F6P) to D-tagatose-6-phosphate (T6P) based on the prediction via structural comparisons with epimerase and molecular docking and the identification of the condensed products of C3 sugars. In vivo, the 4-epimerization activity of FbaA is normally repressed. This can be explained by our results showing the catalytic efficiency of D-fructose-6-phosphate kinase for F6P phosphorylation was significantly higher than that of FbaA for F6P epimerization. Here, we identified the epimerization reactions and the responsible catalytic residues through observation of the reactions of FbaA and L-rhamnulose-1-phosphate aldolases (RhaD) variants with substituted catalytic residues using different substrates. Moreover, we obtained detailed potential epimerization reaction mechanism of FbaA and a general epimerization mechanism of the class II aldolases L-fuculose-1-phosphate aldolase, RhaD, and FbaA. Thus, class II aldolases can be used as 4-epimerases for the stereo-selective synthesis of valuable carbohydrates.

A facile pollutant-free approach toward a series of nutritionally effective calcium phosphate nanomaterials for food and drink additives

NASA Astrophysics Data System (ADS)

Wang, Jieru; Chen, Xiaoyi; Yang, Xianyan; Xu, Sanzhong; Zhang, Xinli; Gou, Zhongru

2011-03-01

Micronutrient malnutrition is widespread and constitutes one of the main nutritional problems worldwide. Vitamins, amino acids, carbohydrates and Ca-phosphate (CaP) minerals are important to human health and disease prevention. Herein we developed a simple wet-chemical method to prepare multinary nutrients-containing CaP nanomaterials in diluted apple, orange, and grape juices. The scanning electron microscopy observation shows that these nanomaterials are short plate-like CaP nanocrystals of 500 nm in length. The X-ray photoelectron spectroscopy, nitrogen adsorption, thermogravimetric analyses confirm the different specific surface area and organic nutrient contents. The Fourier transform infrared and X-ray diffraction analyses indicate there exist similar organic groups (i.e., COO-, HN-CO) but different CaP species in the precipitates. The dissolution test in vitro simulated stomach juice pH condition indicates that these inorganic-organic nanohybrid materials are multidoped by micronutrients (such as Zn, Sr, Mg, K, vitamin c) and can be readily dissolved in the weak acidic aqueous solutions. This highly efficient utilization of fruit juice to produce CaP-based micronutrient composites may minimize the adverse side effect, so that the nanomaterials are promising as functional food/drink additives. Thus, this novel approach is environmentally and biologically friendly to produce edible nutrients while production cost is attained.

Optimization and experimental validation of a thermal cycle that maximizes entropy coefficient fisher identifiability for lithium iron phosphate cells

NASA Astrophysics Data System (ADS)

Mendoza, Sergio; Rothenberger, Michael; Hake, Alison; Fathy, Hosam

2016-03-01

This article presents a framework for optimizing the thermal cycle to estimate a battery cell's entropy coefficient at 20% state of charge (SOC). Our goal is to maximize Fisher identifiability: a measure of the accuracy with which a parameter can be estimated. Existing protocols in the literature for estimating entropy coefficients demand excessive laboratory time. Identifiability optimization makes it possible to achieve comparable accuracy levels in a fraction of the time. This article demonstrates this result for a set of lithium iron phosphate (LFP) cells. We conduct a 24-h experiment to obtain benchmark measurements of their entropy coefficients. We optimize a thermal cycle to maximize parameter identifiability for these cells. This optimization proceeds with respect to the coefficients of a Fourier discretization of this thermal cycle. Finally, we compare the estimated parameters using (i) the benchmark test, (ii) the optimized protocol, and (iii) a 15-h test from the literature (by Forgez et al.). The results are encouraging for two reasons. First, they confirm the simulation-based prediction that the optimized experiment can produce accurate parameter estimates in 2 h, compared to 15-24. Second, the optimized experiment also estimates a thermal time constant representing the effects of thermal capacitance and convection heat transfer.

Development of petri net-based dynamic model for improved production of farnesyl pyrophosphate by integrating mevalonate and methylerythritol phosphate pathways in yeast.

PubMed

Baadhe, Rama Raju; Mekala, Naveen Kumar; Palagiri, Satwik Reddy; Parcha, Sreenivasa Rao

2012-07-01

In this case study, we designed a farnesyl pyrophosphate (FPP) biosynthetic network using hybrid functional Petri net with extension (HFPNe) which is derived from traditional Petri net theory and allows easy modeling with graphical approach of various types of entities in the networks together. Our main objective is to improve the production of FPP in yeast, which is further converted to amorphadiene (AD), a precursor of artemisinin (antimalarial drug). Natively, mevalonate (MEV) pathway is present in yeast. Methyl erythritol phosphate pathways (MEP) are present only in higher plant plastids and eubacteria, but not present in yeast. IPP and DAMP are common isomeric intermediate in these two pathways, which immediately yields FPP. By integrating these two pathways in yeast, we augmented the FPP synthesis approximately two folds higher (431.16 U/pt) than in MEV pathway alone (259.91 U/pt) by using HFPNe technique. Further enhanced FPP levels converted to AD by amorphadiene synthase gene yielding 436.5 U/pt of AD which approximately two folds higher compared to the AD (258.5 U/pt) synthesized by MEV pathway exclusively. Simulation and validation processes performed using these models are reliable with identified biological information and data.

Substrate specificity of pyrimidine nucleoside phosphorylases of NP-II family probed by X-ray crystallography and molecular modeling

NASA Astrophysics Data System (ADS)

Balaev, V. V.; Lashkov, A. A.; Prokofev, I. I.; Gabdulkhakov, A. G.; Seregina, T. A.; Mironov, A. S.; Betzel, C.; Mikhailov, A. M.

2016-09-01

Pyrimidine nucleoside phosphorylases, which are widely used in the biotechnological production of nucleosides, have different substrate specificity for pyrimidine nucleosides. An interesting feature of these enzymes is that the three-dimensional structure of thymidine-specific nucleoside phosphorylase is similar to the structure of nonspecific pyrimidine nucleoside phosphorylase. The three-dimensional structures of thymidine phosphorylase from Salmonella typhimurium and nonspecific pyrimidine nucleoside phosphorylase from Bacillus subtilis in complexes with a sulfate anion were determined for the first time by X-ray crystallography. An analysis of the structural differences between these enzymes demonstrated that Lys108, which is involved in the phosphate binding in pyrimidine nucleoside phosphorylase, corresponds to Met111 in thymidine phosphorylases. This difference results in a decrease in the charge on one of the hydroxyl oxygens of the phosphate anion in thymidine phosphorylase and facilitates the catalysis through SN2 nucleophilic substitution. Based on the results of X-ray crystallography, the virtual screening was performed for identifying a potent inhibitor (anticancer agent) of nonspecific pyrimidine nucleoside phosphorylase, which does not bind to thymidine phosphorylase. The molecular dynamics simulation revealed the stable binding of the discovered compound—2-pyrimidin-2-yl-1H-imidazole-4-carboxylic acid—to the active site of pyrimidine nucleoside phosphorylase.

Scaffolds with a standardized macro-architecture fabricated from several calcium phosphate ceramics using an indirect rapid prototyping technique

PubMed Central

Wilson, C. E.; van Blitterswijk, C. A.; Verbout, A. J.; de Bruijn, J. D.

2010-01-01

Calcium phosphate ceramics, commonly applied as bone graft substitutes, are a natural choice of scaffolding material for bone tissue engineering. Evidence shows that the chemical composition, macroporosity and microporosity of these ceramics influences their behavior as bone graft substitutes and bone tissue engineering scaffolds but little has been done to optimize these parameters. One method of optimization is to place focus on a particular parameter by normalizing the influence, as much as possible, of confounding parameters. This is difficult to accomplish with traditional fabrication techniques. In this study we describe a design based rapid prototyping method of manufacturing scaffolds with virtually identical macroporous architectures from different calcium phosphate ceramic compositions. Beta-tricalcium phosphate, hydroxyapatite (at two sintering temperatures) and biphasic calcium phosphate scaffolds were manufactured. The macro- and micro-architectures of the scaffolds were characterized as well as the influence of the manufacturing method on the chemistries of the calcium phosphate compositions. The structural characteristics of the resulting scaffolds were remarkably similar. The manufacturing process had little influence on the composition of the materials except for the consistent but small addition of, or increase in, a beta-tricalcium phosphate phase. Among other applications, scaffolds produced by the method described provide a means of examining the influence of different calcium phosphate compositions while confidently excluding the influence of the macroporous structure of the scaffolds. PMID:21069558

Microbial electrolysis cell accelerates phosphate remobilisation from iron phosphate contained in sewage sludge.

PubMed

Fischer, Fabian; Zufferey, Géraldine; Sugnaux, Marc; Happe, Manuel

2015-01-01

Phosphate was remobilised from iron phosphate contained in digested sewage sludge using a bio-electric cell. A significant acceleration above former results was caused by strongly basic catholytes. For these experiments a dual chambered microbial electrolysis cell with a small cathode (40 mL) and an 80 times larger anode (2.5 L) was equipped with a platinum sputtered reticulated vitreous carbon cathode. Various applied voltages (0.2-6.0 V) generated moderate to strongly basic catholytes using artificial waste water with pH close to neutral. Phosphate from iron phosphate contained in digested sewage sludge was remobilised most effectively at pH ∼13 with up to 95% yield. Beside minor electrochemical reduction, hydroxyl substitution was the dominating remobilisation mechanism. Particle-fluid kinetics using the "shrinking core" model allowed us to determine the reaction controlling step. Reaction rates changed with temperature (15-40 °C) and an activation energy of Ea = 55 kJ mol(-1) was found. These analyses indicated chemical and physical reaction control, which is of interest for future scale-up work. Phosphate remobilisation rates increased significantly, yields doubled and recovered PO4(3-) concentrations increased four times using a task specific bio-electric system. The result is a sustainable process for decentralized phosphate mining and a green chemical base generator useful also for many other sustainable processing needs.

On the use of 31P NMR for the quantification of hydrosoluble phosphorus-containing compounds in coral host tissues and cultured zooxanthellae.

PubMed

Godinot, Claire; Gaysinski, Marc; Thomas, Olivier P; Ferrier-Pagès, Christine; Grover, Renaud

2016-02-23

(31)P Nuclear Magnetic Resonance (NMR) was assessed to investigate the phosphorus-containing compounds present in the tissues of the scleractinian coral Stylophora pistillata as well as of cultured zooxanthellae (CZ). Results showed that phosphorus-containing compounds observed in CZ were mainly phosphate and phosphate esters. Phosphate accounted for 19 ± 2% of the total phosphorus compounds observed in CZ maintained under low P-levels (0.02 μM). Adding 5 mM of dissolved inorganic phosphorus (KH2PO4) to the CZ culture medium led to a 3.1-fold increase in intracellular phosphate, while adding 5 mM of dissolved organic phosphorus led to a reduction in the concentration of phosphorus compounds, including a 2.5-fold intracellular phosphate decrease. In sharp contrast to zooxanthellae, the host mainly contained phosphonates, and to a lesser extent, phosphate esters and phosphate. Two-months of host starvation decreased the phosphate content by 2.4 fold, while bleaching of fed corals did not modify this content. Based on (31)P NMR analyses, this study highlights the importance of phosphonates in the composition of coral host tissues, and illustrates the impact of phosphorus availability on the phosphorus composition of host tissues and CZ, both through feeding of the host and inorganic phosphorus enrichment of the CZ.

On the use of 31P NMR for the quantification of hydrosoluble phosphorus-containing compounds in coral host tissues and cultured zooxanthellae

NASA Astrophysics Data System (ADS)

Godinot, Claire; Gaysinski, Marc; Thomas, Olivier P.; Ferrier-Pagès, Christine; Grover, Renaud

2016-02-01

31P Nuclear Magnetic Resonance (NMR) was assessed to investigate the phosphorus-containing compounds present in the tissues of the scleractinian coral Stylophora pistillata as well as of cultured zooxanthellae (CZ). Results showed that phosphorus-containing compounds observed in CZ were mainly phosphate and phosphate esters. Phosphate accounted for 19 ± 2% of the total phosphorus compounds observed in CZ maintained under low P-levels (0.02 μM). Adding 5 mM of dissolved inorganic phosphorus (KH2PO4) to the CZ culture medium led to a 3.1-fold increase in intracellular phosphate, while adding 5 mM of dissolved organic phosphorus led to a reduction in the concentration of phosphorus compounds, including a 2.5-fold intracellular phosphate decrease. In sharp contrast to zooxanthellae, the host mainly contained phosphonates, and to a lesser extent, phosphate esters and phosphate. Two-months of host starvation decreased the phosphate content by 2.4 fold, while bleaching of fed corals did not modify this content. Based on 31P NMR analyses, this study highlights the importance of phosphonates in the composition of coral host tissues, and illustrates the impact of phosphorus availability on the phosphorus composition of host tissues and CZ, both through feeding of the host and inorganic phosphorus enrichment of the CZ.

On the use of 31P NMR for the quantification of hydrosoluble phosphorus-containing compounds in coral host tissues and cultured zooxanthellae

PubMed Central

Godinot, Claire; Gaysinski, Marc; Thomas, Olivier P.; Ferrier-Pagès, Christine; Grover, Renaud

2016-01-01

31P Nuclear Magnetic Resonance (NMR) was assessed to investigate the phosphorus-containing compounds present in the tissues of the scleractinian coral Stylophora pistillata as well as of cultured zooxanthellae (CZ). Results showed that phosphorus-containing compounds observed in CZ were mainly phosphate and phosphate esters. Phosphate accounted for 19 ± 2% of the total phosphorus compounds observed in CZ maintained under low P-levels (0.02 μM). Adding 5 mM of dissolved inorganic phosphorus (KH2PO4) to the CZ culture medium led to a 3.1-fold increase in intracellular phosphate, while adding 5 mM of dissolved organic phosphorus led to a reduction in the concentration of phosphorus compounds, including a 2.5-fold intracellular phosphate decrease. In sharp contrast to zooxanthellae, the host mainly contained phosphonates, and to a lesser extent, phosphate esters and phosphate. Two-months of host starvation decreased the phosphate content by 2.4 fold, while bleaching of fed corals did not modify this content. Based on 31P NMR analyses, this study highlights the importance of phosphonates in the composition of coral host tissues, and illustrates the impact of phosphorus availability on the phosphorus composition of host tissues and CZ, both through feeding of the host and inorganic phosphorus enrichment of the CZ. PMID:26902733

Electron attachment to DNA single strands: gas phase and aqueous solution.

PubMed

Gu, Jiande; Xie, Yaoming; Schaefer, Henry F

2007-01-01

The 2'-deoxyguanosine-3',5'-diphosphate, 2'-deoxyadenosine-3',5'-diphosphate, 2'-deoxycytidine-3',5'-diphosphate and 2'-deoxythymidine-3',5'-diphosphate systems are the smallest units of a DNA single strand. Exploring these comprehensive subunits with reliable density functional methods enables one to approach reasonable predictions of the properties of DNA single strands. With these models, DNA single strands are found to have a strong tendency to capture low-energy electrons. The vertical attachment energies (VEAs) predicted for 3',5'-dTDP (0.17 eV) and 3',5'-dGDP (0.14 eV) indicate that both the thymine-rich and the guanine-rich DNA single strands have the ability to capture electrons. The adiabatic electron affinities (AEAs) of the nucleotides considered here range from 0.22 to 0.52 eV and follow the order 3',5'-dTDP > 3',5'-dCDP > 3',5'-dGDP > 3',5'-dADP. A substantial increase in the AEA is observed compared to that of the corresponding nucleic acid bases and the corresponding nucleosides. Furthermore, aqueous solution simulations dramatically increase the electron attracting properties of the DNA single strands. The present investigation illustrates that in the gas phase, the excess electron is situated both on the nucleobase and on the phosphate moiety for DNA single strands. However, the distribution of the extra negative charge is uneven. The attached electron favors the base moiety for the pyrimidine, while it prefers the 3'-phosphate subunit for the purine DNA single strands. In contrast, the attached electron is tightly bound to the base fragment for the cytidine, thymidine and adenosine nucleotides, while it almost exclusively resides in the vicinity of the 3'-phosphate group for the guanosine nucleotides due to the solvent effects. The comparatively low vertical detachment energies (VDEs) predicted for 3',5'-dADP(-) (0.26 eV) and 3',5'-dGDP(-) (0.32 eV) indicate that electron detachment might compete with reactions having high activation barriers such as glycosidic bond breakage. However, the radical anions of the pyrimidine nucleotides with high VDE are expected to be electronically stable. Thus the base-centered radical anions of the pyrimidine nucleotides might be the possible intermediates for DNA single-strand breakage.

[Influence of adhesion on the color of glass infiltrated alumina ceramic restorations].

PubMed

Jiang, Li; Yang, Liu; Xu, Qiang; Guan, Hong-Yu; Wan, Qian-Bing

2006-10-01

To investigate the effects of luting agent on the final color of glass infiltrated alumina ceramic restorations. 12 plate-shaped specimens with 12.5 mm in diameter and 0.5 mm thickness were fabricated from GI-II (color IG2). Vitadur alpha veneering porcelain (color A2) with 1.0 mm thickness was fired to GI- II glass/alumina composite. 12 plate-shaped background specimens simulating the metal alloy post-and-core 12.5 mm in diameter and 2 mm thickness were also made from Ni-Cr alloy. All-ceramic specimens were luted to the metal alloy by Zinc Phosphate cement, glass ionomer cement and composite resin. The color shifts of the specimens were measured by colorimeter. Luting agents had effect on the final color of restorations. The influence of composite resin was least, followed by glass ionomer cement and Zinc Phosphate cement. The color difference between with and without Zinc Phosphate cement could be identified by the eye. To reduce the effect of luting agents, composite resin is recommended to all-ceramic restorations' adhesion.

Paracrystalline Disorder from Phosphate Ion Orientation and Substitution in Synthetic Bone Mineral

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marisa, Mary E.; Zhou, Shiliang; Melot, Brent C.

Hydroxyapatite is an inorganic mineral closely resembling the mineral phase in bone. However, as a biological mineral, it is highly disordered, and its composition and atomistic structure remain poorly understood. Here, synchrotron X-ray total scattering and pair distribution function analysis methods provide insight into the nature of atomistic disorder in a synthetic bone mineral analogue, chemically substituted hydroxyapatite. By varying the effective hydrolysis rate and/or carbonate concentration during growth of the mineral, compounds with varied degrees of paracrystallinity are prepared. From advanced simulations constrained by the experimental pair distribution function and density functional theory, the paracrystalline disorder prevalent in thesemore » materials appears to result from accommodation of carbonate in the lattice through random displacement of the phosphate groups. Though many substitution modalities are likely to occur in concert, the most predominant substitution places carbonate into the mirror plane of an ideal phosphate site. Understanding the mineralogical imperfections of a biologically analogous hydroxyapatite is important not only to potential bone grafting applications but also to biological mineralization processes themselves.« less

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete.

PubMed

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 . After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

NASA Astrophysics Data System (ADS)

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

PubMed Central

Simescu, Florica; Idrissi, Hassane

2008-01-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating. PMID:27878037

The effects of crystallization and residual glass on the chemical durability of iron phosphate waste forms containing 40 wt% of a high MoO3 Collins-CLT waste

NASA Astrophysics Data System (ADS)

Hsu, Jen-Hsien; Bai, Jincheng; Kim, Cheol-Woon; Brow, Richard K.; Szabo, Joe; Zervos, Adam

2018-03-01

The effects of cooling rate on the chemical durability of iron phosphate waste forms containing up to 40 wt% of a high MoO3 Collins-CLT waste simulant were determined at 90 °C using the product consistency test (PCT). The waste form, designated 40wt%-5, meets appropriate Department of Energy (DOE) standards when rapidly quenched from the melt (as-cast) and after slow cooling following the CCC (canister centerline cooling)-protocol, although the quenched glass is more durable. The analysis of samples from the vapor hydration test (VHT) and the aqueous corrosion test (differential recession test) reveals that rare earth orthophosphate (monazite) and Zr-pyrophosphate crystals that form on cooling are more durable than the residual glass in the 40wt%-5 waste form. The residual glass in the CCC-treated samples has a greater average phosphate chain length and a lower Fe/P ratio, and those contribute to its faster corrosion kinetics.

A regenerable potassium and phosphate sorbent system to enhance dialysis efficacy and device portability: an in vitro study.

PubMed

Wester, Maarten; Simonis, Frank; Gerritsen, Karin G; Boer, Walther H; Wodzig, Will K; Kooman, Jeroen P; Joles, Jaap A

2013-09-01

Continuous dialysis could provide benefit by constant removal of potassium and phosphate. This study investigates the suitability of specific potassium and phosphate sorbents for incorporation in an extracorporeal device by capacity and regenerability testing. Capacity testing was performed in uraemic plasma. Regenerability was tested for potassium sorbents, with adsorption based on cationic exchange for sodium, with 0.1 M and 1.0 M NaCl. To regenerate phosphate sorbents, with adsorption based on anionic exchange, 0.1 M and 1.0 M NaHCO3 and NaOH were used. Subsequently, sodium polystyrene divinylbenzene sulphonate (RES-A) and iron oxide hydroxide (FeOOH) beads were incorporated in a cartridge for testing in bovine blood using a recirculating blood circuit and a dialysis circuit separated by a high-flux dialyzer (dynamic setup). Preloading was tested to assess whether this could limit calcium and magnesium adsorption. In the batch-binding assays, zirconium phosphate most potently adsorbed potassium (0.44 ± 0.05 mmol/g) and RES-A was the best regenerable potassium sorbent (92.9 ± 5.7% with 0.1 M NaCl). Zirconium oxide hydroxide (ZIR-hydr) most potently adsorbed phosphate (0.23 ± 0.05 mmol/g) and the polymeric amine sevelamer carbonate was the best regenerable sorbent (85.7 ± 5.2% with 0.1 M NaHCO3). In the dynamic setup, a potassium adsorption of 10.72 ± 2.06 mmol in 3 h was achieved using 111 g of RES-A and a phosphate adsorption of 4.73 ± 0.53 mmol in 3 h using 55 g of FeOOH. Calcium and magnesium preloading was shown to reduce the net adsorption in 3 h from 3.57 ± 0.91 to -0.29 ± 1.85 and 1.02 ± 0.05 to -0.31 ± 0.18 mmol, respectively. RES-A and FeOOH are suitable, regenerizable sorbents for potassium and phosphate removal in dialysate regeneration. Use of zirconium carbonate and ZIR-hydr may further increase phosphate adsorption, but may compromise sorbent regenerability. Use of polymeric amines for phosphate adsorption may enhance sorbent regenerability. Calcium and magnesium preloading considerably reduced net adsorption of these ions.

Interlaboratory studies on in vitro test methods for estimating in vivo resorption of calcium phosphate ceramics.

PubMed

Ito, Atsuo; Sogo, Yu; Yamazaki, Atsushi; Aizawa, Mamoru; Osaka, Akiyoshi; Hayakawa, Satoshi; Kikuchi, Masanori; Yamashita, Kimihiro; Tanaka, Yumi; Tadokoro, Mika; de Sena, Lídia Ágata; Buchanan, Fraser; Ohgushi, Hajime; Bohner, Marc

2015-10-01

A potential standard method for measuring the relative dissolution rate to estimate the resorbability of calcium-phosphate-based ceramics is proposed. Tricalcium phosphate (TCP), magnesium-substituted TCP (MgTCP) and zinc-substituted TCP (ZnTCP) were dissolved in a buffer solution free of calcium and phosphate ions at pH 4.0, 5.5 or 7.3 at nine research centers. Relative values of the initial dissolution rate (relative dissolution rates) were in good agreement among the centers. The relative dissolution rate coincided with the relative volume of resorption pits of ZnTCP in vitro. The relative dissolution rate coincided with the relative resorbed volume in vivo in the case of comparison between microporous MgTCPs with different Mg contents and similar porosity. However, the relative dissolution rate was in poor agreement with the relative resorbed volume in vivo in the case of comparison between microporous TCP and MgTCP due to the superimposition of the Mg-mediated decrease in TCP solubility on the Mg-mediated increase in the amount of resorption. An unambiguous conclusion could not be made as to whether the relative dissolution rate is predictive of the relative resorbed volume in vivo in the case of comparison between TCPs with different porosity. The relative dissolution rate may be useful for predicting the relative amount of resorption for calcium-phosphate-based ceramics having different solubility under the condition that the differences in the materials compared have little impact on the resorption process such as the number and activity of resorbing cells. The evaluation and subsequent optimization of the resorbability of calcium phosphate are crucial in the use of resorbable calcium phosphates. Although the resorbability of calcium phosphates has usually been evaluated in vivo, establishment of a standard in vitro method that can predict in vivo resorption is beneficial for accelerating development and commercialization of new resorbable calcium phosphate materials as well as reducing use of animals. However, there are only a few studies to propose such an in vitro method within which direct comparison was carried out between in vitro and in vivo resorption. We propose here an in vitro method based on measuring dissolution rate. The efficacy and limitations of the method were evaluated by international round-robin tests as well as comparison with in vivo resorption studies for future standardization. This study was carried out as one of Versailles Projects on Advanced Materials and Standards (VAMAS). Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Modeling cell membrane transport: interaction of guanidinylated poly(propylene imine) dendrimers with a liposomal membrane consisting of phosphate-based lipids.

PubMed

Tsogas, Ioannis; Tsiourvas, Dimitris; Nounesis, George; Paleos, Constantinos M

2006-12-19

Mixed anionic liposomes consisting of dihexadecyl phosphate, phosphatidylcholine, and cholesterol were employed as model systems for assessing the ability of a series of functionalized dendrimers, bearing a varying number of guanidinium groups at their surface, to translocate across the liposomal bilayers. At low guanidinium/phosphate molar ratios or when weakly guanidinylated dendrimeric derivatives were employed, the dendrimeric derivative acted as a kind of "molecular glue" leading to a simple adhesion of the liposomes. Liposomal fusion occurred to a certain extent at high guanidinium/phosphate molar ratios or when highly guanidinylated dendrimeric derivatives were employed. Furthermore, translocation of these dendrimeric derivatives to the liposomal core was observed for low to medium guanidinylation and at low guanidinium/phosphate molar ratios which was, however, enhanced when the lipid bilayer was in its fluid liquid-crystalline phase. Thus, an optimum balance is required between the binding strength of guanidinium with the phosphate groups and the degree of hydrophilicity of the guanidinylated dendrimers for the transport of the latter to the liposomal core to occur.

Role of Polymeric Coating on the Phosphate Availability as a Fertilizer: Insight from Phosphate Release by Castor Polyurethane Coatings.

PubMed

da Cruz, Diego Fernandes; Bortoletto-Santos, Ricardo; Guimarães, Gelton Geraldo Fernandes; Polito, Wagner Luiz; Ribeiro, Caue

2017-07-26

The coating of fertilizers with polymers is an acknowledged strategy for controlling the release of nutrients and their availability in soil. However, its effectiveness in the case of soluble phosphate fertilizers is still uncertain, and information is lacking concerning the chemical properties and structures of such coatings. Here, an oil-based hydrophobic polymer system (polyurethane) is proposed for the control of the release of phosphorus from diammonium phosphate (DAP) granules. This material was systematically characterized, with evaluation of the delivery mechanism and the availability of phosphate in an acid soil. The results indicated that thicker coatings can change the maximum nutrient availability toward longer periods, such as 4.5-7.5 wt % DAP coated, that presented the highest concentrations at 336 h, as compared to 168 h for uncoated DAP. In contrast, DAP treated with 9.0 wt % began to increase the concentration after 168 h until it results in maximum release at 672 h. These effects could be attributed to the homogeneity of the polymer and the porosity. The strategy successfully provided long-term availability of a phosphate source.

Pore-Water Carbonate and Phosphate As Predictors of Arsenate Toxicity in Soil.

PubMed

Lamb, Dane T; Kader, Mohammed; Wang, Liang; Choppala, Girish; Rahman, Mohammad Mahmudur; Megharaj, Mallavarapu; Naidu, Ravi

2016-12-06

Phytotoxicity of inorganic contaminants is influenced by the presence of competing ions at the site of uptake. In this study, interaction of soil pore-water constituents with arsenate toxicity was investigated in cucumber (Cucumis sativa L) using 10 contrasting soils. Arsenate phytotoxicity was shown to be related to soluble carbonate and phosphate. The data indicated that dissolved phosphate and carbonate had an antagonistic impact on arsenate toxicity to cucumber. To predict arsenate phytotoxicity in soils with a diverse range of soil solution properties, both carbonate and phosphate were required. The relationship between arsenic and pore-water toxicity parameters was established initially using multiple regression. In addition, based on the relationship with carbonate and phosphate we successively applied a terrestrial biotic ligand-like model (BLM) including carbonate and phosphate. Estimated effective concentrations from the BLM-like parametrization were strongly correlated to measured arsenate values in pore-water (R 2 = 0.76, P < 0.001). The data indicates that an ion interaction model similar to the BLM for arsenate is possible, potentially improving current risk assessments at arsenic and co-contaminated soils.

Fabrication of dicalcium phosphate dihydrate-coated β-TCP granules and evaluation of their osteoconductivity using experimental rats.

PubMed

Shariff, Khairul Anuar; Tsuru, Kanji; Ishikawa, Kunio

2017-06-01

β-Tricalcium phosphate (β-TCP) has attracted much attention as an artificial bone substitute owing to its biocompatibility and osteoconductivity. In this study, osteoconductivity of β-TCP bone substitute was enhanced without using growth factors or cells. Dicalcium phosphate dihydrate (DCPD), which is known to possess the highest solubility among calcium phosphates, was coated on β-TCP granules by exposing their surface with acidic calcium phosphate solution. The amount of coated DCPD was regulated by changing the reaction time between β-TCP granules and acidic calcium phosphate solution. Histomorphometry analysis obtained from histological results revealed that the approximately 10mol% DCPD-coated β-TCP granules showed the largest new bone formation compared to DCPD-free β-TCP granules, approximately 2.5mol% DCPD-coated β-TCP granules, or approximately 27mol% DCPD-coated β-TCP granules after 2 and 4weeks of implantation. Based on this finding, we demonstrate that the osteoconductivity of β-TCP granules could be improved by coating their surface with an appropriate amount of DCPD. Copyright © 2017 Elsevier B.V. All rights reserved.

Mechanisms of Military Coatings Degradation

DTIC Science & Technology

2003-08-01

fluoride (DuPont Inc., Buffalo, NY) release film. Additionally a primer and topcoat system were also prepared onto a stainless steel mesh substrate...Based Epoxy Surface Treatment: TT- C-490 Zinc Phosphate on a steel s B=(64159), LOW VOC and Zero HAP ARMY SYSTEM Top Coat: MIL-DTL-64159 Water...Zinc Phosphate on a steel su C=(85285), NAVY CONTROL SYSTEM Top Coat: MIL-C-85285 Solvent based Polyurethane Alip polyols Primer: MIL-P

Polymeric dental composites based on remineralizing amorphous calcium phosphate fillers

PubMed Central

Skrtic, Drago; Antonucci, Joseph M.

2017-01-01

For over two decades we have systematically explored structure-composition-property relationships of amorphous calcium phosphate (ACP)-based polymeric dental composites. The appeal of these bioactive materials stems from their intrinsic ability to prevent demineralization and/or restore defective tooth structures via sustained release of remineralizing calcium and phosphate ions. Due to the compositional similarity of the ACP to biological tooth mineral, ACP-based composites should exhibit excellent biocompatibility. Research described in this article has already yielded remineralizing sealants and orthodontic adhesives as well as a prototype root canal sealer. Our work has also contributed to a better understanding on how polymer matrix structure and filler/matrix interactions affect the critical properties of these polymeric composites and their overall performance. The addition of antimicrobial compounds to the formulation of ACP composites could increase their medical and dental regenerative treatment applications, thereby benefiting an even greater number of patients. PMID:29599572

Comparative study on in vitro biocompatibility of synthetic octacalcium phosphate and calcium phosphate ceramics used clinically.

PubMed

Morimoto, Shinji; Anada, Takahisa; Honda, Yoshitomo; Suzuki, Osamu

2012-08-01

The present study was designed to investigate the extent to which calcium phosphate bone substitute materials, including osteoconductive octacalcium phosphate (OCP), display cytotoxic and inflammatory responses based on their dissolution in vitro. Hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) ceramics, which are clinically used, as well as dicalcium phosphate dihydrate (DCPD) and synthesized OCP were compared. The materials were well characterized by chemical analysis, x-ray diffraction and Fourier transform infrared spectroscopy. Calcium and phosphate ion concentrations and the pH of culture media after immersion of the materials were determined. The colony forming rate of Chinese hamster lung fibroblasts was estimated with extraction of the materials. Proliferation of bone marrow stromal ST-2 cells and inflammatory cytokine TNF-α production by THP-1 cells grown on the material-coated plates were examined. The materials had characteristics that corresponded to those reported. DCPD was shown to dissolve the most in the culture media, with a marked increase in phosphate ion concentration and a reduction in pH. ST-2 cells proliferated well on the materials, with the exception of DCPD, which markedly inhibited cellular growth. The colony forming capacity was the lowest on DCPD, while that of the other calcium phosphates was not altered. In contrast, TNF-α was not detected even in cells grown on DCPD, suggesting that calcium phosphate materials are essentially non-inflammatory, while the solubility of the materials can affect osteoblastic and fibroblastic cellular attachment. These results indicate that OCP is biocompatible, which is similar to the materials used clinically, such as HA. Therefore, OCP could be clinically used as a biocompatible bone substitute material.

Nucleic and amino acid sequences relating to a novel transketolase, and methods for the expression thereof

DOEpatents

Croteau, Rodney Bruce; Wildung, Mark Raymond; Lange, Bernd Markus; McCaskill, David G.

2001-01-01

cDNAs encoding 1-deoxyxylulose-5-phosphate synthase from peppermint (Mentha piperita) have been isolated and sequenced, and the corresponding amino acid sequences have been determined. Accordingly, isolated DNA sequences (SEQ ID NO:3, SEQ ID NO:5, SEQ ID NO:7) are provided which code for the expression of 1-deoxyxylulose-5-phosphate synthase from plants. In another aspect the present invention provides for isolated, recombinant DXPS proteins, such as the proteins having the sequences set forth in SEQ ID NO:4, SEQ ID NO:6 and SEQ ID NO:8. In other aspects, replicable recombinant cloning vehicles are provided which code for plant 1-deoxyxylulose-5-phosphate synthases, or for a base sequence sufficiently complementary to at least a portion of 1-deoxyxylulose-5-phosphate synthase DNA or RNA to enable hybridization therewith. In yet other aspects, modified host cells are provided that have been transformed, transfected, infected and/or injected with a recombinant cloning vehicle and/or DNA sequence encoding a plant 1-deoxyxylulose-5-phosphate synthase. Thus, systems and methods are provided for the recombinant expression of the aforementioned recombinant 1-deoxyxylulose-5-phosphate synthase that may be used to facilitate its production, isolation and purification in significant amounts. Recombinant 1-deoxyxylulose-5-phosphate synthase may be used to obtain expression or enhanced expression of 1-deoxyxylulose-5-phosphate synthase in plants in order to enhance the production of 1-deoxyxylulose-5-phosphate, or its derivatives such as isopentenyl diphosphate (BP), or may be otherwise employed for the regulation or expression of 1-deoxyxylulose-5-phosphate synthase, or the production of its products.

Combined analysis of field and model data: A case study of the phosphate dynamics in the German Bight in summer 1994

NASA Astrophysics Data System (ADS)

Pohlmann, Th.; Raabe, Th.; Doerffer, R.; Beddig, S.; Brockmann, U.; Dick, S.; Engel, M.; Hesse, K.-J.; König, P.; Mayer, B.; Moll, A.; Murphy, D.; Puls, W.; Rick, H.-J.; Schmidt-Nia, R.; Schönfeld, W.; Sündermann, J.

1999-09-01

The intention of this paper is to analyse a specific phenomenon observed during the KUSTOS campaigns in order to demonstrate the general capability of the KUSTOS and TRANSWATT approach, i.e. the combination of field and modelling activities in an interdisciplinary framework. The selected phenomenon is the increase in phosphate concentrations off the peninsula of Eiderstedt on the North Frisian coast sampled during four subsequent station grids of the KUSTOS summer campaign in 1994. First of all, a characterisation of the observed summer situation is given. The phosphate increase is described in detail in relation to the dynamics of other nutrients. In a second step, a first-order estimate of the dispersion of phosphate is discussed. The estimate is based on the box model approach and will focus on the effects of the river Elbe and Wadden Sea inputs on phosphate dynamics. Thirdly, a fully three-dimensional model system is presented, which was implemented in order to analyse the phosphate development. The model system is discussed briefly, with emphasis on phosphorus-related processes. The reliability of one of the model components, i.e. the hydrodynamical model, is demonstrated by means of a comparison of model results with observed current data. Thereafter, results of the German Bight seston model are employed to interpret the observed phosphate increase. From this combined analysis, it was possible to conclude that the phosphate increase during the first three surveys was due to internal transformation processes within the phosphorus cycle. On the other hand, the higher phosphate concentrations measured in the last station grid survey were caused by a horizontal transport of phosphate being remobilised in the Wadden Sea.

Massive hyperphosphatemia in a patient with neuronal intestinal dysplasia after bowel preparation with oral sodium phosphate.

PubMed

Arikan, Hakki; Guler, Derya; Birdal, Gurdal; Nalcaci, Serdar; Aykut, Emre; Ozcan, Ceren; Irmak, Rahmi; Banzragch, Munkhtsetseg; Arzu, Velioglu

2013-07-01

Oral sodium phosphate-based laxatives are frequently used for bowel preparation or relief of constipation in some countries. However, these agents are not without risk. Small and clinical insignificant increments on serum phosphorus levels are observed in almost all individuals after use of oral sodium phosphate. Some patients are prone to severe hyperphosphatemia such as elders, those with chronic or acute renal disease and those with poor bowel motility. Severe hyperphosphatemia accompanied with hypocalcemia may be life-threatening in these patients. We present an 18-year-old woman with neuronal intestinal dysplasia who developed symptomatic and severe hyperphosphatemia after bowel preparation with oral sodium phosphate enema. Urgent hemodialysis was performed two times for severe hyperphosphatemia.

Calcium phosphate-based coatings on titanium and its alloys.

PubMed

Narayanan, R; Seshadri, S K; Kwon, T Y; Kim, K H

2008-04-01

Use of titanium as biomaterial is possible because of its very favorable biocompatibility with living tissue. Titanium implants having calcium phosphate coatings on their surface show good fixation to the bone. This review covers briefly the requirements of typical biomaterials and narrowly focuses on the works on titanium. Calcium phosphate ceramics for use in implants are introduced and various methods of producing calcium phosphate coating on titanium substrates are elaborated. Advantages and disadvantages of each type of coating from the view point of process simplicity, cost-effectiveness, stability of the coatings, coating integration with the bone, cell behavior, and so forth are highlighted. Taking into account all these factors, the efficient method(s) of producing these coatings are indicated finally.

Macroporous Calcium Phosphate/Chitosan Composites Prepared via Unidirectional Ice Segregation and Subsequent Freeze-Drying

PubMed Central

Aranaz, Inmaculada; Martínez-Campos, Enrique; Moreno-Vicente, Carolina; Civantos, Ana; García-Arguelles, Sara; del Monte, Francisco

2017-01-01

Calcium phosphate chitosan-based composites have gained much interest in recent years for biomedical purposes. In this paper, three-dimensional calcium phosphate chitosan-based composites with different mineral contents were produced using a green method called ice segregation induced self-assembly (ISISA). In this methodology, ice crystals were used as a template to produce porous structures from an aqueous solution of chitosan (CS) and hydroxyapatite (Hap) also containing acetic acid (pH = 4.5). For better characterization of the nature of the inorganic matter entrapped within the resulting composite, we performed either oxygen plasma or calcination processes to remove the organic matter. The nature of the phosphate salts was studied by XRD and NMR studies. Amorphous calcium phosphate (ACP) was identified as the mineral phase in the composites submitted to oxygen plasma, whereas crystalline Hap was obtained after calcination. SEM microscopy revealed the formation of porous structures (porosity around 80–85%) in the original composites, as well as in the inorganic matrices obtained after calcination, with porous channels of up to 50 µm in diameter in the former case and of up to 20 µm in the latter. The biocompatibility of the composites was assessed using two different cell lines: C2C12GFP premyoblastic cells and MC3T3 preosteoblastic cells. PMID:28772874

Phosphate Treatment of Lead-Contaminated Soil: Effects on Water Quality, Plant Uptake, and Lead Speciation

EPA Science Inventory

Water quality threats associated with using phosphate-based amendments to remediate Pb-contaminated soils are a concern, particularly in riparian areas. This study investigated the effects of P application rates to a Pb-contaminated alluvial soil on Pb and P loss via surface wat...

Technology for recovery of phosphorus from animal wastewater through calcium phosphate precipitation

USDA-ARS?s Scientific Manuscript database

A wastewater treatment process was developed for removal of phosphorus from livestock wastewater. The phosphorus is recovered as calcium phosphate with addition of only small quantities of liquid lime. The process is based on the distinct chemical equilibrium between phosphorus and calcium ions when...

Practical Implications from Observed Lead Pipe Scale Mineralogy in a Blended Phosphate Treated System - slides

EPA Science Inventory

Many water utilities in the United States rely on the addition of phosphate-based corrosion inhibitors to optimize their corrosion control and comply with requirements of the Lead and Copper Rule. Orthophosphate is used on the theory of forming low solubility Pb(II)-orthophosphat...

The calcium phosphate coating of soy lecithin nanoemulsion with performance in stability and as an oxygen carrier

NASA Astrophysics Data System (ADS)

Han, Kyu B.

This work studied the relationship between surfactant, oil, and water, by building ternary phase diagrams, the goal of which was to identify the oil-in-water phase composition. The resulting nano-sized emulsion was coated with dicalcium phosphate by utilizing the ionic affinity between calcium ions and the emulsion surface. Since the desired function of the particle is as an oxygen carrier, the particle stability, oxygen capacity, and oxygen release rate were investigated. The first step in the process was to construct ternary phase diagrams with 1,2-dioleoyl-sn-glycero-3-phosphate (DOPA) and soy derived lecithin. The results showed that the lecithin surfactant formed an oil-in-water phase region that was 36 times greater than that of DOPA. With the desired phase composition set, the lecithin emulsion was extruded, resulting in a well-dispersed nanosized particle. A pH titration study of the emulsion found an optimized calcium phosphate coating condition at pH 8.8, at which, the calcium ion had a greater affinity for the emulsion surface than phosphate. A Hill plot was used to show calcium cooperativeness on the emulsion surface which suggested one calcium ion binds to one lecithin molecule. The lecithin emulsion particles were then coated with calcium phosphate using a layering technique that allowed for careful control of the coating thickness. The overall particle hydrodynamic radius was consistent with the growth of the calcium phosphate coating, from 8 nm to 28 nm. This observation was further supported with cryo-TEM measurements. The stability of the coated emulsion was tested in conditions that simulate practical thermal, physical, and time-dependent conditions. Throughout the tests, the coated emulsion exhibited a constant mono-dispersed particle size, while the uncoated emulsion size fluctuated greatly and exhibited increased polydispersion. The fast mixing method with the stopped-flow apparatus was employed to test the product as an oxygen carrier, and it was shown that particles with thicker calcium phosphate coatings released smaller amounts of oxygen in a given timeframe. This study proved the hypothesis by showing a fundamental understanding of emulsion science, coating the flexible emulsion surface with a biocompatible material, and a strong particle performance with regard to stability and as an oxygen carrier.

Long Term Dynamic Stream Nitrate and Phosphate Changes Following Watershed Wildfires

NASA Technical Reports Server (NTRS)

Ambrosia, Vincent G.; Brass, James A.; Riggan, Philip J.; Ewing, Roy; Sebesta, Paul D.; Peterson, David L. (Technical Monitor)

1994-01-01

During and following the 1988 Yellowstone National Park wildfires, airborne remotely sensed data were collected in order to characterize various vegetative components, fire front movements and bum intensities. ER-2 derived Thematic Mapper Simulator (TMS) data were used in conjunction with water sampling and chemistry analysis to determine fire intensities in various watersheds and aquatic system condition changes. The airborne Daedalus multispectral TMS data allowed the characterization of various bum intensities in watersheds. Stream sampling was then conducted in those various burned watersheds to determine nitrate and phosphate concentration changes. Six stream watersheds were monitored for five years (1989-1993) during non-snow periods (May/June through September): Cache Creek (intensely burned), Blacktail Deer Creek (intensely burned), Snake River (moderately burned), Lamar River (mixed burning), Soda Butte Creek (lightly burned), and Amphitheatre Creek (unburned). One litre samples were collected from those streams with ISCO water samplers every 12 hours. The samples were removed every 14 days .(28 Samples), and water chemistry analysis was performed. Chemistry analysis indicated that nitrate and phosphate concentrations were elevated in moderately burned watersheds and significantly elevated in severely burned watersheds. The results during the five year study indicate that bum intensities regulate stream water nitrate and phosphate concentrations, and that remotely sensed data can be used effectively to predict watershed chemical changes which will affect aquatic conditions.

Investigation of phosphoserine and cytidine 5'-phosphate by heteronuclear two-dimensional spectroscopy: samples with strong proton coupling

NASA Astrophysics Data System (ADS)

Bolton, Philip H.

Heteronuclear two-dimensional magnetic resonance is a novel method for investigating the conformations of cellular phosphates. The two-dimensional proton spectra are detected indirectly via the phosphorus-31 nucleus and thus allow determination of proton chemical shifts and coupling constants in situations in which the normal proton spectrum is obscured. Previous investigations of cellular phosphates with relatively simple spin systems have shown that the two-dimensional proton spectrum can be readily related to the normal proton spectrum by subspectral analysis. The normal proton spectrum can be decomposed into two subspectra, one for each polarization of the phosphorus-31 nucleus. The two-dimensional spectrum arises from the difference between the subspectra, and the normal proton spectrum is the sum. This allows simulation of the two-dimensional spectra and hence determination of the proton chemical shifts and coupling constants. Many cellular phosphates of interest, such as 5'-nucleotides and phosphoserine, contain three protons coupled to the phosphorus which are strongly coupled to one another. These samples are amenable to the two-dimensional method and the straightforward subspectral analysis is preserved when a 90° pulse is applied to the protons in the magnetization transfer step. The two-dimensional proton spectra of the samples investigated here have higher resolution than the normal proton spectra, revealing spectral features not readily apparent in the normal proton spectra.

Sol gel derived hydroxyapatite coatings on titanium and its alloy Ti6Al4V

NASA Astrophysics Data System (ADS)

Stoch, A.; Jastrzebski, W.; Długoń, E.; Lejda, W.; Trybalska, B.; Stoch, G. J.; Adamczyk, A.

2005-06-01

Titanium has been used for many medical and dental applications; however, its joining to a living bone is not satisfactorily good or the implant integration with bone tissue takes several months.The aim of this work is to produce hydroxyapatite (HAP) coatings on titanium and its alloy for facilitating and shortening the processes towards osseointegration. HAP coatings were obtained by sol-gel method with sol solutions prepared from calcium nitrate tetrahydrate and triammonium phosphate trihydrate as the calcium and phosphorous sources. Two types of gelatine were added to the sol: agar-agar or animals gelatine. Both were found to enhance the formation and stability of amorphous HAP using soluble salts as the sources of calcium and phosphate. HAP coatings were deposited from HAP-GEL sol using dip-withdrawal technique, then the plates were dried and annealed at temperatures 460-750 °C. FTIR spectroscopy and XRD analysis were used to study the phase composition of phosphate coatings. Morphology and chemical analysis of HAP layers was performed using a scanning electron microscope equipped with an energy dispersive X-ray analyser (SEM+EDX). The biological activity of sol-gel phosphate coatings was observed during thermostatic held in simulated body fluid (SBF). It was found that chemical composition and structure of HAP coatings depends on pH and final thermal treatment of the layer.

5-Substituents in the uridine moiety and their effect on the conformation of ApU-type dinucleoside phosphates.

PubMed

Hillen, W; Gassen, G

1978-03-29

The ApU analogues ApT, Apcl5U, Apbr5U, Apa5U and Apno5(2)U were synthesized with the aid of ribonuclease U2 starting from 2',3'-cyclic Ap and the respective uridine derivatives. For these compounds the ultraviolet data, the difference spectra, the hypochromism and the temperature dependence of the CD spectra are reported. The dimerisation shifts of the pyrimidine protons which were obtained from the 100 MHz PMR spectra confirm the optical results. The influence of the substituents in the 5 position of the uracil ring on base-base interaction and the conformation of the dinucleoside phosphates is discussed with respect to the van der Waals radii and the electronic effects of these groups. As calculated from the hypochromism the dinucleoside phosphates can be arranged according to decreasing base-base interaction: Apno5(2)U greater than Apbr5U approximately ApT greater than Apcl5U greater than ApU greater than Apa5U.

Effect of medium acidity on the thermodynamics and kinetics of the reaction of pyridoxal 5'-phosphate with isoniazid in an aqueous solution

NASA Astrophysics Data System (ADS)

Gamov, G. A.; Zavalishin, M. N.; Usacheva, T. R.; Sharnin, V. A.

2017-05-01

Thermodynamic characteristics of the formation of the Schiff base between isoniazid and pyridoxal 5'-phosphate in an aqueous solution at different pH values of a medium are determined by means of spectrophotometry and calorimetric titration. The process kinetics is studied spectrophotometrically, and the reaction rate constants for the formation of the imine at different acidities of a medium are determined. Biochemical aspects of the binding of pyridoxal 5'-phosphate into stable compounds are discussed.

Mechanical behaviour of degradable phosphate glass fibres and composites-a review.

PubMed

Colquhoun, R; Tanner, K E

2015-12-23

Biodegradable materials are potentially an advantageous alternative to the traditional metallic fracture fixation devices used in the reconstruction of bone tissue defects. This is due to the occurrence of stress shielding in the surrounding bone tissue that arises from the absence of mechanical stimulus to the regenerating bone due to the mismatch between the elastic modulus of bone and the metal implant. However although degradable polymers may alleviate such issues, these inert materials possess insufficient mechanical properties to be considered as a suitable alternative to current metallic devices at sites of sufficient mechanical loading. Phosphate based glasses are an advantageous group of materials for tissue regenerative applications due to their ability to completely degrade in vivo at highly controllable rates based on the specific glass composition. Furthermore the release of the glass's constituent ions can evoke a therapeutic stimulus in vivo (i.e. osteoinduction) whilst also generating a bioactive response. The processing of these materials into fibres subsequently allows them to act as reinforcing agents in degradable polymers to simultaneously increase its mechanical properties and enhance its in vivo response. However despite the various review articles relating to the compositional influences of different phosphate glass systems, there has been limited work summarising the mechanical properties of different phosphate based glass fibres and their subsequent incorporation as a reinforcing agent in degradable composite materials. As a result, this review article examines the compositional influences behind the development of different phosphate based glass fibre compositions intended as composite reinforcing agents along with an analysis of different potential composite configurations. This includes variations in the fibre content, matrix material and fibre architecture as well as other novel composites designs.

The theoretical and experimental study on dicalcium phosphate dehydrate loading with protocatechuic aldehyde.

PubMed

Guo, Yuehua; Qu, Shuxin; Lu, Xiong; Xie, Haodong; Zhang, Hongping; Weng, Jie

2010-07-01

The aim of this study is to investigate the interaction between dicalcium phosphate dihydrate (CaHPO(4) x 2H(2)O, DCPD) and Protocatechuic aldehyde (C(7)H(6)O(3), Pca), which is the water-soluble constituents of Chinese Medicine, Salvia Miltiorrhiza Bunge (SMB), by calculating the absorption energy through molecular dynamics simulation. Furthermore, the effects of functional groups of Pca and temperature on Pca adsorbed by DCPD are calculated respectively. DCPD/Pca and DCPD were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TG). The simulation results showed that Pca mostly absorbed on the (0 2 0) surface of DCPD. The aldehyde group of Pca played a moren important role on the adsorption of Pca on DCPD than hydroxyl did, while temperature had no distinct effects on the adsorption. XRD results indicated that Pca induced the preferential growth of (0 2 0) crystal surface in DCPC/Pca whereas it had no influence on the crystal structure, the crystallinity and grain size of DCPD. FTIR and TG results showed that the characteristic peak of Pca was at 1295 cm(-1) and the content of Pca in DCPD was 16%, respectively. The present results show that molecular dynamics simulation is a very effective and complementary method to study the interaction between materials and medicine.

The effect of simulated acid rain on the stabilization of cadmium in contaminated agricultural soils treated with stabilizing agents.

PubMed

Zhu, Hao; Wu, Chunfa; Wang, Jun; Zhang, Xumei

2018-04-16

Stabilization technology is one of widely used remediation technologies for cadmium (Cd)-contaminated agricultural soils, but stabilized Cd in soil may be activated again when external conditions such as acid rain occurred. Therefore, it is necessary to study the effect of acid rain on the performance of different stabilizing agents on Cd-polluted agriculture soils. In this study, Cd-contaminated soils were treated with mono-calcium phosphate (MCP), mono-ammonium phosphate (MAP), and artificial zeolite (AZ) respectively and incubated 3 months. These treatments were followed by two types of simulated acid rain (sulfuric acid rain and mixed acid rain) with three levels of acidity (pH = 3.0, 4.0, and 5.6). The chemical forms of Cd in the soils were determined by Tessier's sequential extraction procedure, and the leaching toxicities of Cd in the soils were assessed by toxicity characteristic leaching procedure (TCLP). The results show that the three stabilizing agents could decrease the mobility of Cd in soil to some degree with or without simulated acid rain (SAR) treatment. The stabilization performances followed the order of AZ < MAP < MCP. Acid rain soaking promoted the activation of Cd in stabilized soil, and both anion composition and pH of acid rain were two important factors that influenced the stabilization effect of Cd.

The Role of Magnesium for Geometry and Charge in GTP Hydrolysis, Revealed by Quantum Mechanics/Molecular Mechanics Simulations

PubMed Central

Rudack, Till; Xia, Fei; Schlitter, Jürgen; Kötting, Carsten; Gerwert, Klaus

2012-01-01

The coordination of the magnesium ion in proteins by triphosphates plays an important role in catalytic hydrolysis of GTP or ATP, either in signal transduction or energy conversion. For example, in Ras the magnesium ion contributes to the catalysis of GTP hydrolysis. The cleavage of GTP to GDP and Pi in Ras switches off cellular signaling. We analyzed GTP hydrolysis in water, Ras, and Ras·Ras-GTPase-activating protein using quantum mechanics/molecular mechanics simulations. By comparison of the theoretical IR-difference spectra for magnesium ion coordinated triphosphate to experimental ones, the simulations are validated. We elucidated thereby how the magnesium ion contributes to catalysis. It provides a temporary storage for the electrons taken from the triphosphate and it returns them after bond cleavage and Pi release back to the diphosphate. Furthermore, the Ras·Mg2+ complex forces the triphosphate into a stretched conformation in which the β- and γ-phosphates are coordinated in a bidentate manner. In this conformation, the triphosphate elongates the bond, which has to be cleaved during hydrolysis. Furthermore, the γ-phosphate adopts a more planar structure, driving the conformation of the molecule closer to the hydrolysis transition state. GTPase-activating protein enhances these changes in GTP conformation and charge distribution via the intruding arginine finger. PMID:22853907

Bone substitute material composition and morphology differentially modulate calcium and phosphate release through osteoclast-like cells.

PubMed

Konermann, A; Staubwasser, M; Dirk, C; Keilig, L; Bourauel, C; Götz, W; Jäger, A; Reichert, C

2014-04-01

The aim of this study was to determine the material composition and cell-mediated remodelling of different calcium phosphate-based bone substitutes. Osteoclasts were cultivated on bone substitutes (Cerabone, Maxresorb, and NanoBone) for up to 5 days. Bafilomycin A1 addition served as the control. To determine cellular activity, the supernatant content of calcium and phosphate was measured by inductively coupled plasma optical emission spectrometry. Cells were visualized on the materials by scanning electron microscopy. Material composition and surface characteristics were assessed by energy-dispersive X-ray spectroscopy. Osteoclast-induced calcium and phosphate release was material-specific. Maxresorb exhibited the highest ion release to the medium (P = 0.034; calcium 40.25mg/l day 5, phosphate 102.08 mg/l day 5) and NanoBone the lowest (P = 0.021; calcium 8.43 mg/l day 5, phosphate 15.15 mg/l day 5); Cerabone was intermediate (P = 0.034; calcium 16.34 mg/l day 5, phosphate 30.6 mg/l day 5). All investigated materials showed unique resorption behaviours. The presented methodology provides a new perspective on the investigation of bone substitute biodegradation, maintaining the material-specific micro- and macrostructure. Copyright © 2013 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

Metal Phosphides and Phosphates-based Electrodes for Electrochemical Supercapacitors.

PubMed

Li, Xin; Elshahawy, Abdelnaby M; Guan, Cao; Wang, John

2017-10-01

Phosphorus compounds, such as metal phosphides and phosphates have shown excellent performances and great potential in electrochemical energy storage, which are demonstrated by research works published in recent years. Some of these metal phosphides and phosphates and their hybrids compare favorably with transition metal oxides/hydroxides, which have been studied extensively as a class of electrode materials for supercapacitor applications, where they have limitations in terms of electrical and ion conductivity and device stability. To be specific, metal phosphides have both metalloid characteristics and good electric conductivity. For metal phosphates, the open-framework structures with large channels and cavities endow them with good ion conductivity and charge storage capacity. In this review, we present the recent progress on metal phosphides and phosphates, by focusing on their advantages/disadvantages and potential applications as a new class of electrode materials in supercapacitors. The synthesis methods to prepare these metal phosphides/phosphates are looked into, together with the scientific insights involved, as they strongly affect the electrochemical energy storage performance. Particular attentions are paid to those hybrid-type materials, where strong synergistic effects exist. In the summary, the future perspectives and challenges for the metal phosphides, phosphates and hybrid-types are proposed and discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of tetracalcium phosphate/monetite toothpaste on dentin remineralization and tubule occlusion in vitro.

PubMed

Medvecky, L; Stulajterova, R; Giretova, M; Mincik, J; Vojtko, M; Balko, J; Briancin, J

2018-03-01

To investigate the tubule occlusion and remineralization potential of a novel toothpaste with active tetracalcium phosphate/monetite mixtures under de/remineralization cycling. Dentin de/remineralization cycling protocol consisted of demineralization in 1% citric acid at pH 4.6 with following remineralization with toothpastes and soaking in artificial saliva. Effectiveness of toothpastes to promote remineralization was evaluated by measurement of microhardness recovery, analysis of surface roughness, thickness of coating and scanning electron microscopy. The novel tetracalcium phosphate/monetite dentifrice had comparable remineralization potential as commercial calcium silicate/phosphate (SENSODYNE ® ) and magnesium aluminum silicate (Colgate ® ) toothpastes and significantly higher than control saliva (p<0.02). Surface roughness was significantly lower after treatment with prepared and SENSODYNE ® dentifirice (p<0.05). The coatings on dentin surfaces was significantly thicker after applying toothpastes as compared to negative control (p<0.001). The new fluoride toothpaste formulation with bioactive tetracalcium phosphate/monetite calcium phosphate mixture effectively occluded dentin tubules and showed good dentin remineralization potential under de/remineralization cycling. It could replace professional powder preparation based on this mixture. It was demonstrated that prepared dentifrice had comparable properties with commercial fluoride calcium silicate/phosphate or magnesium aluminum silicate dentifrices. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A turn-on coordination nanoparticle-based fluorescent probe for phosphate in human serum

NASA Astrophysics Data System (ADS)

Lin, Na; Li, Jian; Lu, Zhixiang; Bian, Longchun; Zheng, Liyan; Cao, Qiue; Ding, Zhongtao

2015-03-01

Coordination nanoparticles (CNPs) are becoming attractive platforms for chemical sensing applications because their unique adjustable properties offer the opportunity to design various luminescent nanoprobes. Here, we present a CNP-based fluorescent nanoprobe, in which fluorophores (rhodamine B, RB) and quenchers (methylene blue, MB) were spontaneously enfolded by coordination networks self-assembled of adenine, biphenyl-4,4'-dicarboxylic acid (BDA) and zinc ions. The aggregation of fluorophores and quenchers in CNPs resulted in a quenched state fluorescence of RB. RB and MB could be released from CNPs in the presence of phosphate, which triggered the fluorescence of RB. On the basis of recognition-driven disassembly principle, a novel turn-on fluorescent probe for the determination of PO43- with a wide response range (0.5-50 μM) has been successfully applied in the detection of phosphate in human serum samples. This work not only develops a probe for phosphate but also provides a general strategy for designing nanoprobes or nanocarriers towards various targets by altering organic linkers or metal ions.Coordination nanoparticles (CNPs) are becoming attractive platforms for chemical sensing applications because their unique adjustable properties offer the opportunity to design various luminescent nanoprobes. Here, we present a CNP-based fluorescent nanoprobe, in which fluorophores (rhodamine B, RB) and quenchers (methylene blue, MB) were spontaneously enfolded by coordination networks self-assembled of adenine, biphenyl-4,4'-dicarboxylic acid (BDA) and zinc ions. The aggregation of fluorophores and quenchers in CNPs resulted in a quenched state fluorescence of RB. RB and MB could be released from CNPs in the presence of phosphate, which triggered the fluorescence of RB. On the basis of recognition-driven disassembly principle, a novel turn-on fluorescent probe for the determination of PO43- with a wide response range (0.5-50 μM) has been successfully applied in the detection of phosphate in human serum samples. This work not only develops a probe for phosphate but also provides a general strategy for designing nanoprobes or nanocarriers towards various targets by altering organic linkers or metal ions. Electronic supplementary information (ESI) available: Supplementary figures. See DOI: 10.1039/c5nr00515a

Assessment of two carrier materials for phosphate solubilizing biofertilizers and their effect on growth of wheat (Triticum aestivum L.).

PubMed

Mukhtar, Salma; Shahid, Izzah; Mehnaz, Samina; Malik, Kauser A

2017-12-01

Biofertilizers are usually carrier-based inoculants containing beneficial microorganisms. Incorporation of microorganisms in carrier material enables easy-handling, long-term storage and high effectiveness of biofertilizers. Objective of the present study was to assess enriched biogas sludge and soil as biofertilizer carriers on growth and yield of wheat. Six phosphate solubilizing strains were used in this study. Three phosphate solubilizing strains, 77-NS2 (Bacillus endophyticus), 77-CS-S1 (Bacillus sphaericus) and 77-NS5 (Enterobacter aerogenes) were isolated from the rhizosphere of sugarcane, two strains, PSB5 (Bacillus safensis) and PSB12 (Bacillus megaterium) from the rhizosphere of wheat and one halophilic phosphate solubilizing strain AT2RP3 (Virgibacillus sp.) from the rhizosphere of Atriplex amnicola, were used as bioinoculants. Phosphate solubilization ability of these strains was checked in vitro in Pikovskaya medium, containing rock phosphate (RP) as insoluble P source, individually supplemented with three different carbon sources, i.e., glucose, sucrose and maltose. Maximum phosphate solubilization; 305.6μg/ml, 217.2μg/ml and 148.1μg/ml was observed in Bacillus strain PSB12 in Pikovskaya medium containing sucrose, maltose and glucose respectively. A field experiment and pot experiments in climate control room were conducted to study the effects of biogas sludge and enriched soil based phosphorous biofertilizers on growth of wheat. Bacillus strain PSB12 significantly increased root and shoot dry weights and lengths using biogas sludge as carrier material in climate control room experiments. While in field conditions, significant increase in root and shoot dry weights, lengths and seed weights was seen by PSB12 and PSB5 (Bacillus) and Enterobacter strain 77-NS5 using biogas sludge as carrier. PSB12 also significantly increased both root and shoot dry weights and lengths in field conditions when used as enriched soil based inoculum. These results indicated that bacterial isolates having plant beneficial traits such as P solubilization are more promising candidates as biofertilizer when used with carrier materials. Copyright © 2017 Elsevier GmbH. All rights reserved.

Remediation of Uranium in the Hanford Vadose Zone Using Gas-Transported Reactants: Laboratory Scale Experiments in Support of the Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Truex, Michael J.; Zhong, Lirong

2010-01-04

This laboratory-scale investigation is focused on decreasing mobility of uranium in subsurface contaminated sediments in the vadose zone by in situ geochemical manipulation at low water content. This geochemical manipulation of the sediment surface phases included reduction, pH change (acidic and alkaline), and additions of chemicals (phosphate, ferric iron) to form specific precipitates. Reactants were advected into 1-D columns packed with Hanford 200 area U-contaminated sediment as a reactive gas (for CO2, NH3, H2S, SO2), with a 0.1% water content mist (for NaOH, Fe(III), HCl, PO4) and with a 1% water content foam (for PO4). Uranium is present in themore » sediment in multiple phases that include (in decreasing mobility): aqueous U(VI) complexes, adsorbed U, reduced U(IV) precipitates, rind-carbonates, total carbonates, oxides, silicates, phosphates, and in vanadate minerals. Geochemical changes were evaluated in the ability to change the mixture of surface U phases to less mobile forms, as defined by a series of liquid extractions that dissolve progressively less soluble phases. Although liquid extractions provide some useful information as to the generalized uranium surface phases (and are considered operational definitions of extracted phases), positive identification (by x-ray diffraction, electron microprobe, other techniques) was also used to positively identify U phases and effects of treatment. Some of the changes in U mobility directly involve U phases, whereas other changes result in precipitate coatings on U surface phases. The long-term implication of the U surface phase changes to alter U mass mobility in the vadose zone was then investigated using simulations of 1-D infiltration and downward migration of six U phases to the water table. In terms of the short-term decrease in U mobility (in decreasing order), NH3, NaOH mist, CO2, HCl mist, and Fe(III) mist showed 20% to 35% change in U surface phases. Phosphate addition (mist or foam advected) showed inconsistent change in aqueous and adsorbed U, but significant coating (likely phosphates) on U-carbonates. The two reductive gas treatments (H2S and SO2) showed little change. For long-term decrease in U reduction, mineral phases created that had low solubility (phosphates, silicates) were desired, so NH3, phosphates (mist and foam delivered), and NaOH mist showed the greatest formation of these minerals. In addition, simulations showed the greatest decrease in U mass transport time to reach groundwater (and concentration) for these silicate/phosphate minerals. Advection of reactive gasses was the easiest to implement at the laboratory scale (and presumably field scale). Both mist and foam advection show promise and need further development, but current implementation move reactants shorter distances relative to reactive gasses. Overall, the ammonia and carbon dioxide gas had the greatest overall geochemical performance and ability to implement at field scale. Corresponding mist-delivered technologies (NaOH mist for ammonia and HCl mist for carbon dioxide) performed as well or better geochemically, but are not as easily upscaled. Phosphate delivery by mist was rated slightly higher than by foam delivery simply due to the complexity of foam injection and unknown effect of U mobility by the presence of the surfactant.« less

Comment on: "Recent revisions of phosphate rock reserves and resources: a critique" by Edixhoven et al. (2014) - Phosphate reserves and resources: what conceptions and data do stakeholders need for sustainable action?

NASA Astrophysics Data System (ADS)

Scholz, R. W.; Wellmer, F.-W.

2015-01-01

Several recent papers predict a scarcity of phosphate reserves in the near future. The paper by Edixhoven et al. (2014), for instance, expresses the doubts about whether the upward estimate of reserves by the IFDC (2010) and the USGS (2010) provide an accurate, reliable, and comparable picture, as they are based on reports that do not clearly differentiate between phosphate ore and phosphate products (i.e., marketable phosphate rock concentrate). Further the indistinct use of the terms reserves and resources is criticized. Edixhoven et al. ask for a differentiated inventory of world phosphate reserves including "guidelines which determine the appropriate drill hole distances." The claim that humanity is on the safe side with respect to future phosphate is supply is doubted as the validity of the IFDC's upgrading of the Moroccan data to 50 Gt phosphate is questioned. The present paper identifies and discusses basic conceptual errors of the paper by Edixhoven et al. and related papers that predict a short or mid-term phosphorus scarcity. These include the non-acknowledgment of the dynamic nature of reserves (which depends on price, technology, and innovation for exploiting low-grade deposits, etc.), the mixing of finiteness and staticness of the ultimate recoverable resources (i.e., phosphorus that may be mined economically in the long-term future), the improper use of the Hubbert analysis (which, e.g., simply uses the USGS estimates of reserves as a substitute of an estimate of ultimate recoverable resources) and the geostatistical naive/unprofessional demand for fixed drilling plans to assess reserves. We reconstruct the IFDC and USGS estimates and conclude that there is no evidence for considering the 50 Gt phosphate concentrate as an unreasonable estimate for Moroccan reserves. However, the partial mixing of different units (e.g., phosphate ore and phosphate concentrate or marketable product) in the USGS data may be avoided by improving the data base and using proper conversion factors. When applying these factors and assess all reserves in marketable Gt of phosphate rock (PR-M), which is a common scale for measuring annual consumption, the magnitude of the USGS estimates 2014 of 67 Gt PR reserves does not change essentially yet decrease to 64 (IFDC assessment) to 58.3 Gt PR-M (worst case calculation). We argue that, a better harmonization of the (national) classification systems is meaningful. The discussion suggests that the discrepant estimates of resource estimates that can be found in literature are due to different system understandings, different conceptions of sciences, and diverging worldviews. Finally, we discuss in what way an independent and scientifically sound assessment of the phosphate resources can be realized in the long-term. We suggest the establishment of a solidly funded, international standing committee that regularly analyzes global geopotential as the source of future resources and reserves. Such a committee may be hosted by international science associations of geoscientists, given that a comparative assessment with other environmental threats reveals that investments in this field are proportional and meaningful.

Molecular Data for a Biochemical Model of DNA Radiation Damage: Electron Impact Ionization and Dissociative Ionization of DNA Bases and Sugar-Phosphate Backbone

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Fletcher, Graham D.

2004-01-01

As part of the database for building up a biochemical model of DNA radiation damage, electron impact ionization cross sections of sugar-phosphate backbone and DNA bases have been calculated using the improved binary-encounter dipole (iBED) model. It is found that the total ionization cross sections of C3'- and C5'-deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 10%. Of the four DNA bases, the ionization cross section of guanine is the largest, then in decreasing order, adenine, thymine, and cytosine. The order is in accordance with the known propensity of oxidation of the bases by ionizing radiation. Dissociative ionization (DI), a process that both ionizes and dissociates a molecule, is investigated for cytosine. The DI cross section for the formation of H and (cytosine-Hl)(+), with the cytosine ion losing H at the 1 position, is also reported. The threshold of this process is calculated to be 17.1 eV. Detailed analysis of ionization products such as in DI is important to trace the sequential steps in the biochemical process of DNA damage.

Phosphate binder use and mortality among hemodialysis patients in the Dialysis Outcomes and Practice Patterns Study (DOPPS): evaluation of possible confounding by nutritional status.

PubMed

Lopes, Antonio Alberto; Tong, Lin; Thumma, Jyothi; Li, Yun; Fuller, Douglas S; Morgenstern, Hal; Bommer, Jürgen; Kerr, Peter G; Tentori, Francesca; Akiba, Takashi; Gillespie, Brenda W; Robinson, Bruce M; Port, Friedrich K; Pisoni, Ronald L

2012-07-01

Poor nutritional status and both hyper- and hypophosphatemia are associated with increased mortality in maintenance hemodialysis (HD) patients. We assessed associations of phosphate binder prescription with survival and indicators of nutritional status in maintenance HD patients. Prospective cohort study (DOPPS [Dialysis Outcomes and Practice Patterns Study]), 1996-2008. 23,898 maintenance HD patients at 923 facilities in 12 countries. Patient-level phosphate binder prescription and case-mix-adjusted facility percentage of phosphate binder prescription using an instrumental-variable analysis. All-cause mortality. Overall, 88% of patients were prescribed phosphate binders. Distributions of age, comorbid conditions, and other characteristics showed small differences between facilities with higher and lower percentages of phosphate binder prescription. Patient-level phosphate binder prescription was associated strongly at baseline with indicators of better nutrition, ie, higher values for serum creatinine, albumin, normalized protein catabolic rate, and body mass index and absence of cachectic appearance. Overall, patients prescribed phosphate binders had 25% lower mortality (HR, 0.75; 95% CI, 0.68-0.83) when adjusted for serum phosphorus level and other covariates; further adjustment for nutritional indicators attenuated this association (HR, 0.88; 95% CI, 0.80-0.97). However, this inverse association was observed for only patients with serum phosphorus levels ≥3.5 mg/dL. In the instrumental-variable analysis, case-mix-adjusted facility percentage of phosphate binder prescription (range, 23%-100%) was associated positively with better nutritional status and inversely with mortality (HR for 10% more phosphate binders, 0.93; 95% CI, 0.89-0.96). Further adjustment for nutritional indicators reduced this association to an HR of 0.95 (95% CI, 0.92-0.99). Results were based on phosphate binder prescription; phosphate binder and nutritional data were cross-sectional; dietary restriction was not assessed; observational design limits causal inference due to possible residual confounding. Longer survival and better nutritional status were observed for maintenance HD patients prescribed phosphate binders and in facilities with a greater percentage of phosphate binder prescription. Understanding the mechanisms for explaining this effect and ruling out possible residual confounding require additional research. Copyright © 2012 National Kidney Foundation, Inc. Published by Elsevier Inc. All rights reserved.

The role of molecular structure of sugar-phosphate backbone and nucleic acid bases in the formation of single-stranded and double-stranded DNA structures.

PubMed

Poltev, Valeri; Anisimov, Victor M; Danilov, Victor I; Garcia, Dolores; Sanchez, Carolina; Deriabina, Alexandra; Gonzalez, Eduardo; Rivas, Francisco; Polteva, Nina

2014-06-01

Our previous DFT computations of deoxydinucleoside monophosphate complexes with Na(+)-ions (dDMPs) have demonstrated that the main characteristics of Watson-Crick (WC) right-handed duplex families are predefined in the local energy minima of dDMPs. In this work, we study the mechanisms of contribution of chemically monotonous sugar-phosphate backbone and the bases into the double helix irregularity. Geometry optimization of sugar-phosphate backbone produces energy minima matching the WC DNA conformations. Studying the conformational variability of dDMPs in response to sequence permutation, we found that simple replacement of bases in the previously fully optimized dDMPs, e.g. by constructing Pyr-Pur from Pur-Pyr, and Pur-Pyr from Pyr-Pur sequences, while retaining the backbone geometry, automatically produces the mutual base position characteristic of the target sequence. Based on that, we infer that the directionality and the preferable regions of the sugar-phosphate torsions, combined with the difference of purines from pyrimidines in ring shape, determines the sequence dependence of the structure of WC DNA. No such sequence dependence exists in dDMPs corresponding to other DNA conformations (e.g., Z-family and Hoogsteen duplexes). Unlike other duplexes, WC helix is unique by its ability to match the local energy minima of the free single strand to the preferable conformations of the duplex. Copyright © 2013 Wiley Periodicals, Inc.

The 2',4'-dihydroxychalcone could be explored to develop new inhibitors against the glycerol-3-phosphate dehydrogenase from Leishmania species.

PubMed

Passalacqua, Thais G; Torres, Fábio A E; Nogueira, Camila T; de Almeida, Leticia; Del Cistia, Mayara L; dos Santos, Mariana B; Dutra, Luis A; Bolzani, Vanderlan da Silva; Regasini, Luis O; Graminha, Márcia A S; Marchetto, Reinaldo; Zottis, Aderson

2015-09-01

The enzyme glycerol-3-phosphate dehydrogenase (G3PDH) from Leishmania species is considered as an attractive target to design new antileishmanial drugs and a previous in silico study reported on the importance of chalcones to achieve its inhibition. Here, we report the identification of a synthetic chalcone in our in vitro assays with promastigote cells from Leishmania amazonensis, its biological activity in animal models, and docking followed by molecular dynamics simulation to investigate the molecular interactions and structural patterns that are crucial to achieve the inhibition complex between this compound and G3PDH. A molecular fragment of this natural product derivative can provide new inhibitors with increased potency and selectivity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Phytic acid derived bioactive CaO-P2O5-SiO2 gel-glasses.

PubMed

Li, Ailing; Qiu, Dong

2011-12-01

The possibility of using phytic acid as a precursor to synthesize CaO-P(2)O(5)-SiO(2) glasses by sol-gel method has been explored and the pseudo ternary phase diagram has been established. It was shown that gel-glasses over a broader range of compositions could be prepared compared to other phosphorus precursors or melt-quenching method. Furthermore, phytic acid was found to assist calcium being incorporated into glass networks. In vitro tests in simulated body fluid (SBF) were performed on the above gel-glasses and it was found that they were bioactive over a much broader compositional range especially at high phosphate content, thus enabling one to design bioactive materials with various degradation rates by adjusting the phosphate content.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catalano, Jeffrey G.; Giammar, Daniel E.; Wang, Zheming

Phosphate addition is an in situ remediation approach that may enhance the sequestration of uranium without requiring sustained reducing conditions. However, the geochemical factors that determine the dominant immobilization mechanisms upon phosphate addition are insufficiently understood to design efficient remediation strategies or accurately predict U(VI) transport. The overall objective of our project is to determine the dominant mechanisms of U(VI)-phosphate reactions in subsurface environments. Our research approach seeks to determine the U(VI)-phosphate solid that form in the presence of different groundwater cations, characterize the effects of phosphate on U(VI) adsorption and precipitation on smectite and iron oxide minerals, examples ofmore » two major reactive mineral phases in contaminated sediments, and investigate how phosphate affects U(VI) speciation and fate during water flow through sediments from contaminated sites. The research activities conducted for this project have generated a series of major findings. U(VI) phosphate solids from the autunite mineral family are the sole phases to form during precipitation, with uranyl orthophosphate not occurring despite its predicted greater stability. Calcium phosphates may take up substantial quantities of U(VI) through three different removal processes (adsorption, coprecipitation, and precipitation) but the dominance of each process varies with the pathway of reaction. Phosphate co-adsorbs with U(VI) onto smectite mineral surfaces, forming a mixed uranium-phosphate surface complex over a wide range of conditions. However, this molecular-scale association of uranium and phosphate has not effect on the overall extent of uptake. In contrast, phosphate enhanced U(VI) adsorption to iron oxide minerals at acidic pH conditions but suppresses such adsorption at neutral and alkaline pH, despite forming mixed uranium-phosphate surface complexes during adsorption. Nucleation barriers exist that inhibit U(VI) phosphate solids from precipitating in the presence of smectite and iron oxide minerals as well as sediments from contaminated sites. Phosphate addition enhances retention of U(VI) by sediments from the Rifle, CO and Hanford, WA field research sites, areas containing substantial uranium contamination of groundwater. This enhanced retention is through adsorption processes. Both fast and slow uptake and release behavior is observed, indicating that diffusion of uranium between sediment grains has a substantial effect of U(VI) fate in flowing groundwater systems. This project has revealed the complexity of U(VI)-phosphate reactions in subsurface systems. Distinct chemical processes occur in acidic and alkaline groundwater systems. For the latter, calcium phosphate formation, solution complexation, and competition between phosphate and uranium for adsorption sites may serve to either enhance or inhibit U(VI) removal from groundwater. Under the groundwater conditions present at many contaminated sites in the U.S., phosphate appears to general enhance U(VI) retention and limit transport. However, formation of low-solubility uranium phosphate solids does not occur under field-relevant conditions, despite this being the desired product of phosphate-based remediation approaches. In addition, simple equilibrium approaches fail to well-predict uranium fate in contaminated sediments amended with phosphate, with reactive transport models that include reaction rates and mass transport through occluded domains needed to properly describe the system. Phosphate addition faces challenges to being effective as a stand-alone groundwater treatment approach but would prove beneficial as an add-on to other treatment methods that will further limit uranium migration in the subsurface.« less

Synthesis, characterization and bioactivity of a calcium-phosphate glass-ceramics obtained by the sol-gel processing method.

PubMed

Jmal, Nouha; Bouaziz, Jamel

2017-02-01

In this work, a calcium-phosphate glass-ceramics was successfully obtained by heat treatment of a mixture of 26.52 in wt.% of fluorapatite (Fap) and 73.48 in wt.% of 77S (77 SiO 2 14 CaO9 P 2 O 5 in wt.%) gel. The calcium phosphate-glass-ceramics was prepared by sol-gel process with tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP), calcium nitrate and fluorapatite. The synthesized powders were characterized by some commonly used tools such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), 31 P magic angle spinning nuclear magnetic resonance (MAS-NMR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and thin-film X-ray diffraction (TF-XRD). The obtained results seemed to confirm the nucleation and growth of hydroxyapatite (Hap) nano-phase in the glass. Moreover, an in-vitro evaluation of the glass-ceramic was performed. In addition, to assess its bioactive capacity, it was soaked in simulated body fluid (SBF) at different time intervals. The SEM, EDS and TF-XRD analyses showed the deposition of hydroxyapatite on the surface of the specimens after three days of immersion in SBF solution. The mechanical properties of the obtained material such as rupture strength, Vickers hardness and elastic modulus were measured. In addition, the friction coefficient of calcium phosphate-glass-ceramics was tested. The values of the composite of rupture strength (24MPa), Vickers hardness (214Hv), Young's modulus (52.3GPa), shear modulus (19GPa) and friction coefficient (0.327) were obtained. This glass-ceramics can have useful applications in dental prostheses. Indeed, this material may have promising applications for implants because of its content of fluorine, the effective protector against dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

Internal loading of phosphate in Lake Erie Central Basin.

PubMed

Paytan, Adina; Roberts, Kathryn; Watson, Sue; Peek, Sara; Chuang, Pei-Chuan; Defforey, Delphine; Kendall, Carol

2017-02-01

After significant reductions in external phosphorus (P) loads, and subsequent water quality improvements in the early 1980s, the water quality of Lake Erie has declined considerably over the past decade. The frequency and magnitude of harmful algal blooms (primarily in the western basin) and the extent of hypoxic bottom waters in the central basin have increased. The decline in ecosystem health, despite meeting goals for external P loads, has sparked a renewed effort to understand P cycling in the lake. We use pore-water P concentration profiles and sediment cores incubation experiments to quantify the P flux from Lake Erie central basin sediments. In addition, the oxygen isotopes of phosphate were investigated to assess the isotopic signature of sedimentary phosphate inputs relative to the isotopic signature of phosphate in lake water. Extrapolating the total P sediment flux based on the pore-water profiles to the whole area of the central basin ranged from 300 to 1250metric tons per year and using the flux based on core incubation experiments an annual flux of roughly 2400metric tons of P is calculated. These estimates amount to 8-20% of the total external input of P to Lake Erie. The isotopic signature of phosphate in the extractable fraction of the sediments (~18‰) can explain the non-equilibrium isotope values of dissolved phosphate in the deep water of the central basin of Lake Erie, and this is consistent with sediments as an important internal source of P in the Lake. Copyright © 2016 Elsevier B.V. All rights reserved.

The pentose phosphate pathway of glucose metabolism. Hormonal and dietary control of the oxidative and non-oxidative reactions of the cycle in liver

PubMed Central

Novello, F.; Gumaa, J. A.; McLean, Patricia

1969-01-01

1. Measurements were made of the non-oxidative reactions of the pentose phosphate cycle in liver (transketolase, transaldolase, ribulose 5-phosphate epimerase and ribose 5-phosphate isomerase activities) in a variety of hormonal and nutritional conditions. In addition, glucose 6-phosphate dehydrogenase and 6-phosphogluconate dehydrogenase activities were measured for comparison with the oxidative reactions of the cycle; hexokinase, glucokinase and phosphoglucose isomerase activities were also included. Starvation for 2 days caused significant lowering of activity of all the enzymes of the pentose phosphate cycle based on activity in the whole liver. Re-feeding with a high-carbohydrate diet restored all the enzyme activities to the range of the control values with the exception of that of glucose 6-phosphate dehydrogenase, which showed the well-known `overshoot' effect. Re-feeding with a high-fat diet also restored the activities of all the enzymes of the pentose phosphate cycle and of hexokinase; glucokinase activity alone remained unchanged. Expressed as units/g. of liver or units/mg. of protein hexokinase, glucose 6-phosphate dehydrogenase, transketolase and pentose phosphate isomerase activities were unchanged by starvation; both 6-phosphogluconate dehydrogenase and ribulose 5-phosphate epimerase activities decreased faster than the liver weight or protein content. 2. Alloxan-diabetes resulted in a decrease of approx. 30–40% in the activities of 6-phosphogluconate dehydrogenase, ribose 5-phosphate isomerase, ribulose 5-phosphate epimerase and transketolase; in contrast with this glucose 6-phosphate dehydrogenase, transaldolase and phosphoglucose isomerase activities were unchanged. Treatment of alloxan-diabetic rats with protamine–zinc–insulin for 3 days caused a very marked increase to above normal levels of activity in all the enzymes of the pentose phosphate pathway except ribulose 5-phosphate epimerase, which was restored to the control value. Hexokinase activity was also raised by this treatment. After 7 days treatment of alloxan-diabetic rats with protamine–zinc–insulin the enzyme activities returned towards the control values. 3. In adrenalectomized rats the two most important changes were the rise in hexokinase activity and the fall in transketolase activity; in addition, ribulose 5-phosphate epimerase activity was also decreased. These effects were reversed by cortisone treatment. In addition, in cortisone-treated adrenalectomized rats glucokinase activity was significantly lower than the control value. 4. In thyroidectomized rats both ribose 5-phosphate isomerase and transketolase activities were decreased; in contrast with this transaldolase activity did not change significantly. Hypophysectomy caused a 50% fall in transketolase activity that was partially reversed by treatment with thyroxine and almost fully reversed by treatment with growth hormone for 8 days. 5. The results are discussed in relation to the hormonal control of the non-oxidative reactions of the pentose phosphate cycle, the marked changes in transketolase activity being particularly outstanding. PMID:5791534

Uranium(VI) Scavenging by Amorphous Iron Phosphate Encrusting Sphaerotilus natans Filaments.

PubMed

Seder-Colomina, Marina; Morin, Guillaume; Brest, Jessica; Ona-Nguema, Georges; Gordien, Nilka; Pernelle, Jean-Jacques; Banerjee, Dipanjan; Mathon, Olivier; Esposito, Giovanni; van Hullebusch, Eric D

2015-12-15

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.

Phosphate Remediation and Recovery from Lake Water using Modified Iron Oxide-based Adsorbents

EPA Science Inventory

Adsorption behavior of Bayoxide ® E33 (E33) and three E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese and nanoparticles. Characterization was done by X-ray diffract...

Thermal behavior of epoxidized cardanol diethyl phosphate as novel renewable plasticizer for poly(vinyl chloride)

USDA-ARS?s Scientific Manuscript database

A novel plasticizer, epoxidized cardanol diethyl phosphate (ECEP), based on cardanol was synthesized. Chemical structure of ECEP was characterized by fourier transform infrared (FTIR), 1H-nuclear magnetic resonance(1H NMR) and 13C-nuclear magnetic resonance(13C NMR) spectroscopy. Effects of ECEP sub...

Adsorption of Phosphate on Goethite: An Undergraduate Research Laboratory Project

ERIC Educational Resources Information Center

Tribe, Lorena; Barja, Beatriz C.

2004-01-01

A laboratory experiment on the adsorption of phosphate on goethite is presented, which also includes discussion on surface properties, interfaces, acid-base equilibrium, molecular structure and solid state chemistry. It was seen that many students were able to produce qualitatively correct results for a complex system of real interest and they…

A Phos-tag-based magnetic-bead method for rapid and selective separation of phosphorylated biomolecules.

PubMed

Tsunehiro, Masaya; Meki, Yuma; Matsuoka, Kanako; Kinoshita-Kikuta, Emiko; Kinoshita, Eiji; Koike, Tohru

2013-04-15

A simple and efficient method based on magnetic-bead technology has been developed for the separation of phosphorylated and nonphosphorylated low-molecular-weight biomolecules, such as nucleotides, phosphorylated amino acids, or phosphopeptides. The phosphate-binding site on the bead is an alkoxide-bridged dinuclear zinc(II) complex with 1,3-bis(pyridin-2-ylmethylamino)propan-2-olate (Phos-tag), which is linked to a hydrophilic cross-linked agarose coating on a magnetic core particle. All steps for the phosphate-affinity separation are conducted in buffers of neutral pH with 50 μL of the magnetic beads in a 1.5-mL microtube. The entire separation protocol for phosphomonoester-type compounds, from addition to elution, requires less than 12 min per sample if the buffers and the zinc(II)-bound Phos-tag magnetic beads have been prepared in advance. The phosphate-affinity magnetic beads are reusable at least 15 times without a decrease in their phosphate-binding ability and they are stable for three months in propan-2-ol. Copyright © 2013 Elsevier B.V. All rights reserved.

Removal of fluoride ion by bone char produced from animal biomass.

PubMed

Kawasaki, Naohito; Ogata, Fumihiko; Tominaga, Hisato; Yamaguchi, Isao

2009-01-01

Bone char (BC) was prepared by carbonizing four types of animal biomass, and the adsorption of fluoride ions and elution of phosphate ions were investigated. It was found that the BC yield decreased as carbonization temperature increased, and that carbonization temperature had no significant effect on surface pH, base or acid consumptions. Fluoride ion adsorption was increased in BC produced at a low carbonization temperature. The adsorption mechanism of fluoride ion on BCs might be monolayer adsorption. BC can potentially be used to remove fluoride ions in drinking water. However, it was found that phosphate ions from BC are eluted due to adsorption of fluoride ions, and that ingestion of large amounts of phosphate ions inhibits reabsorption of calcium in the human body. Thus there is a need to study the elution behavior of phosphate ions. The adsorption mechanisms of fluoride ions onto BC would be a physical adsorption onto BC and phosphate ion in BC is exchanged to fluoride ion.

"Fabrication of arbitrarily shaped carbonate apatite foam based on the interlocking process of dicalcium hydrogen phosphate dihydrate".

PubMed

Sugiura, Yuki; Tsuru, Kanji; Ishikawa, Kunio

2017-08-01

Carbonate apatite (CO 3 Ap) foam with an interconnected porous structure is highly attractive as a scaffold for bone replacement. In this study, arbitrarily shaped CO 3 Ap foam was formed from α-tricalcium phosphate (α-TCP) foam granules via a two-step process involving treatment with acidic calcium phosphate solution followed by hydrothermal treatment with NaHCO 3 . The treatment with acidic calcium phosphate solution, which is key to fabricating arbitrarily shaped CO 3 Ap foam, enables dicalcium hydrogen phosphate dihydrate (DCPD) crystals to form on the α-TCP foam granules. The generated DCPD crystals cause the α-TCP granules to interlock with each other, inducing an α-TCP/DCPD foam. The interlocking structure containing DCPD crystals can survive hydrothermal treatment with NaHCO 3 . The arbitrarily shaped CO 3 Ap foam was fabricated from the α-TCP/DCPD foam via hydrothermal treatment at 200 °C for 24 h in the presence of a large amount of NaHCO 3 .

A safer disposal of hazardous phosphate coating sludge by formation of an amorphous calcium phosphate matrix.

PubMed

Navarro-Blasco, I; Duran, A; Pérez-Nicolás, M; Fernández, J M; Sirera, R; Alvarez, J I

2015-08-15

Phosphate coating hazardous wastes originated from the automotive industry were efficiently encapsulated by an acid-base reaction between phosphates present in the sludge and calcium aluminate cement, yielding very inert and stable monolithic blocks of amorphous calcium phosphate (ACP). Two different compositions of industrial sludge were characterized and loaded in ratios ranging from 10 to 50 wt.%. Setting times and compressive strengths were recorded to establish the feasibility of this method to achieve a good handling and a safe landfilling of these samples. Short solidification periods were found and leaching tests showed an excellent retention for toxic metals (Zn, Ni, Cu, Cr and Mn) and for organic matter. Retentions over 99.9% for Zn and Mn were observed even for loadings as high as 50 wt.% of the wastes. The formation of ACP phase of low porosity and high stability accounted for the effective immobilization of the hazardous components of the wastes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Extrusion-based, three-dimensional printing of calcium-phosphate scaffolds

NASA Astrophysics Data System (ADS)

Witek, Lukasz

Small or large bone defects, can occur due to a variety of reasons: congenital disorders, infections, tumors, or traumas which can lead to significant disabilities. There is an assortment of bone grafting procedures, each having their own respective advantages and disadvantages and exhibiting certain essential characteristics. Among the available grafts, autogenous (autograft), allograft, xenograft, and alloplasts, all exhibit a minimum of two-thirds of the essential characteristics and have been proven useful in fully or partially repairing skeletal defects. However, different host-to-grafting material responses have been reported and should be taken into consideration when determining treatment options. A large range of physical and chemical properties can be achieved with calcium phosphate based materials, which possess two of the ideal characteristics for grafting procedures: osteoconduction and osseointegration. Calcium phosphate based scaffolds composed of hydroxyapatite (HA), beta-tri-calcium phosphate (beta-TCP), or a combination of both (HA/beta-TCP) were investigated as materials for three-dimensional printing process to create layer-by-layer structures for use as bone regeneration scaffolds. Different calcium-phosphate phases will result in different degrees of in vivo dissolution and/or cell-mediated resorption. There has been a growing interest in BCP because it has been shown that this material improves the formation of new bone inside the implanted scaffold. The literature indicates that the faster dissolution rate of ?-TCP would be greatly responsible of this enhancement. However, in vitro tests indicate that fast dissolution can decrease the mechanical strength of BCP scaffolds. Furthermore, studies reported that HA has higher mechanical strength and lower degradation rate than beta-TCP. Therefore, the HA/beta-TCP ratio is a key parameter controlling the performance of the scaffold for bone repair applications, since it determines degradation rate, calcium (Ca2+) and phosphate (PO4) release and mechanical properties of the material.

Multifunctional phosphate-based inorganic-organic hybrid nanoparticles.

PubMed

Heck, Joachim G; Napp, Joanna; Simonato, Sara; Möllmer, Jens; Lange, Marcus; Reichardt, Holger M; Staudt, Reiner; Alves, Frauke; Feldmann, Claus

2015-06-17

Phosphate-based inorganic-organic hybrid nanoparticles (IOH-NPs) with the general composition [M](2+)[Rfunction(O)PO3](2-) (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3](2-) is a fluorescent dye anion ([RdyeOPO3](2-)), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO](2+)[PUP](2-), [ZrO](2+)[MFP](2-), [ZrO](2+)[RRP](2-), and [ZrO](2+)[DUT](2-) (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3](2-)), drug transport and release of anti-inflammatory ([ZrO](2+)[BMP](2-)) and antitumor agents ([ZrO](2+)[FdUMP](2-)) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5'-fluoro-2'-deoxyuridine 5'-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO](2+)[BMP](2-)0.996[DUT](2-)0.004. Merging of functional anions, in general, results in [ZrO](2+)([RdrugOPO3]1-x[RdyeOPO3]x)(2-) nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO](2+)[RaminePO3](2-) IOH-NPs, finally, show CO2 sorption (up to 180 mg g(-1)) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP](2-), 1-aminoethyl phosphonate [1AEP](2-), 2-aminoethyl phosphonate [2AEP](2-), aminopropyl phosphonate [APP](2-), and aminobutyl phosphonate [ABP](2-). All [M](2+)[Rfunction(O)PO3](2-) IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.

Radioactivity contents in dicalcium phosphate and the potential radiological risk to human populations.

PubMed

Casacuberta, N; Masqué, P; Garcia-Orellana, J; Bruach, J M; Anguita, M; Gasa, J; Villa, M; Hurtado, S; Garcia-Tenorio, R

2009-10-30

Potentially harmful phosphate-based products derived from the wet acid digestion of phosphate rock represent one of the most serious problems facing the phosphate industry. This is particularly true for dicalcium phosphate (DCP), a food additive produced from either sulphuric acid or hydrochloric acid digestion of raw rock material. This study determined the natural occurring radionuclide concentrations of 12 DCP samples and 4 tricalcium phosphate (TCP) samples used for animal and human consumption, respectively. Metal concentrations (Al, Fe, Zn, Cd, Cr, As, Hg, Pb and Mg) were also determined. Samples were grouped into three different clusters (A, B, C) based on their radionuclide content. Whereas group A is characterized by high activities of 238U, 234U (approximately 10(3) Bq kg(-1)), 210Pb (2 x 10(3) Bq kg(-1)) and (210)Po ( approximately 800 Bq kg(-1)); group B presents high activities of (238)U, (234)U and (230)Th (approximately 10(3) Bq kg(-1)). Group C was characterized by very low activities of all radionuclides (< 50 Bq kg(-1)). Differences between the two groups of DCP samples for animal consumption (groups A and B) were related to the wet acid digestion method used, with group A samples produced from hydrochloric acid digestion, and group B samples produced using sulphuric acid. Group C includes more purified samples required for human consumption. High radionuclide concentrations in some DCP samples (reaching 2 x 10(3) and 10(3) Bq kg(-1) of 210Pb and 210Po, respectively) may be of concern due to direct or indirect radiological exposure via ingestion. Our experimental results based on 210Pb and 210Po within poultry consumed by humans, suggest that the maximum radiological doses are 11 +/- 2 microSv y(-1). While these results suggest that human health risks are small, additional testing should be conducted.

Optimized design of Yb3+/Er3+-codoped cross-coupled integrated microring resonator arrays

NASA Astrophysics Data System (ADS)

Gǎlǎtus, Ramona; Vallés, Juan A.

2014-09-01

In this work the analytical model of the scattering response of a highly Yb3+/Er3+-codoped phosphate glass microring resonator array is developed. The microscopic statistical formalism is used to simulate its performance as a wavelengthselective amplifier. The performance of the integrated add-drop filter was investigated based on the signal transfer functions for Through and Drop ports, correlated the with gain coefficient and its dependence on pump power, signal power and Yb3+/Er3+- dopants concentration. In consequence, microring arrays with gain operating in the near infrared spectral range and, in particular, in the 1.5-mm wavelength band (emission band of Er-doped fiber amplifiers and lasers, already used in several bio/chemical sensing tasks) are highly attractive.

Influence of pulse ratio on codeposition of copper species with calcium phosphate coatings on titanium by means of electrochemically assisted deposition.

PubMed

Wolf-Brandstetter, Cornelia; Oswald, Steffen; Bierbaum, Susanne; Wiesmann, Hans-Peter; Scharnweber, Dieter

2014-01-01

Aim of this study was to combine the well-known biocompatibility and ostoeconductivity of thin calcium phosphate coatings on titanium with proangiogenic signals from codeposited copper species. Copper species could be integrated in mineral layers based on hydroxyapatite by means of electrochemically assisted deposition from electrolytes containing calcium, phosphate, and copper ions. Different combinations of duration and intensity of galvanostatic pulses result in different amounts of deposited calcium phosphate and of copper species even for the same applied total charge. Absolute amounts of copper varied between 2.1 and 6.9 μg/cm², and the copper was distributed homogeneously as shown by EDX mapping. The presence of copper did not change the crystalline phase of deposited calcium phosphate (hydroxyapatite) but provoked a significant decrease in deposited amounts by factor 3 to 4. The copper was deposited mainly as Cu(I) species with a minor fraction of basic copper phosphates. Reduction of copper occurred not only at the surface of titanium but also within the hydroxyapatite coating due to the reaction with hydrogen produced by the electrolysis of water during the cathodic polarization of the substrate. Copyright © 2013 Wiley Periodicals, Inc.

A first report of hydroxylated apatite as structural biomineral in Loasaceae - plants’ teeth against herbivores

NASA Astrophysics Data System (ADS)

Ensikat, Hans-Jürgen; Geisler, Thorsten; Weigend, Maximilian

2016-05-01

Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix.

Urban storm-runoff modelling; Madison, Wisconsin

USGS Publications Warehouse

Grant, R. Stephen; Goddard, Gerald

1979-01-01

A brief inconclusive evaluation of the water-quality subroutines of the model was made. Close agreement was noted between observed and simulated loads for nitrates, organic nitrogen, total phosphate, and total solids. Ammonia nitrogen and orthophosphate computed by the model ranged 7 to 11 times greater than the observed loads. Observed loads are doubtful because of the sparsity of water-quality data.

Aircraft Recirculation Filter for Air-Quality and Incident Assessment

PubMed Central

Eckels, Steven J.; Jones, Byron; Mann, Garrett; Mohan, Krishnan R.; Weisel, Clifford P.

2015-01-01

The current research examines the possibility of using recirculation filters from aircraft to document the nature of air-quality incidents on aircraft. These filters are highly effective at collecting solid and liquid particulates. Identification of engine oil contaminants arriving through the bleed air system on the filter was chosen as the initial focus. A two-step study was undertaken. First, a compressor/bleed air simulator was developed to simulate an engine oil leak, and samples were analyzed with gas chromatograph-mass spectrometry. These samples provided a concrete link between tricresyl phosphates and a homologous series of synthetic pentaerythritol esters from oil and contaminants found on the sample paper. The second step was to test 184 used aircraft filters with the same gas chromatograph-mass spectrometry system; of that total, 107 were standard filters, and 77 were nonstandard. Four of the standard filters had both markers for oil, with the homologous series synthetic pentaerythritol esters being the less common marker. It was also found that 90% of the filters had some detectable level of tricresyl phosphates. Of the 77 nonstandard filters, 30 had both markers for oil, a significantly higher percent than the standard filters. PMID:25641977

The behaviour of tributyl phosphate in an organic diluent

NASA Astrophysics Data System (ADS)

Leay, Laura; Tucker, Kate; Del Regno, Annalaura; Schroeder, Sven L. M.; Sharrad, Clint A.; Masters, Andrew J.

2014-09-01

Tributyl phosphate (TBP) is used as a complexing agent in the Plutonium Uranium Extraction (PUREX) liquid-liquid phase extraction process for recovering uranium and plutonium from spent nuclear reactor fuel. Here, we address the molecular and microstructure of the organic phases involved in the extraction process, using molecular dynamics to show that when TBP is mixed with a paraffinic diluent, the TBP self-assembles into a bi-continuous phase. The underlying self-association of TBP is driven by intermolecular interaction between its polar groups, resulting in butyl moieties radiating out into the organic solvent. Simulation predicts a TBP diffusion constant that is anomalously low compared to what might normally be expected for its size; experimental nuclear magnetic resonance (NMR) studies also indicate an extremely low diffusion constant, consistent with a molecular aggregation model. Simulation of TBP at an oil/water interface shows the formation of a bilayer system at low TBP concentrations. At higher concentrations, a bulk bi-continuous structure is observed linking to this surface bilayer. We suggest that this structure may be intimately connected with the surprisingly rapid kinetics of the interfacial mass transport of uranium and plutonium from the aqueous to the organic phase in the PUREX process.

Inter-atomic potentials for radiation damage studies in CePO4 monazite

NASA Astrophysics Data System (ADS)

Jolley, Kenny; Asuvathraman, Rajaram; Smith, Roger

2017-02-01

An original empirical potential used for modelling phosphate glasses is adapted to be suitable for use with monazite (CePO4) so as to have a consistent formulation for radiation damage studies of phosphates. This is done by adding a parameterisation for the Ce-O interaction to the existing potential set. The thermal and structural properties of the resulting computer model are compared to experimental results. The parameter set gives a stable monazite structure where the volume of the unit cell is almost identical to that measured experimentally, but with some shrinkage in the a and b lengths and a small expansion in the c direction compared to experiment. The thermal expansion, specific heat capacity and estimates of the melting point are also determined. The estimate of the melting temperature of 2500 K is comparable to the experimental value of 2318 ± 20 K, but the simulated thermal expansion of 49 ×10-6 K-1 is larger than the usually reported value. The simulated specific heat capacity at constant pressure was found to be approximately constant at 657 J kg-1 K-1 in the range 300-1000 K, however, this is not observed experimentally or in more detailed ab initio calculations.

Aircraft Recirculation Filter for Air-Quality and Incident Assessment.

PubMed

Eckels, Steven J; Jones, Byron; Mann, Garrett; Mohan, Krishnan R; Weisel, Clifford P

The current research examines the possibility of using recirculation filters from aircraft to document the nature of air-quality incidents on aircraft. These filters are highly effective at collecting solid and liquid particulates. Identification of engine oil contaminants arriving through the bleed air system on the filter was chosen as the initial focus. A two-step study was undertaken. First, a compressor/bleed air simulator was developed to simulate an engine oil leak, and samples were analyzed with gas chromatograph-mass spectrometry. These samples provided a concrete link between tricresyl phosphates and a homologous series of synthetic pentaerythritol esters from oil and contaminants found on the sample paper. The second step was to test 184 used aircraft filters with the same gas chromatograph-mass spectrometry system; of that total, 107 were standard filters, and 77 were nonstandard. Four of the standard filters had both markers for oil, with the homologous series synthetic pentaerythritol esters being the less common marker. It was also found that 90% of the filters had some detectable level of tricresyl phosphates. Of the 77 nonstandard filters, 30 had both markers for oil, a significantly higher percent than the standard filters.

Effects of Simulated Rare Earth Recycling Wastewaters on Biological Nitrification.

PubMed

Fujita, Yoshiko; Barnes, Joni; Eslamimanesh, Ali; Lencka, Malgorzata M; Anderko, Andrzej; Riman, Richard E; Navrotsky, Alexandra

2015-08-18

Increasing rare earth element (REE) supplies by recycling and expanded ore processing will result in generation of new wastewaters. In some cases, disposal to a sewage treatment plant may be favored, but plant performance must be maintained. To assess the potential effects of such wastewaters on biological treatment, model nitrifying organisms Nitrosomonas europaea and Nitrobacter winogradskyi were exposed to simulated wastewaters containing varying levels of yttrium or europium (10, 50, and 100 ppm), and the extractant tributyl phosphate (TBP, at 0.1 g/L). Y and Eu additions at 50 and 100 ppm inhibited N. europaea, even when virtually all of the REE was insoluble. Provision of TBP with Eu increased N. europaea inhibition, although TBP alone did not substantially alter activity. For N. winogradskyi cultures, Eu or Y additions at all tested levels induced significant inhibition, and nitrification shut down completely with TBP addition. REE solubility was calculated using the previously developed MSE (Mixed-Solvent Electrolyte) thermodynamic model. The model calculations reveal a strong pH dependence of solubility, typically controlled by the precipitation of REE hydroxides but also likely affected by the formation of unknown phosphate phases, which determined aqueous concentrations experienced by the microorganisms.

Quantifying Dimer and Trimer Formation by Tri- n -butyl Phosphates in n -Dodecane: Molecular Dynamics Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vo, Quynh N.; Dang, Liem X.; Nilsson, Mikael

2016-07-21

Tri-n-butyl phosphate (TBP), a representative of neutral organophosphorous ligands, is an important extractant used in solvent extraction process for the recovery of uranium and plutonium from spent nuclear fuel. Microscopic pictures of TBP isomerism and its behavior in n-dodecane diluent were investigated utilizing MD simulations with previously optimized force field parameters for TBP and n-dodecane. Potential Mean Force (PMF) calculations on a single TBP molecule show seven probable TBP isomers. Radial Distribution Functions (RDF) of TBP suggests the existence of TBP trimers at high TBP concentrations in addition to dimers. 2D PMF calculations were performed to determine the angle andmore » distance criteria for TBP trimers. The dimerization and trimerization constants of TBP in n-dodecane were obtained and match our own experimental values using FTIR technique. The new insights into the conformational behaviors of TBP molecule as a monomer and as part of an aggregate could greatly aid the understanding of the complexation between TBP and metal ions in solvent extraction system. The U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences funded the work performed by LXD.« less

Origin of Cretaceous phosphorites from the onshore of Tamil Nadu, India

NASA Astrophysics Data System (ADS)

Purnachandra Rao, V.; Kessarkar, Pratima M.; Nagendra, R.; Babu, E. V. S. S. K.

2007-12-01

Cretaceous phosphorites from the onshore of Tamil Nadu have been investigated for their origin and compared with those in the offshore. Cretaceous phosphorites occur as light brown to yellowish brown or white nodules in Karai Shale of the Uttatur Group in the onshore Cauvery basin. Nodules exhibit phosphatic nucleus encrusted by a chalky shell of carbonate. The nucleus of the nodules consists of light and dark coloured laminae, phosphate peloids/coated grains and detrital particles interspersed between the laminae. Scanning electron microscope (SEM) studies reveal trapping and binding activity of microbial filaments. A mat structure with linearly arranged microbial filaments and hollow, cell-based coccoid cyanobacterial mat are present. Nodules contain abundant carbonate fluorapatite, followed by minor calcite, quartz and feldspar. The P2O5 content of the phosphorites ranges from 18 to 26%. The CaO/P2O5, Sr and F contents are higher than that of pure carbonate fluorapatite. Concentrations of Si, Al, K, Fe, and Ti are low. We suggest that the nuclei of the nodules represent phosphate clasts related to phosphate stromatolites formed at intertidal conditions. At high energy levels the microbial mats were disintegrated into phosphate clasts, coated with carbonate and then reworked into Karai Shale. On the other hand, Quaternary phosphorites occur as irregular to rounded, grey coloured phosphate clasts at water depths between 180 and 320m on the continental shelf of Tamil Nadu. They exhibit grain-supported texture. Despite Quaternary in age, they also resemble phosphate stromatolites of intertidal origin and reworked as phosphate clasts onto the shelf margin depressions. Benthic microbial mats probably supplied high phosphorus to the sediments. Availability of excess phosphorus seems to be a pre-requisite for the formation of phosphate stromatolites.

Evaluation of Cytokine Synthesis in Human Whole Blood by Enzyme Linked Immunoassay (ELISA), Reverse Transcriptase Polymerase Chain Reaction (RT-PCR), and Flow Cytometry

DTIC Science & Technology

2007-05-08

deoxynucleotide triphosphates, from Sigma. Sequences for glyceraldehyde-3-phosphate dehydrogenase ( G3PDH ), IL-8,and TNF-a were amplified with primer...This was accomplished by normalizing all samples to the mRNA for the moderately expressed housekeeping function glyceraldehyde-3 -phosphate...without and with isolation of cells before reverse transcription and PCR. G3PDH mRNA target amplifies at 983 base pairs. The 630 base pair band is the

A molecular dynamics study of slow base flipping in DNA using conformational flooding.

PubMed

Bouvier, Benjamin; Grubmüller, Helmut

2007-08-01

Individual DNA bases are known to be able to flip out of the helical stack, providing enzymes with access to the genetic information otherwise hidden inside the helix. Consequently, base flipping is a necessary first step to many more complex biological processes such as DNA transcription or replication. Much remains unknown about this elementary step, despite a wealth of experimental and theoretical studies. From the theoretical point of view, the involved timescale of milliseconds or longer requires the use of enhanced sampling techniques. In contrast to previous theoretical studies employing umbrella sampling along a predefined flipping coordinate, this study attempts to induce flipping without prior knowledge of the pathway, using information from a molecular dynamics simulation of a B-DNA fragment and the conformational flooding method. The relevance to base flipping of the principal components of the simulation is assayed, and a combination of modes optimally related to the flipping of the base through either helical groove is derived for each of the two bases of the central guanine-cytosine basepair. By applying an artificial flooding potential along these collective coordinates, the flipping mechanism is accelerated to within the scope of molecular dynamics simulations. The associated free energy surface is found to feature local minima corresponding to partially flipped states, particularly relevant to flipping in isolated DNA; further transitions from these minima to the fully flipped conformation are accelerated by additional flooding potentials. The associated free energy profiles feature similar barrier heights for both bases and pathways; the flipped state beyond is a broad and rugged attraction basin, only a few kcal/mol higher in energy than the closed conformation. This result diverges from previous works but echoes some aspects of recent experimental findings, justifying the need for novel approaches to this difficult problem: this contribution represents a first step in this direction. Important structural factors involved in flipping, both local (sugar-phosphate backbone dihedral angles) and global (helical axis bend), are also identified.

Interactions between calcium precipitation and the polyphosphate-accumulating bacteria metabolism.

PubMed

Barat, R; Montoya, T; Borrás, L; Ferrer, J; Seco, A

2008-07-01

A sequencing batch reactor that is operated for biological phosphorus removal has been operated under different influent calcium concentrations to study the precipitation process and the possible effects of phosphorus precipitation in the biological phosphorus removal process. Four experiments were carried out under different influent calcium concentrations ranging from 10 to 90 g Ca m(-3). The experimental results and the equilibrium study, which are based on the saturation index calculation, confirm that the process controlling the calcium behaviour is the calcium phosphate precipitation. This precipitation takes place at two stages: initially, precipitation of the amorphous calcium phosphate, and later crystallization of hydroxyapatite. Also the accumulation of phosphorus precipitated was observed when the influent calcium concentration was increased. In all the experiments, the influent wastewater ratio P/COD was kept constant. It has been observed that, at high calcium concentration, the ratio between phosphate release and acetate uptake (P(rel)/Ac(uptake)) decreases. Changes in the polyphosphate-accumulating organism (PAO) population and in the glycogen-accumulating organism (GAO) population during the experimental period were ruled out by means of fluorescence in situ hybridization. These results could suggest that PAO are able to change their metabolic pathways based on external conditions, such as influent calcium concentration. The accumulation of phosphorus precipitated as calcium phosphate at high influent calcium concentration throughout the experimental period confirmed that phosphate precipitation is a process that can affect the PAO metabolism.

Method for producing redox shuttles

DOEpatents

Pupek, Krzysztof Z.; Dzwiniel, Trevor L.; Krumdick, Gregory K.

2015-03-03

A single step method for producing a redox shuttle having the formula 2,5-di-tert-butyl-1,4-phenylene tetraethyl bis(phosphate) is provided, the method comprising phosphorylating tert butyl hydroquinone with a phosphate-containing reagent. Also provided is method for producing 2,5-di-tert-butyl-1,4-phenylene tetraethyl bis(phosphate), the method comprising solubilizing tert-butyl hydroquinone and tetrabutylammonium bromide with methyltetrahydrofuran to create a mixture; heating the mixture while adding base to the mixture in an amount to turn the mixture orange; and adding diethyl chlorophosphate to the orange mixture in an amount to phosphorylate the hydroquinone.

Synthesis of β-tricalcium phosphate.

PubMed

Chaair, H; Labjar, H; Britel, O

2017-09-01

Ceramics play a key role in several biomedical applications. One of them is bone grafting, which is used for treating bone defects caused by injuries or osteoporosis. Calcium-phosphate based ceramic are preferred as bone graft biomaterials in hard tissue surgery because their chemical composition is close to the composition of human bone. They also have a marked bioresorbability and bioactivity. In this work, we have developed methods for synthesis of β-tricalcium phosphate apatite (β-TCP). These products were characterized by different techniques such as X-ray diffraction, infrared spectroscopy, scanning electron microscopy and chemical analysis. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Molecular dynamics simulations of apo, holo, and inactivator bound GABA-at reveal the role of active site residues in PLP dependent enzymes.

PubMed

Gökcan, Hatice; Monard, Gerald; Sungur Konuklar, F Aylin

2016-07-01

The pyridoxal 5-phosphate (PLP) cofactor is a significant organic molecule in medicinal chemistry. It is often found covalently bound to lysine residues in proteins to form PLP dependent enzymes. An example of this family of PLP dependent enzymes is γ-aminobutyric acid aminotransferase (GABA-AT) which is responsible for the degradation of the neurotransmitter GABA. Its inhibition or inactivation can be used to prevent the reduction of GABA concentration in brain which is the source of several neurological disorders. As a test case for PLP dependent enzymes, we have performed molecular dynamics simulations of GABA-AT to reveal the roles of the protein residues and its cofactor. Three different states have been considered: the apoenzyme, the holoenzyme, and the inactive state obtained after the suicide inhibition by vigabatrin. Different protonation states have also been considered for PLP and two key active site residues: Asp298 and His190. Together, 24 independent molecular dynamics trajectories have been simulated for a cumulative total of 2.88 µs. Our results indicate that, unlike in aqueous solution, the PLP pyridine moiety is protonated in GABA-AT. This is a consequence of a pKa shift triggered by a strong charge-charge interaction with an ionic "diad" formed by Asp298 and His190 that would help the activation of the first half-reaction of the catalytic mechanism in GABA-AT: the conversion of PLP to free pyridoxamine phosphate (PMP). In addition, our MD simulations exhibit additional strong hydrogen bond networks between the protein and PLP: the phosphate group is held in place by the donation of at least three hydrogen bonds while the carbonyl oxygen of the pyridine ring interacts with Gln301; Phe181 forms a π-π stacking interaction with the pyridine ring and works as a gate keeper with the assistance of Val300. All these interactions are hypothesized to help maintain free PMP in place inside the protein active site to facilitate the second half-reaction in GABA-AT: the regeneration of PLP-bound GABA-AT (i.e., the holoenzyme). Proteins 2016; 84:875-891. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Calcium phosphate deposition rate, structure and osteoconductivity on electrospun poly(l-lactic acid) matrix using electrodeposition or simulated body fluid incubation

PubMed Central

He, Chuanglong; Jin, Xiaobing; Ma, Peter X.

2013-01-01

Mineralized nanofibrous scaffolds have been proposed as promising scaffolds for bone regeneration due to their ability to mimic both nanoscale architecture and chemical composition of natural bone extracellular matrix (ECM). In this study, a novel electrodeposition method was compared with an extensively explored simulated body fluid (SBF) incubation method in terms of the deposition rate, chemical composition, and morphology of calcium phosphate formed on electrospun fibrous thin matrices with a fiber diameter in the range from about 200 nm to about 1400 nm prepared using 6, 8, 10 and 12 wt% poly(l-lactic acid) (PLLA) solutions in a mixture of dichloromethane and acetone (2:1 in volume). The effects of the surface modification using the two mineralization techniques on osteoblastic cell (MC3T3-E1) proliferation and differentiation were also examined. It was found that electrodeposition was two to three orders of magnitude faster than the SBF method in mineralizing the fibrous matrices, reducing the mineralization time from about two weeks to an hour to achieve the same amounts of mineralization. The mineralization rate also varied with the fiber diameter but in opposite directions between the two mineralization methods. As a general trend, the increase of fiber diameter resulted in a faster mineralization rate for the electrodeposition method but a slower mineralization rate for the SBF incubation method. Using the electrodeposition method, one can control the chemical composition and morphology of the calcium phosphate by varying the electric deposition potential and electrolyte temperature to tune the mixture of dicalcium phosphate dihydrate (DCPD) and hydroxy apatite (HAp). Using the SBF method, one can only obtain a low crystallinity HAp. The mineralized electrospun PLLA fibrous matrices from either method similarly facilitate the proliferation and osteogenic differentiation of preosteoblastic MC3T3-E1 cells as compared to neat PLLA matrices. Therefore, the electrodeposition method can be utilized as a fast and versatile technique to fabricate mineralized nanofibrous scaffolds for bone tissue engineering. PMID:24012605

Biomechanical evaluation of fixation of intra-articular fractures of the distal part of the radius in cadavera: Kirschner wires compared with calcium-phosphate bone cement.

PubMed

Yetkinler, D N; Ladd, A L; Poser, R D; Constantz, B R; Carter, D

1999-03-01

The purpose of this study was to compare the biomechanical efficacy of an injectable calcium-phosphate bone cement (Skeletal Repair System [SRS]) with that of Kirschner wires for the fixation of intraarticular fractures of the distal part of the radius. Colles fractures (AO pattern, C2.1) were produced in ten pairs of fresh-frozen human cadaveric radii. One radius from each pair was randomly chosen for stabilization with SRS bone cement. These ten radii were treated with open incision, impaction of loose cancellous bone with use of a Freer elevator, and placement of the SRS bone cement by injection. In the ten control specimens, the fracture was stabilized with use of two horizontal and two oblique Kirschner wires. The specimens were cyclically loaded to a peak load of 200 newtons for 2000 cycles to evaluate the amount of settling, or radial shortening, under conditions simulating postoperative loading with the limb in a cast. Each specimen then was loaded to failure to determine its ultimate strength. The amount of radial shortening was highly variable among the specimens, but it was consistently higher in the Kirschner-wire constructs than in the bone fixed with SRS bone cement within each pair of radii. The range of shortening for all twenty specimens was 0.18 to 4.51 millimeters. The average amount of shortening in the SRS constructs was 50 percent of that in the Kirschner-wire constructs (0.51+/-0.34 compared with 1.01+/-1.23 millimeters; p = 0.015). With the numbers available, no significant difference in ultimate strength was detected between the two fixation groups. This study showed that fixation of an intra-articular fracture of the distal part of a cadaveric radius with biocompatible calcium-phosphate bone cement produced results that were biomechanically comparable with those produced by fixation with Kirschner wires. However, the constructs that were fixed with calcium-phosphate bone cement demonstrated less shortening under simulated cyclic load-bearing.

Nanostructured hydroxyapatite/poly(lactic-co-glycolic acid) composite coating for controlling magnesium degradation in simulated body fluid.

PubMed

Johnson, Ian; Akari, Khalid; Liu, Huinan

2013-09-20

Biodegradable magnesium (Mg) and its alloys have many attractive properties (e.g. comparable mechanical properties to cortical bone) for orthopedic implant applications, but they degrade too rapidly in the human body to meet clinical requirements. Nanostructured hydroxyapatite (nHA)/poly(lactic-co-glycolic acid) (PLGA) composite coatings provide synergistic properties for controlling degradation of Mg-based substrates and improving bone-implant integration. In this study, nHA/PLGA composites were spin coated onto Mg-based substrates and the results showed that the nHA/PLGA coatings retained nano-scale features with nHA dispersed in PLGA matrix. In comparison with non-coated Mg, the nHA/PLGA composite coated Mg increased the corrosion potential and decreased the corrosion current in revised simulated body fluid (rSBF). After 24 h of immersion in rSBF, increased calcium phosphate (CaP) deposition and formation of Mg-substituted CaP rosettes were observed on the surface of the nHA/PLGA coated Mg, indicating greater bioactivity. In contrast, no significant CaP was deposited on the PLGA coated Mg. Since both PLGA coating and nHA/PLGA coating showed some degree of delamination from Mg-based substrates during extended immersion in rSBF, the coating processing and properties should be further optimized in order to take full advantage of biodegradable Mg and nHA/PLGA nanocomposites for orthopedic applications.

Nanostructured hydroxyapatite/poly(lactic-co-glycolic acid) composite coating for controlling magnesium degradation in simulated body fluid

NASA Astrophysics Data System (ADS)

Johnson, Ian; Akari, Khalid; Liu, Huinan

2013-09-01

Biodegradable magnesium (Mg) and its alloys have many attractive properties (e.g. comparable mechanical properties to cortical bone) for orthopedic implant applications, but they degrade too rapidly in the human body to meet clinical requirements. Nanostructured hydroxyapatite (nHA)/poly(lactic-co-glycolic acid) (PLGA) composite coatings provide synergistic properties for controlling degradation of Mg-based substrates and improving bone-implant integration. In this study, nHA/PLGA composites were spin coated onto Mg-based substrates and the results showed that the nHA/PLGA coatings retained nano-scale features with nHA dispersed in PLGA matrix. In comparison with non-coated Mg, the nHA/PLGA composite coated Mg increased the corrosion potential and decreased the corrosion current in revised simulated body fluid (rSBF). After 24 h of immersion in rSBF, increased calcium phosphate (CaP) deposition and formation of Mg-substituted CaP rosettes were observed on the surface of the nHA/PLGA coated Mg, indicating greater bioactivity. In contrast, no significant CaP was deposited on the PLGA coated Mg. Since both PLGA coating and nHA/PLGA coating showed some degree of delamination from Mg-based substrates during extended immersion in rSBF, the coating processing and properties should be further optimized in order to take full advantage of biodegradable Mg and nHA/PLGA nanocomposites for orthopedic applications.

Molecular dynamics simulation for the test of calibrated OPLS-AA force field for binary liquid mixture of tri-iso-amyl phosphate and n-dodecane.

PubMed

Das, Arya; Ali, Sk Musharaf

2018-02-21

Tri-isoamyl phosphate (TiAP) has been proposed to be an alternative for tri-butyl phosphate (TBP) in the Plutonium Uranium Extraction (PUREX) process. Recently, we have successfully calibrated and tested all-atom optimized potentials for liquid simulations using Mulliken partial charges for pure TiAP, TBP, and dodecane by performing molecular dynamics (MD) simulation. It is of immense importance to extend this potential for the various molecular properties of TiAP and TiAP/n-dodecane binary mixtures using MD simulation. Earlier, efforts were devoted to find out a suitable force field which can explain both structural and dynamical properties by empirical parameterization. Therefore, the present MD study reports the structural, dynamical, and thermodynamical properties with different mole fractions of TiAP-dodecane mixtures at the entire range of mole fraction of 0-1 employing our calibrated Mulliken embedded optimized potentials for liquid simulation (OPLS) force field. The calculated electric dipole moment of TiAP was seen to be almost unaffected by the TiAP concentration in the dodecane diluent. The calculated liquid densities of the TiAP-dodecane mixture are in good agreement with the experimental data. The mixture densities at different temperatures are also studied which was found to be reduced with temperature as expected. The plot of diffusivities for TiAP and dodecane against mole fraction in the binary mixture intersects at a composition in the range of 25%-30% of TiAP in dodecane, which is very much closer to the TBP/n-dodecane composition used in the PUREX process. The excess volume of mixing was found to be positive for the entire range of mole fraction and the excess enthalpy of mixing was shown to be endothermic for the TBP/n-dodecane mixture as well as TiAP/n-dodecane mixture as reported experimentally. The spatial pair correlation functions are evaluated between TiAP-TiAP and TiAP-dodecane molecules. Further, shear viscosity has been computed by performing the non-equilibrium molecular dynamics employing the periodic perturbation method. The calculated shear viscosity of the binary mixture is found to be in excellent agreement with the experimental values. The use of the newly calibrated OPLS force field embedding Mulliken charges is shown to be equally reliable in predicting the structural and dynamical properties for the mixture without incorporating any arbitrary scaling in the force field or Lennard-Jones parameters. Further, the present MD simulation results demonstrate that the Stokes-Einstein relation breaks down at the molecular level. The present methodology might be adopted to evaluate the liquid state properties of an aqueous-organic biphasic system, which is of great significance in the interfacial science and technology.

Molecular dynamics simulation for the test of calibrated OPLS-AA force field for binary liquid mixture of tri-iso-amyl phosphate and n-dodecane

NASA Astrophysics Data System (ADS)

Das, Arya; Ali, Sk. Musharaf

2018-02-01

Tri-isoamyl phosphate (TiAP) has been proposed to be an alternative for tri-butyl phosphate (TBP) in the Plutonium Uranium Extraction (PUREX) process. Recently, we have successfully calibrated and tested all-atom optimized potentials for liquid simulations using Mulliken partial charges for pure TiAP, TBP, and dodecane by performing molecular dynamics (MD) simulation. It is of immense importance to extend this potential for the various molecular properties of TiAP and TiAP/n-dodecane binary mixtures using MD simulation. Earlier, efforts were devoted to find out a suitable force field which can explain both structural and dynamical properties by empirical parameterization. Therefore, the present MD study reports the structural, dynamical, and thermodynamical properties with different mole fractions of TiAP-dodecane mixtures at the entire range of mole fraction of 0-1 employing our calibrated Mulliken embedded optimized potentials for liquid simulation (OPLS) force field. The calculated electric dipole moment of TiAP was seen to be almost unaffected by the TiAP concentration in the dodecane diluent. The calculated liquid densities of the TiAP-dodecane mixture are in good agreement with the experimental data. The mixture densities at different temperatures are also studied which was found to be reduced with temperature as expected. The plot of diffusivities for TiAP and dodecane against mole fraction in the binary mixture intersects at a composition in the range of 25%-30% of TiAP in dodecane, which is very much closer to the TBP/n-dodecane composition used in the PUREX process. The excess volume of mixing was found to be positive for the entire range of mole fraction and the excess enthalpy of mixing was shown to be endothermic for the TBP/n-dodecane mixture as well as TiAP/n-dodecane mixture as reported experimentally. The spatial pair correlation functions are evaluated between TiAP-TiAP and TiAP-dodecane molecules. Further, shear viscosity has been computed by performing the non-equilibrium molecular dynamics employing the periodic perturbation method. The calculated shear viscosity of the binary mixture is found to be in excellent agreement with the experimental values. The use of the newly calibrated OPLS force field embedding Mulliken charges is shown to be equally reliable in predicting the structural and dynamical properties for the mixture without incorporating any arbitrary scaling in the force field or Lennard-Jones parameters. Further, the present MD simulation results demonstrate that the Stokes-Einstein relation breaks down at the molecular level. The present methodology might be adopted to evaluate the liquid state properties of an aqueous-organic biphasic system, which is of great significance in the interfacial science and technology.

Remobilization of Phytol from Chlorophyll Degradation Is Essential for Tocopherol Synthesis and Growth of Arabidopsis

PubMed Central

vom Dorp, Katharina; Hölzl, Georg; Plohmann, Christian; Eisenhut, Marion; Abraham, Marion

2015-01-01

Phytol from chlorophyll degradation can be phosphorylated to phytyl-phosphate and phytyl-diphosphate, the substrate for tocopherol (vitamin E) synthesis. A candidate for the phytyl-phosphate kinase from Arabidopsis thaliana (At1g78620) was identified via a phylogeny-based approach. This gene was designated VITAMIN E DEFICIENT6 (VTE6) because the leaves of the Arabidopsis vte6 mutants are tocopherol deficient. The vte6 mutant plants are incapable of photoautotrophic growth. Phytol and phytyl-phosphate accumulate, and the phytyl-diphosphate content is strongly decreased in vte6 leaves. Phytol feeding and enzyme assays with Arabidopsis and recombinant Escherichia coli cells demonstrated that VTE6 has phytyl-P kinase activity. Overexpression of VTE6 resulted in increased phytyl-diphosphate and tocopherol contents in seeds, indicating that VTE6 encodes phytyl-phosphate kinase. The severe growth retardation of vte6 mutants was partially rescued by introducing the phytol kinase mutation vte5. Double mutant plants (vte5 vte6) are tocopherol deficient and contain more chlorophyll, but reduced amounts of phytol and phytyl-phosphate compared with vte6 mutants, suggesting that phytol or phytyl-phosphate are detrimental to plant growth. Therefore, VTE6 represents the missing phytyl-phosphate kinase, linking phytol release from chlorophyll with tocopherol synthesis. Moreover, tocopherol synthesis in leaves depends on phytol derived from chlorophyll, not on de novo synthesis of phytyl-diphosphate from geranylgeranyl-diphosphate. PMID:26452599

Poly(trimethylene carbonate)-based composite materials for reconstruction of critical-sized cranial bone defects in sheep.

PubMed

Zeng, Ni; van Leeuwen, Anne C; Grijpma, Dirk W; Bos, Ruud R M; Kuijer, Roel

2017-02-01

The use of ceramic materials in repair of bone defects is limited to non-load-bearing sites. We tested poly(trimethylene carbonate) (PTMC) combined with β-tricalcium phosphate or biphasic calcium phosphate particles for reconstruction of cranial defects. PTMC-calcium phosphate composite matrices were implanted in cranial defects in sheep for 3 and 9 months. Micro-computed tomography quantification and histological observation were performed for analysis. No differences were found in new bone formation among the defects left unfilled, filled with PTMC scaffolds, or filled with either kind of PTMC-calcium phosphate composite scaffolds. Porous β-TCP scaffolds as control led to a larger amount of newly formed bone in the defects than all other materials. Histology revealed abundant new bone formation in the defects filled with porous β-TCP scaffolds. New bone formation was limited in defects filled with PTMC scaffolds or different PTMC-calcium phosphate matrices. PTMC matrices were degraded uneventfully. New bone formation within the defects followed an orderly pattern. PTMC did not interfere with bone regeneration in sheep cranial defects and is suitable as a polymer matrix for incorporating calcium phosphate particles. Increasing the content of calcium phosphate particles in the composite matrices may enhance the beneficial effects of the particles on new bone formation. Copyright © 2016 European Association for Cranio-Maxillo-Facial Surgery. Published by Elsevier Ltd. All rights reserved.

Effects of Nano-Aluminum Nitride on the Performance of an Ultrahigh-Temperature Inorganic Phosphate Adhesive Cured at Room Temperature

PubMed Central

Ma, Chengkun; Chen, Hailong; Wang, Chao; Zhang, Jifeng; Qi, Hui; Zhou, Limin

2017-01-01

Based on the optimal proportion of resin and curing agent, an ultrahigh-temperature inorganic phosphate adhesive was prepared with aluminum dihydric phosphate, aluminium oxide (α-Al2O3), etc. and cured at room temperature (RT). Then, nano-aluminum nitride (nano-AlN), nano-Cupric oxide (nano-CuO), and nano-titanium oxide (nano-TiO2) were added into the adhesive. Differential scanning calorimetry was conducted using the inorganic phosphate adhesive to analyze the phosphate reactions during heat treatment, and it was found that 15 wt % nano-AlN could clearly decrease the curing temperature. Scanning electron microscopy was used to observe the microphenomenon of the modified adhesive at ultrahigh-temperature. The differential thermal analysis of the inorganic phosphate adhesive showed that the weight loss was approximately 6.5 wt % when the mass ratio of resin to curing agent was 1:1.5. An X-ray diffraction analysis of the adhesive with 10% nano-AlN showed that the phase structure changed from AlPO4(11-0500) to the more stable AlPO4(10-0423) structure after heat treatment. The shear strength of the adhesive containing 10% nano-AlN reached 7.3 MPa at RT due to the addition of nano-AlN, which promoted the formation of phosphate and increased the Al3+. PMID:29099812

Fast and Sustained Degradation of Chemical Warfare Agent Simulants Using Flexible Self-Supported Metal-Organic Framework Filters.

PubMed

Liang, Huixin; Yao, Aonan; Jiao, Xiuling; Li, Cheng; Chen, Dairong

2018-06-20

Self-detoxification filters against lethal chemical warfare agents (CWAs) are highly desirable for the protection of human beings and the environment. In this report, flexible self-supported filters of a series of Zr(IV)-based metal-organic frameworks (MOFs) including UiO-66, UiO-67, and UiO-66-NH 2 were successfully prepared and exhibited fast and sustained degradation of CWA simulants. A half-life as short as 2.4 min was obtained for the catalytic hydrolysis of dimethyl 4-nitrophenyl phosphate, and the percent conversion remained above 90% over a long-term exposure of 120 min, well exceeding those of the previously reported composite MOF filters and the corresponding MOF powders. The outstanding detoxification performance of the self-supported fibrous filter comes from the exceptionally high surface area, excellent pore accessibility, and hierarchical structure from the nano- to macroscale. This work demonstrates, for the first time, MOF-only filters as efficient self-detoxification media, which will offer new opportunities for the design and fabrication of functional materials for toxic chemical protection.

Conformational Flexibility of Human Casein Kinase Catalytic Subunit Explored by Metadynamics

PubMed Central

Gouron, Aurélie; Milet, Anne; Jamet, Helene

2014-01-01

Casein kinase CK2 is an essential enzyme in higher organisms, catalyzing the transfer of the γ phosphate from ATP to serine and threonine residues on protein substrates. In a number of animal tumors, CK2 activity has been shown to escape normal cellular control, making it a potential target for cancer therapy. Several crystal structures of human CK2 have been published with different conformations for the CK2α catalytic subunit. This variability reflects a high flexibility for two regions of CK2α: the interdomain hinge region, and the glycine-rich loop (p-loop). Here, we present a computational study simulating the equilibrium between three conformations involving these regions. Simulations were performed using well-tempered metadynamics combined with a path collective variables approach. This provides a reference pathway describing the conformational changes being studied, based on analysis of free energy surfaces. The free energies of the three conformations were found to be close and the paths proposed had low activation barriers. Our results indicate that these conformations can exist in water. This information should be useful when designing inhibitors specific to one conformation. PMID:24606937

Phosphate removal by refined aspen wood fiber treated with carboxymethyl cellulose and ferrous chloride

Treesearch

Thomas L. Eberhardt; Soo-Hong Min; James S. Han

2006-01-01

Biomass-based filtration media are of interest as an economical means to remove pollutants and nutrients found in stormwater runoff. Refined aspen wood fiber samples treated with iron salt solutions demonstrated limited capacities to remove (ortho)phosphate from test solutions. To provide additional sites for iron complex formation, and thereby impart a greater...

Chemical Speciation Analysis of Sports Drinks by Acid-Base Titrimetry and Ion Chromatography: A Challenging Beverage Formulation Project

ERIC Educational Resources Information Center

Drossman, Howard

2007-01-01

Students have standardized a sodium hydroxide solution and analyzed commercially available sports drinks by titrimetric analysis of the triprotic citric acid, dihydrogen phosphate, and dihydrogen citrate and by ion chromatography for chloride, total phosphate and citrate. These experiments are interesting examples of analyzing real-world food and…

Cone calorimeter evaluation of two flame retardant cotton fabrics

Treesearch

Robert H. White; Sunghyun Nam; Dharnidhar V. Parikh

2012-01-01

Unbleached (gray) cotton needle-punched nonwoven (NW) fabrics with 12.5% polypropylene scrim were treated with two phosphate–nitrogen-based flame retardant (FR) formulations, Southern Regional Research Center (SRRC)-1 and SRRC-2. The SRRC-1 formulation contains diammonium phosphate as the FR chemical along with urea and dimethyloldihydroxyethyleneurea. Because a trace...

Multifunctional cerium-based nanomaterials and methods for producing the same

DOEpatents

O'Keefe, Matthew J.; Castano Londono, Carlos E.; Fahrenholtz, William G.

2018-01-09

Embodiments relate to a cerium-containing nano-coating composition, the composition including an amorphous matrix including one or more of cerium oxide, cerium hydroxide, and cerium phosphate; and crystalline regions including one or more of crystalline cerium oxide, crystalline cerium hydroxide, and crystalline cerium phosphate. The diameter of each crystalline region is less than about 50 nanometers.

Novel insights into structure–function mechanism and tissue-specific expression profiling of full-length dxr gene from Cymbopogon winterianus

PubMed Central

Devi, Kamalakshi; Dehury, Budheswar; Phukon, Munmi; Modi, Mahendra Kumar; Sen, Priyabrata

2015-01-01

The 1-deoxy-d-xylulose-5-phosphate reductoisomerase (DXR; EC1.1.1.267), an NADPH-dependent reductase, plays a pivotal role in the methylerythritol 4-phosphate pathway (MEP), in the conversion of 1-deoxy-d-xylulose-5-phosphate (DXP) into MEP. The sheath and leaf of citronella (Cymbopogon winterianus) accumulates large amount of terpenes and sesquiterpenes with proven medicinal value and economic uses. Thus, sequencing of full length dxr gene and its characterization seems to be a valuable resource in metabolic engineering to alter the flux of isoprenoid active ingredients in plants. In this study, full length DXR from citronella was characterized through in silico and tissue-specific expression studies to explain its structure–function mechanism, mode of cofactor recognition and differential expression. The modelled DXR has a three-domain architecture and its active site comprised of a cofactor (NADPH) binding pocket and the substrate-binding pocket. Molecular dynamics simulation studies indicated that DXR model retained most of its secondary structure during 10 ns simulation in aqueous solution. The modelled DXR superimposes well with its closest structural homolog but subtle variations in the charge distribution over the cofactor recognition site were noticed. Molecular docking study revealed critical residues aiding tight anchoring NADPH within the active pocket of DXR. Tissue-specific differential expression analysis using semi-quantitative RT-PCR and qRT-PCR in various tissues of citronella plant revealed distinct differential expression of DXR. To our knowledge, this is the first ever report on DXR from the important medicinal plant citronella and further characterization of this gene will open up better avenues for metabolic engineering of secondary metabolite pathway genes from medicinal plants in the near future. PMID:25941629

Mobility of rare earth elements, yttrium and scandium from a phosphogypsum stack: Environmental and economic implications.

PubMed

Cánovas, Carlos Ruiz; Macías, Francisco; Pérez López, Rafael; Nieto, José Miguel

2018-03-15

This paper investigates the mobility and fluxes of REE, Y and Sc under weathering conditions from an anomalously metal-rich phosphogypsum stack in SW Spain. The interactions of the phosphogypsum stack with rainfall and organic matter-rich solutions, simulating the weathering processes observed due to its location on salt-marshes, were simulated by leaching tests (e.g. EN 12457-2 and TCLP). Despite the high concentration of REE, Y and Sc contained in the phosphogypsum stack, their mobility during the leaching tests was very low; <0.66% and 1.8% of the total content of these elements were released during both tests. Chemical and mineralogical evidences suggest that phosphate minerals may act as sources of REE and Y in the phosphogypsum stack while fluoride minerals may act as sinks, controlling their mobility. REE fractionation processes were identified in the phosphogypsum stack; a depletion of LREE in the saturated zone was identified due probably to the dissolution of secondary LREE phosphates previously formed during apatite dissolution in the industrial process. Thus, the vadose zone of the stack would preserve the original REE signature of phosphate rocks. On the other hand, an enrichment of MREE in relation to HREE of edge outflows is observed due to the higher influence of estuarine waters on the leaching process of the phosphogypsum stack. Despite the low mobility of REE, Y and Sc in the phosphogypsum, around 104kg/yr of REE and 40kg/yr of Y and Sc are released from the stack to the estuary, which may imply an environmental concern. The information obtained in this study could be used to optimize extraction methods aimed to recover REE, Y and Sc from phosphogypsum, mitigating the pollution to the environment. Copyright © 2017 Elsevier B.V. All rights reserved.

Phosphate sorption and desorption on pyrite in primitive aqueous scenarios: relevance of acidic --> alkaline transitions.

PubMed

de Souza-Barros, Fernando; Braz-Levigard, Raphael; Ching-San, Yonder; Monte, Marisa M B; Bonapace, José A P; Montezano, Viviane; Vieyra, Adalberto

2007-02-01

Phosphate (P(i)) sorption assays onto pyrite in media simulating primeval aquatic scenarios affected by hydrothermal emissions, reveal that acidic conditions favour P(i) sorption whereas mild alkaline media--as well as those simulating sulfur oxidation to SO(2-) (4)--revert this capture process. Several mechanisms relevant to P(i) availability in prebiotic eras are implicated in the modulation of these processes. Those favouring sorption are: (a) hydrophobic coating of molecules, such as acetate that could be formed in the vicinity of hydrothermal vents; (b) water and Mg(2+) bridging in the interface mineral-aqueous media; (c) surface charge neutralization by monovalent cations (Na+ and K+). The increase of both the medium pH and the SO(2-) (4) trapping by the mineral interface would provoke the release of sorbed P(i) due to charge polarization. Moreover it is shown that P(i) self-modulates its sorption, a mechanism that depends on the abundance of SO(2-) (4) in the interface. The relevance of the proposed mechanisms of P(i) capture, release and trapping arises from the need of abundant presence of this molecule for primitive phosphorylations, since--similarly to contemporary aqueous media--inorganic phosphate concentrations in primitive seas should have been low. It is proposed that the presence of sulphide minerals with high affinity to P(i) could have trapped this molecule in an efficient manner, allowing its concentration in specific niches. In these niches, the conditions studied in the present work would have been relevant for its availability in soluble form, specially in primitive insulated systems with pH gradients across the wall.

The Effect of Calcium Phosphate Particle Shape and Size on their Antibacterial and Osteogenic Activity in the Delivery of Antibiotics in vitro

PubMed Central

Uskoković, Vuk; Batarni, Samir Shariff; Schweicher, Julien; King, Andrew; Desai, Tejal A.

2013-01-01

Powders composed of four morphologically different calcium phosphate particles were prepared by precipitation from aqueous solutions: flaky, brick-like, elongated orthogonal, and spherical. The particles were then loaded with either clindamycin phosphate as the antibiotic of choice, or fluorescein, a model molecule used to assess the drug release properties. A comparison was carried out of the comparative effect of such antibiotic-releasing materials on: sustained drug release profiles; Staphylococcus aureus growth inhibition; and osteogenic propensities in vitro. Raman spectroscopic analysis indicated the presence of various calcium phosphate phases, including monetite (flaky and elongated orthogonal particles), octacalcium phosphate (brick-shaped particles) and hydroxyapatite (spherical particles). Testing the antibiotic-loaded calcium phosphate powders for bacterial growth inhibition demonstrated satisfying antibacterial properties both in broths and on agar plates. All four calcium-phosphate-fluorescein powders exhibited sustained drug release over 21 days. The calcium phosphate sample with the highest specific surface area and the smallest, spherical particle size was the most effective in both drug loading and release, consequently having the highest antibacterial efficiency. Moreover, the highest cell viability, the largest gene expression upregulation of three different osteogenic markers – osteocalcin, osteopontin and Runx2 - as well as the least disrupted cell cytoskeleton and cell morphologies were also noticed for the calcium phosphate powder composed of smallest, spherical nanosized particles. Still, all four powders exerted a viable effect on osteoblastic MC3T3-E1 cells in vitro, as evidenced by both morphological assessments on fluorescently stained cells and measurements of their mitochondrial activity. The obtained results suggest that the nanoscale particle size and the corresponding coarseness of the surface of particle conglomerates as the cell attachment points may present a favorable starting point for the development of calcium-phosphate-based osteogenic drug delivery devices. PMID:23484624

Structure of L-Xylulose-5-Phosphate 3-Epimerase (UlaE) from the Anaerobic L-Ascorbate Utilization Pathway of Escherichia coli: Identification of a Novel Phosphate Binding Motif within a TIM Barrel Fold

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Rong; Pineda, Marco; Ajamian, Eunice

2009-01-15

Three catabolic enzymes, UlaD, UlaE, and UlaF, are involved in a pathway leading to fermentation of L-ascorbate under anaerobic conditions. UlaD catalyzes a {beta}-keto acid decarboxylation reaction to produce L-xylulose-5-phosphate, which undergoes successive epimerization reactions with UlaE (L-xylulose-5-phosphate 3-epimerase) and UlaF (L-ribulose-5-phosphate 4-epimerase), yielding D-xylulose-5-phosphate, an intermediate in the pentose phosphate pathway. We describe here crystallographic studies of UlaE from Escherichia coli O157:H7 that complete the structural characterization of this pathway. UlaE has a triosephosphate isomerase (TIM) barrel fold and forms dimers. The active site is located at the C-terminal ends of the parallel {beta}-strands. The enzyme binds Zn{sup 2+},more » which is coordinated by Glu155, Asp185, His211, and Glu251. We identified a phosphate-binding site formed by residues from the {beta}1/{alpha}1 loop and {alpha}3' helix in the N-terminal region. This site differs from the well-characterized phosphate-binding motif found in several TIM barrel superfamilies that is located at strands {beta}7 and {beta}8. The intrinsic flexibility of the active site region is reflected by two different conformations of loops forming part of the substrate-binding site. Based on computational docking of the L-xylulose 5-phosphate substrate to UlaE and structural similarities of the active site of this enzyme to the active sites of other epimerases, a metal-dependent epimerization mechanism for UlaE is proposed, and Glu155 and Glu251 are implicated as catalytic residues. Mutation and activity measurements for structurally equivalent residues in related epimerases supported this mechanistic proposal.« less

Design and Synthesis of Phosphotyrosine Peptidomimetic Prodrugs

PubMed Central

Garrido-Hernandez, Hugo; Moon, Kyung D.; Geahlen, Robert L.; Borch, Richard F.

2008-01-01

A novel approach to the intracellular delivery of aryl phosphates has been developed that utilizes a phosphoramidate-based prodrug approach. The prodrugs contain an ester group that undergoes reductive activation intracellularly with concomitant expulsion of a phosphoramidate anion. This anion undergoes intramolecular cyclization and hydrolysis to generate aryl phosphate exclusively with a t1/2 = ∼ 20 min. Phosphoramidate prodrugs (8-10) of phosphate-containing peptidomimetics that target the SH2 domain were synthesized. Evaluation of these peptidomimetic prodrugs in a growth inhibition assay and, in a cell-based transcriptional assay, demonstrated that the prodrugs had IC50 values in the low micromolar range. Synthesis of phosphorodiamidate analogs containing a P-NH-Ar linker (16 – 18) was also carried out in the hope that the phosphoramidates released might be phosphatase-resistant. Comparable activation rates and cell-based activities were observed for these prodrugs, but the intermediate phosphoramidate dianion underwent spontaneous hydrolysis with a t1/2 = ∼ 30 min. PMID:16722656

Magnetic hyperthermia in water based ferrofluids: Effects of initial susceptibility and size polydispersity on heating efficiency

NASA Astrophysics Data System (ADS)

Lahiri, B. B.; Ranoo, Surojit; Muthukumaran, T.; Philip, John

2018-04-01

The effects of initial susceptibility and size polydispersity on magnetic hyperthermia efficiency in two water based ferrofluids containing phosphate and TMAOH coated superparamagnetic Fe3O4 nanoparticles were studied. Experiments were performed at a fixed frequency of 126 kHz on four different concentrations of both samples and under different external field amplitudes. It was observed that for field amplitudes beyond 45.0 kAm-1, the maximum temperature rise was in the vicinity of 42°C (hyperthermia limit) which indicated the suitability of the water based ferrofluids for hyperthermia applications. The maximum temperature rise and specific absorption rate were found to vary linearly with square of the applied field amplitudes, in accordance with theoretical predictions. It was further observed that for a fixed sample concentration, specific absorption rate was higher for the phosphate coated samples which was attributed to the higher initial static susceptibility and lower size polydispersity of phosphate coated Fe3O4.

Improved degradation and bioactivity of amorphous aerosol derived tricalcium phosphate nanoparticles in poly(lactide-co-glycolide)

NASA Astrophysics Data System (ADS)

Loher, Stefan; Reboul, Valentine; Brunner, Tobias J.; Simonet, Marc; Dora, Claudio; Neuenschwander, Peter; Stark, Wendelin J.

2006-04-01

The industrially used flame synthesis of silica polymer fillers was extended to amorphous tricalcium phosphate (a-TCP) nanoparticles and resulted in a similar morphology as the traditionally used polymer fillers. Doping of poly(lactide-co-glycolide) (PLGA) with such highly agglomerated a-TCP was investigated for mechanical properties, increased in vitro biodegradation and the formation of a hydroxyapatite layer on the surface of the nanocomposite. PLGA films with particle loadings ranging from 0 to 30 wt% were prepared by solvent casting. Degradation in simulated body fluid (SBF) at 37 °C under sterile conditions for up to 42 days was followed by Raman spectroscopy, scanning electron microscopy (SEM), thermal analysis and tensile tests. The presence of nanoparticles in the PLGA matrix slightly increased the Young's modulus up to 30% compared to pure polymer reference materials. The nanoparticle doped films showed a significantly increased loss of polymer mass during degradation. Scanning electron microscopy images of doped films showed that the SBF degraded the PLGA by corrosion as facilitated by the incorporation of nanoparticulate calcium phosphate. Raman spectroscopy revealed that the deposition of about 10 nm sized hydroxyapatite crystallites on the surface of doped PLGA films was strongly increased by the addition of tricalcium phosphate fillers. The combination of increased hydroxyapatite formation and enhanced polymer degradation may suggest the use of such amorphous, aerosol derived a-TCP fillers for applications in non-load-bearing implant sites.

Removal of lead contaminated dusts from hard surfaces.

PubMed

Lewis, Roger D; Condoor, Sridhar; Batek, Joe; Ong, Kee Hean; Backer, Denis; Sterling, David; Siria, Jeff; Chen, John J; Ashley, Peter

2006-01-15

Government guidelines have widely recommended trisodium phosphate (TSP) or "lead-specific" cleaning detergents for removal of lead-contaminated dust (LCD) from hard surfaces, such as floors and window areas. The purpose of this study was to determine if low-phosphate, non-lead-specific cleaners could be used to efficiently remove LCD from 3 types of surfaces (vinyl flooring, wood, and wallpaper). Laboratory methods were developed and validated for simulating the doping, embedding, and sponge cleaning of the 3 surface types with 4 categories of cleaners: lead-specific detergents, nonionic cleaners, anionic cleaners, and trisodium phosphate (TSP). Vinyl flooring and wood were worn using artificial means. Materials were ashed, followed by ultrasound extraction, and anodic stripping voltammetry (ASV). One-way analysis of variance approach was used to evaluate the surface and detergent effects. Surface type was found to be a significant factor in removal of lead (p < 0.001). Vinyl flooring cleaned better than wallpaper by over 14% and wood cleaned better than wallpaper by 13%. There was no difference between the cleaning action of vinyl flooring and wood. No evidence was found to support the use of TSP or lead-specific detergents over all-purpose cleaning detergents for removal of lead-contaminated dusts. No-phosphate, non-lead-specific detergents are effective in sponge cleaning of lead-contaminated hard surfaces and childhood lead prevention programs should consider recommending all-purpose household detergents for removal of lead-contaminated dust after appropriate vacuuming.

New perspectives for the design of sustainable bioprocesses for phosphorus recovery from waste.

PubMed

Tarayre, Cédric; De Clercq, Lies; Charlier, Raphaëlle; Michels, Evi; Meers, Erik; Camargo-Valero, Miller; Delvigne, Frank

2016-04-01

Phosphate rock has long been used for the production of phosphorus based chemicals. However, considering the depletion of the reservoirs and the decrease of the quality of phosphate rocks, a potential market is now emerging for the recovery of phosphate from waste and its reuse for different applications. Notably, phosphate recovery from wastewater could be included in a circular economy approach. This review focuses on the use of microbial systems for phosphorus accumulation and recovery, by considering the actual range of analytical techniques available for the monitoring of phosphorus accumulating organisms, as well as the actual biochemical and metabolic engineering toolbox available for the optimization of bioprocesses. In this context, knowledge gathered from process, system and synthetic biology could potentially lead to innovative process design. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hypophosphatemic rickets: Revealing Novel Control Points for Phosphate Homeostasis

PubMed Central

White, Kenneth E.; Hum, Julia M.; Econs, Michael J.

2014-01-01

Rapid and somewhat surprising advances have recently been made towards understanding the molecular mechanisms causing heritable disorders of hypophosphatemia. The results of clinical, genetic, and translational studies have interwoven novel concepts underlying the endocrine control of phosphate metabolism, with far-reaching implications for treatment of both rare, Mendelian diseases as well as common disorders of blood phosphate excess such as chronic kidney disease (CKD). In particular, diseases caused by changes in the expression and proteolytic control of the phosphaturic hormone Fibroblast growth factor-23 (FGF23) have come to the forefront in terms of directing new models explaining mineral metabolism. These hypophosphatemic disorders, as well as others resulting from independent defects in phosphate transport or metabolism, will be reviewed herein, and implications for emerging therapeutic strategies based upon these new findings will be discussed. PMID:24980542

Nature-Inspired Design of Artificial Solar-to-Fuel Conversion Systems based on Copper Phosphate Microflowers.

PubMed

Wang, Jing; Zhu, Ting; Ho, Ghim Wei

2016-07-07

Phosphates play significant roles in plant photosynthesis by mediating electron transportation and furnishing energy for CO2 reduction. Motivated by this, we demonstrate herein an artificial solar-to-fuel conversion system, involving versatile copper phosphate microflowers as template and titanium dioxide nanoparticles as host photocatalyst. The elaborate flowerlike architectures, coupled with a unique proton-reduction cycle from interchangeability of different species of orthophosphate ions, not only offer a 2D nanosheet platform for an optimal heterostructure interface but also effectively augment charge-carrier transfer, thereby contributing to enhanced photoactivity and hydrogen generation. These nature-inspired, phosphate-derived nanocomposites advance the synthesis of a large variety of functional materials, which holds great potential for photochemical, photoelectric and catalytic applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conversion of D-ribulose 5-phosphate to D-xylulose 5-phosphate : new insights from structural and biochemical studies on human RPE.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, W.; Ouyang, S.; Shaw, N.

2011-02-01

The pentose phosphate pathway (PPP) confers protection against oxidative stress by supplying NADPH necessary for the regeneration of glutathione, which detoxifies H{sub 2}O{sub 2} into H{sub 2}O and O{sub 2}. RPE functions in the PPP, catalyzing the reversible conversion of D-ribulose 5-phosphate to D-xylulose 5-phosphate and is an important enzyme for cellular response against oxidative stress. Here, using structural, biochemical, and functional studies, we show that human D-ribulose 5-phosphate 3-epimerase (hRPE) uses Fe{sup 2+} for catalysis. Structures of the binary complexes of hRPE with D-ribulose 5-phosphate and D-xylulose 5-phosphate provide the first detailed molecular insights into the binding mode ofmore » physiological ligands and reveal an octahedrally coordinated Fe{sup 2+} ion buried deep inside the active site. Human RPE folds into a typical ({beta}/{alpha}){sub 8} triosephosphate isomerase (TIM) barrel with a loop regulating access to the active site. Two aspartic acids are well positioned to carry out the proton transfers in an acid-base type of reaction mechanism. Interestingly, mutating Ser-10 to alanine almost abolished the enzymatic activity, while L12A and M72A mutations resulted in an almost 50% decrease in the activity. The binary complexes of hRPE reported here will aid in the design of small molecules for modulating the activity of the enzyme and altering flux through the PPP.« less

Acute Phosphate Restriction Leads to Impaired Fracture Healing and Resistance to BMP-2

PubMed Central

Wigner, Nathan A; Luderer, Hilary F; Cox, Megan K; Sooy, Karen; Gerstenfeld, Louis C; Demay, Marie B

2010-01-01

Hypophosphatemia leads to rickets and osteomalacia, the latter of which results in decreased biomechanical integrity of bones, accompanied by poor fracture healing. Impaired phosphate-dependent apoptosis of hypertrophic chondrocytes is the molecular basis for rickets. However, the underlying pathophysiology of impaired fracture healing has not been characterized previously. To address the role of phosphate in fracture repair, mice were placed on a phosphate-restricted diet 2 days prior to or 3 days after induction of a mid-diaphyseal femoral fracture to assess the effects of phosphate deficiency on the initial recruitment of mesenchymal stem cells and their subsequent differentiation. Histologic and micro-computed tomographic (µCT) analyses demonstrated that both phosphate restriction models dramatically impaired fracture healing primarily owing to a defect in differentiation along the chondrogenic lineage. Based on Sox9 and Sox5 mRNA levels, neither the initial recruitment of cells to the callus nor their lineage commitment was effected by hypophosphatemia. However, differentiation of these cells was impaired in association with impaired bone morphogenetic protein (BMP) signaling. In vivo ectopic bone-formation assays and in vitro investigations in ST2 stromal cells confirmed that phosphate restriction leads to BMP-2 resistance. Marrow ablation studies demonstrate that hypophosphatemia has different effects on injury-induced intramembranous bone formation compared with endochondral bone formation. Thus phosphate plays an important role in the skeleton that extends beyond mineralized matrix formation and growth plate maturation and is critical for endochondral bone repair. © 2010 American Society for Bone and Mineral Research. PMID:19839770

Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

PubMed

Jaisi, Deb P; Li, Hui; Wallace, Adam F; Paudel, Prajwal; Sun, Mingjing; Balakrishna, Avula; Lerch, Robert N

2016-11-16

Degradation of glyphosate in the presence of manganese oxide and UV light was analyzed using phosphate oxygen isotope ratios and density function theory (DFT). The preference of C-P or C-N bond cleavage was found to vary with changing glyphosate/manganese oxide ratios, indicating the potential role of sorption-induced conformational changes on the composition of intermediate degradation products. Isotope data confirmed that one oxygen atom derived solely from water was incorporated into the released phosphate during glyphosate degradation, and this might suggest similar nucleophilic substitution at P centers and C-P bond cleavage both in manganese oxide- and UV light-mediated degradation. The DFT results reveal that the C-P bond could be cleaved by water, OH - or • OH, with the energy barrier opposing bond dissociation being lowest in the presence of the radical species, and that C-N bond cleavage is favored by the formation of both nitrogen- and carbon-centered radicals. Overall, these results highlight the factors controlling the dominance of C-P or C-N bond cleavage that determines the composition of intermediate/final products and ultimately the degradation pathway.

Computational Assessment of Potassium and Magnesium Ion Binding to a Buried Pocket in GTPase-Associating Center RNA

PubMed Central

2016-01-01

An experimentally well-studied model of RNA tertiary structures is a 58mer rRNA fragment, known as GTPase-associating center (GAC) RNA, in which a highly negative pocket walled by phosphate oxygen atoms is stabilized by a chelated cation. Although such deep pockets with more than one direct phosphate to ion chelation site normally include magnesium, as shown in one GAC crystal structure, another GAC crystal structure and solution experiments suggest potassium at this site. Both crystal structures also depict two magnesium ions directly bound to the phosphate groups comprising this controversial pocket. Here, we used classical molecular dynamics simulations as well as umbrella sampling to investigate the possibility of binding of potassium versus magnesium inside the pocket and to better characterize the chelation of one of the binding magnesium ions outside the pocket. The results support the preference of the pocket to accommodate potassium rather than magnesium and suggest that one of the closely binding magnesium ions can only bind at high magnesium concentrations, such as might be present during crystallization. This work illustrates the complementary utility of molecular modeling approaches with atomic-level detail in resolving discrepancies between conflicting experimental results. PMID:27983843

Computational Assessment of Potassium and Magnesium Ion Binding to a Buried Pocket in GTPase-Associating Center RNA.

PubMed

Hayatshahi, Hamed S; Roe, Daniel R; Galindo-Murillo, Rodrigo; Hall, Kathleen B; Cheatham, Thomas E

2017-01-26

An experimentally well-studied model of RNA tertiary structures is a 58mer rRNA fragment, known as GTPase-associating center (GAC) RNA, in which a highly negative pocket walled by phosphate oxygen atoms is stabilized by a chelated cation. Although such deep pockets with more than one direct phosphate to ion chelation site normally include magnesium, as shown in one GAC crystal structure, another GAC crystal structure and solution experiments suggest potassium at this site. Both crystal structures also depict two magnesium ions directly bound to the phosphate groups comprising this controversial pocket. Here, we used classical molecular dynamics simulations as well as umbrella sampling to investigate the possibility of binding of potassium versus magnesium inside the pocket and to better characterize the chelation of one of the binding magnesium ions outside the pocket. The results support the preference of the pocket to accommodate potassium rather than magnesium and suggest that one of the closely binding magnesium ions can only bind at high magnesium concentrations, such as might be present during crystallization. This work illustrates the complementary utility of molecular modeling approaches with atomic-level detail in resolving discrepancies between conflicting experimental results.

Preliminary research on a novel bioactive silicon doped calcium phosphate coating on AZ31 magnesium alloy via electrodeposition.

PubMed

Qiu, Xun; Wan, Peng; Tan, Lili; Fan, Xinmin; Yang, Ke

2014-03-01

A silicon doped calcium phosphate coating was obtained successfully on AZ31 alloy substrate via pulse electrodeposition. A novel dual-layer structure was observed with a porous lamellar-like and outer block-like apatite layer. In vitro immersion tests were adopted in simulated body fluid within 28 days of immersion. Slow degradation rate obtained from weight loss was observed for the Si-doped Ca-P coating, which was also consistent with the results of electrochemical experiments showing an enhanced corrosion resistance for the coating. Further formation of an apatite-like layer on the surface after immersion proved better integrity and biomineralization performance of the coating. Biological characterization was carried out for viability, proliferation and differentiation of MG63 osteoblast-like cells. The coating showed a good cell growth and an enhanced cell proliferation. Moreover, an increased activity of osteogenic marker ALP was found. All the results demonstrated that the Si-doped calcium phosphate was perspective to be used as a coating for magnesium alloy implants to control the degradation rate and enhance the bioactivity, which would facilitate the rapidity of bone tissue repair. Copyright © 2013 Elsevier B.V. All rights reserved.

The adaptive buffered force QM/MM method in the CP2K and AMBER software packages

DOE PAGES

Mones, Letif; Jones, Andrew; Götz, Andreas W.; ...

2015-02-03

We present the implementation and validation of the adaptive buffered force (AdBF) quantum-mechanics/molecular-mechanics (QM/MM) method in two popular packages, CP2K and AMBER. The implementations build on the existing QM/MM functionality in each code, extending it to allow for redefinition of the QM and MM regions during the simulation and reducing QM-MM interface errors by discarding forces near the boundary according to the buffered force-mixing approach. New adaptive thermostats, needed by force-mixing methods, are also implemented. Different variants of the method are benchmarked by simulating the structure of bulk water, water autoprotolysis in the presence of zinc and dimethyl-phosphate hydrolysis usingmore » various semiempirical Hamiltonians and density functional theory as the QM model. It is shown that with suitable parameters, based on force convergence tests, the AdBF QM/MM scheme can provide an accurate approximation of the structure in the dynamical QM region matching the corresponding fully QM simulations, as well as reproducing the correct energetics in all cases. Adaptive unbuffered force-mixing and adaptive conventional QM/MM methods also provide reasonable results for some systems, but are more likely to suffer from instabilities and inaccuracies.« less

The adaptive buffered force QM/MM method in the CP2K and AMBER software packages

PubMed Central

Mones, Letif; Jones, Andrew; Götz, Andreas W; Laino, Teodoro; Walker, Ross C; Leimkuhler, Ben; Csányi, Gábor; Bernstein, Noam

2015-01-01

The implementation and validation of the adaptive buffered force (AdBF) quantum-mechanics/molecular-mechanics (QM/MM) method in two popular packages, CP2K and AMBER are presented. The implementations build on the existing QM/MM functionality in each code, extending it to allow for redefinition of the QM and MM regions during the simulation and reducing QM-MM interface errors by discarding forces near the boundary according to the buffered force-mixing approach. New adaptive thermostats, needed by force-mixing methods, are also implemented. Different variants of the method are benchmarked by simulating the structure of bulk water, water autoprotolysis in the presence of zinc and dimethyl-phosphate hydrolysis using various semiempirical Hamiltonians and density functional theory as the QM model. It is shown that with suitable parameters, based on force convergence tests, the AdBF QM/MM scheme can provide an accurate approximation of the structure in the dynamical QM region matching the corresponding fully QM simulations, as well as reproducing the correct energetics in all cases. Adaptive unbuffered force-mixing and adaptive conventional QM/MM methods also provide reasonable results for some systems, but are more likely to suffer from instabilities and inaccuracies. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. PMID:25649827

The adaptive buffered force QM/MM method in the CP2K and AMBER software packages

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mones, Letif; Jones, Andrew; Götz, Andreas W.

We present the implementation and validation of the adaptive buffered force (AdBF) quantum-mechanics/molecular-mechanics (QM/MM) method in two popular packages, CP2K and AMBER. The implementations build on the existing QM/MM functionality in each code, extending it to allow for redefinition of the QM and MM regions during the simulation and reducing QM-MM interface errors by discarding forces near the boundary according to the buffered force-mixing approach. New adaptive thermostats, needed by force-mixing methods, are also implemented. Different variants of the method are benchmarked by simulating the structure of bulk water, water autoprotolysis in the presence of zinc and dimethyl-phosphate hydrolysis usingmore » various semiempirical Hamiltonians and density functional theory as the QM model. It is shown that with suitable parameters, based on force convergence tests, the AdBF QM/MM scheme can provide an accurate approximation of the structure in the dynamical QM region matching the corresponding fully QM simulations, as well as reproducing the correct energetics in all cases. Adaptive unbuffered force-mixing and adaptive conventional QM/MM methods also provide reasonable results for some systems, but are more likely to suffer from instabilities and inaccuracies.« less

Geology and phosphate resources of the Hawley Creek area, Lemhi County, Idaho

USGS Publications Warehouse

Oberlindacher, Peter; Hovland, Robert David

1979-01-01

Phosphate resources occur within the Retort Phosphatic Shale Member of the Permian Phosphoria Formation in the Hawley Creek area, near Leadore, in east-central Idaho. About 12 square miles (31 km2 ) of the Retort Member and enclosing rocks were mapped at a scale of 1:12,000 to evaluate the leasable Federal mineral resources. The Retort has an average thickness of 73 feet (22.3 m) and 12.9 linear miles (20.8 linear km) of outcrop within the area mapped. Rock samples taken from a bulldozer trench were analyzed for phosphate content and for minor trace elements. Analyses show a cumulative thickness of 8.7 feet ( 2.7 m) of medium-grade phosphate rock ( 24 to 31 percent P2O5) and 33.4 feet (10.2 m) of low-grade phosphate rock (16 to 24 percent P2O5). Minor elements in the Retort include uranium, vanadium, fluorine, cadmium, chromium, nickel, molybdenum, silver, and rare earths. These minor elements are potential byproducts of any future phosphate production in the Hawley Creek area. In addition, analyses of six phosphate rock samples taken from a prospect trench show a cumulative thickness of 14.9 ft (4.5 m) at 17.6 percent P2O5. Indicated phosphate resources are calculated for phosphate beds under less than 600 feet (183.0 m) of overburden. Approximately 36.5 feet (11.1 m), representing 50 percent of the total Retort Member, were measured in trench CP-71. There are 80.42 million short tons (72.96 million metric tons) of medium-grade phosphate rock, and 308.76 million short tons ( 280.10 million metric tons) of low-grade phosphate rock in the Retort Member within the map area. Because the thickness and grade of the phosphate beds for each block are based on the recovered section from CP-71, the calculated phosphate resource estimates represent a minimum. Other mineral resources in the area are thorium (35 ppm) in a Precambrian (?) granite body located immediately west of the Hawley Creek area; oil and gas accumulations may occur beneath the Medicine Lodge thrust system in this part of the Beaverhead Mountains. Paleozoic, Mesozoic, and Cenozoic rocks are present in the Hawley Creek area. Fold axes and thrust faults have a dominant northwest trend. These thrusts and folds are probably associated with the northeast-oriented stress field that existed in Late Cretaceous time. Evidence of younger, high-angle normal and reverse faults in the area also exists.

In Vivo Predictive Dissolution: Comparing the Effect of Bicarbonate and Phosphate Buffer on the Dissolution of Weak Acids and Weak Bases.

PubMed

Krieg, Brian J; Taghavi, Seyed Mohammad; Amidon, Gordon L; Amidon, Gregory E

2015-09-01

Bicarbonate is the main buffer in the small intestine and it is well known that buffer properties such as pKa can affect the dissolution rate of ionizable drugs. However, bicarbonate buffer is complicated to work with experimentally. Finding a suitable substitute for bicarbonate buffer may provide a way to perform more physiologically relevant dissolution tests. The dissolution of weak acid and weak base drugs was conducted in bicarbonate and phosphate buffer using rotating disk dissolution methodology. Experimental results were compared with the predicted results using the film model approach of (Mooney K, Mintun M, Himmelstein K, Stella V. 1981. J Pharm Sci 70(1):22-32) based on equilibrium assumptions as well as a model accounting for the slow hydration reaction, CO2 + H2 O → H2 CO3 . Assuming carbonic acid is irreversible in the dehydration direction: CO2 + H2 O ← H2 CO3 , the transport analysis can accurately predict rotating disk dissolution of weak acid and weak base drugs in bicarbonate buffer. The predictions show that matching the dissolution of weak acid and weak base drugs in phosphate and bicarbonate buffer is possible. The phosphate buffer concentration necessary to match physiologically relevant bicarbonate buffer [e.g., 10.5 mM (HCO3 (-) ), pH = 6.5] is typically in the range of 1-25 mM and is very dependent upon drug solubility and pKa . © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Modeling the biogeochemical impact of atmospheric phosphate deposition from desert dust and combustion sources to the Mediterranean Sea

NASA Astrophysics Data System (ADS)

Richon, Camille; Dutay, Jean-Claude; Dulac, François; Wang, Rong; Balkanski, Yves

2018-04-01

Daily modeled fields of phosphate deposition to the Mediterranean from natural dust, anthropogenic combustion and wildfires were used to assess the effect of this external nutrient on marine biogeochemistry. The ocean model used is a high-resolution (1/12°) regional coupled dynamical-biogeochemical model of the Mediterranean Sea (NEMO-MED12/PISCES). The input fields of phosphorus are for 2005, which are the only available daily resolved deposition fields from the global atmospheric chemical transport model LMDz-INCA. Traditionally, dust has been suggested to be the main atmospheric source of phosphorus, but the LMDz-INCA model suggests that combustion is dominant over natural dust as an atmospheric source of phosphate (PO4, the bioavailable form of phosphorus in seawater) for the Mediterranean Sea. According to the atmospheric transport model, phosphate deposition from combustion (Pcomb) brings on average 40.5×10-6 mol PO4 m-2 yr-1 over the entire Mediterranean Sea for the year 2005 and is the primary source over the northern part (e.g., 101×10-6 mol PO4 m-2 yr-1 from combustion deposited in 2005 over the north Adriatic against 12.4×10-6 from dust). Lithogenic dust brings 17.2×10-6 mol PO4 m-2 yr-1 on average over the Mediterranean Sea in 2005 and is the primary source of atmospheric phosphate to the southern Mediterranean Basin in our simulations (e.g., 31.8×10-6 mol PO4 m-2 yr-1 from dust deposited in 2005 on average over the south Ionian basin against 12.4×10-6 from combustion). The evaluation of monthly averaged deposition flux variability of Pdust and Pcomb for the 1997-2012 period indicates that these conclusions may hold true for different years. We examine separately the two atmospheric phosphate sources and their respective flux variability and evaluate their impacts on marine surface biogeochemistry (phosphate concentration, chlorophyll a, primary production). The impacts of the different phosphate deposition sources on the biogeochemistry of the Mediterranean are found localized, seasonally varying and small, but yet statistically significant. Differences in the geographical deposition patterns between phosphate from dust and from combustion will cause contrasted and significant changes in the biogeochemistry of the basin. We contrast the effects of combustion in the northern basin (Pcomb deposition effects are found to be 10 times more important in the northern Adriatic, close to the main source region) to the effects of dust in the southern basin. These different phosphorus sources should therefore be accounted for in modeling studies.

Semiautomated model building for RNA crystallography using a directed rotameric approach.

PubMed

Keating, Kevin S; Pyle, Anna Marie

2010-05-04

Structured RNA molecules play essential roles in a variety of cellular processes; however, crystallographic studies of such RNA molecules present a large number of challenges. One notable complication arises from the low resolutions typical of RNA crystallography, which results in electron density maps that are imprecise and difficult to interpret. This problem is exacerbated by the lack of computational tools for RNA modeling, as many of the techniques commonly used in protein crystallography have no equivalents for RNA structure. This leads to difficulty and errors in the model building process, particularly in modeling of the RNA backbone, which is highly error prone due to the large number of variable torsion angles per nucleotide. To address this, we have developed a method for accurately building the RNA backbone into maps of intermediate or low resolution. This method is semiautomated, as it requires a crystallographer to first locate phosphates and bases in the electron density map. After this initial trace of the molecule, however, an accurate backbone structure can be built without further user intervention. To accomplish this, backbone conformers are first predicted using RNA pseudotorsions and the base-phosphate perpendicular distance. Detailed backbone coordinates are then calculated to conform both to the predicted conformer and to the previously located phosphates and bases. This technique is shown to produce accurate backbone structure even when starting from imprecise phosphate and base coordinates. A program implementing this methodology is currently available, and a plugin for the Coot model building program is under development.

Allosteric Communication Disrupted by a Small Molecule Binding to the Imidazole Glycerol Phosphate Synthase Protein-Protein Interface.

PubMed

Rivalta, Ivan; Lisi, George P; Snoeberger, Ning-Shiuan; Manley, Gregory; Loria, J Patrick; Batista, Victor S

2016-11-29

Allosteric enzymes regulate a wide range of catalytic transformations, including biosynthetic mechanisms of important human pathogens, upon binding of substrate molecules to an orthosteric (or active) site and effector ligands at distant (allosteric) sites. We find that enzymatic activity can be impaired by small molecules that bind along the allosteric pathway connecting the orthosteric and allosteric sites, without competing with endogenous ligands. Noncompetitive allosteric inhibitors disrupted allostery in the imidazole glycerol phosphate synthase (IGPS) enzyme from Thermotoga maritima as evidenced by nuclear magnetic resonance, microsecond time-scale molecular dynamics simulations, isothermal titration calorimetry, and kinetic assays. The findings are particularly relevant for the development of allosteric antibiotics, herbicides, and antifungal compounds because IGPS is absent in mammals but provides an entry point to fundamental biosynthetic pathways in plants, fungi, and bacteria.

Partitioning of dopant cations between β-tricalcium phosphate and fluorapatite

NASA Astrophysics Data System (ADS)

Jay, E. E.; Mallinson, P. M.; Fong, S. K.; Metcalfe, B. L.; Grimes, R. W.

2011-07-01

Mixed crystalline phase composite ceramics offer the possibility of partitioning defect species between the phases as well as occupancy of specific sites within a given phase. Here we use atomic scale simulations to study the site preference of an extensive range of divalent and trivalent substitutional ions across the five cation sites in β-tricalcium phosphate ( β-TCP) and the two cations sites in fluorapatite (FAp). This study indicates that in β-TCP small dopant species occupy the smaller of the five cation sites and vice versa. Conversely, in FAp, small divalent species occupy the nominally larger Ca(1) site while larger cations occupy the Ca(2) site. Partition energies between the two phases indicate that divalent species strongly segregate to β-TCP as do Al 3+ and Ga 3+, whereas all other (larger) trivalent ions exhibit little preference.

Graph-Theoretic Analysis of Monomethyl Phosphate Clustering in Ionic Solutions.

PubMed

Han, Kyungreem; Venable, Richard M; Bryant, Anne-Marie; Legacy, Christopher J; Shen, Rong; Li, Hui; Roux, Benoît; Gericke, Arne; Pastor, Richard W

2018-02-01

All-atom molecular dynamics simulations combined with graph-theoretic analysis reveal that clustering of monomethyl phosphate dianion (MMP 2- ) is strongly influenced by the types and combinations of cations in the aqueous solution. Although Ca 2+ promotes the formation of stable and large MMP 2- clusters, K + alone does not. Nonetheless, clusters are larger and their link lifetimes are longer in mixtures of K + and Ca 2+ . This "synergistic" effect depends sensitively on the Lennard-Jones interaction parameters between Ca 2+ and the phosphorus oxygen and correlates with the hydration of the clusters. The pronounced MMP 2- clustering effect of Ca 2+ in the presence of K + is confirmed by Fourier transform infrared spectroscopy. The characterization of the cation-dependent clustering of MMP 2- provides a starting point for understanding cation-dependent clustering of phosphoinositides in cell membranes.

Energetic Profile of the Basketball Exercise Simulation Test in Junior Elite Players.

PubMed

Latzel, Richard; Hoos, Olaf; Stier, Sebastian; Kaufmann, Sebastian; Fresz, Volker; Reim, Dominik; Beneke, Ralph

2017-11-28

To analyze the energetic profile of the basketball exercise simulation test (BEST). 10 male elite junior basketball players (age: 15.5±0.6yrs, height: 180±9cm, body mass: 66.1±11.2kg) performed a modified BEST (20 circuits consisting of jumping, sprinting, jogging, shuffling, and short breaks) simulating professional basketball game play. Circuit time, sprint time, sprint decrement, oxygen uptake (VO2), heart rate (HR), and blood lactate concentration (BLC) were obtained. Metabolic energy and metabolic power above rest (W tot , P tot ) as well as energy share in terms of aerobic (W aer ), glycolytic (W blc ), and high energy phosphates (W PCr ) were calculated from VO2 during exercise, net lactate production, and the fast component of post-exercise VO2 kinetics, respectively. W aer , W blc , and W PCr reflect 89±2%, 5±1%, and 6±1% of total energy needed, respectively. Assuming an aerobic replenishment of PCr energy stores during short breaks, the adjusted energy share yielded W aer : 66±4%, W blc : 5±1%, and W PCr : 29±1%. W aer and W PCr were negatively correlated (-0.72, -0.59) with sprint time, which was not the case for W blc . Consistent with general findings on energy system interaction during repeated high intensity exercise bouts, the intermittent profile of the BEST relies primarily on aerobic energy combined with repetitive supplementation by anaerobic utilization of high energy phosphates.

Kinetics of thermal and photo-initiated release of tris (1,3-dichloro-2-propyl) phosphate (TDCP) flame retardant from polyurethane foam materials.

PubMed

Ghanem, Raed A

2015-01-01

Kinetics of thermal and photo-initiated release of Tris (1.3-dichloro-2-propyl) phosphate (TDCP) from the polyurethane foam (PUF) materials were studied using a validated chromatographic method with linear calibration curve in the range of 0.03-400 μg mL(-1). Time dependence of TDCP leaching from foam samples was found to follow first-order kinetics; with rate constants directly dependent on ageing temperatures and intensity of UV radiation, rate constants for the thermally and photo initiated were 3.6 × 10(-3), 1.03 × 10(-2), 3.6 × 10(-2) and 3.94 × 10(-2) day(-1), respectively. Migration of TDCP from foam samples simulating skin or oral exposure were observed from all samples regardless of their ageing history, the presence of biological fluids found to enhance the migration rate. Oral exposure to foam material contains TDCP, which was simulated using the Head-over-Heels test, reveals that an average amount of ∼ 1.7% wt./wt. of the total amount of TDCP was found to leach into biological fluids, and it significantly increased to ∼ 6.0% wt./wt. due to ageing conditions. Direct contact between foam material and skin simulated by using the Contact Blotting test reveals that TDCP is transferred from both aged and un-aged samples at different rates, due to the presence of biological fluids; the transferred amount is increased with ageing conditions.

Thermal diffusion through amalgam and cement base: comparison of in vitro and in vivo measurements.

PubMed

Tibbetts, V R; Schnell, R J; Swartz, M L; Phillips, R W

1976-01-01

Thermal diffusion was measured in vitro and in vivo through amalgam and amalgam underlaid with bases of zinc phosphate, zinc oxide-eugenol, and calcium hydroxide cements. Although the magnitudes differed, there generally was good agreement between in vitro and in vivo data with respect to the relative rates of thermal diffusivity through amalgam restorations underlaid with bases of each of the three materials. In all tests, both in vitro and in vivo, the zinc oxide-eugenol base proved to be the best thermal insulator. Calcium hydroxide was the next best thermal barrier and was followed by zinc phosphate cement. In vitro tests indicated dentin to be a better thermal insulator than zinc phosphate cement but inferior to the zinc oxide-eugenol and calcium hydroxide base materials used here. Although a method has been presented here for the in vivo assessment of the efficacy of thermal insulating bases and a number of in vivo experiments were conducted, much research remains to be done in this area. Additional investigation is needed to better define the parameters of thermal change beneath various types of restoratives and also to establish more exactly the role of base thickness in providing thermal protection beneath clinical metallic restorations.

Catalysis of CO₂ absorption in aqueous solution by inorganic oxoanions and their application to post combustion capture.

PubMed

Phan, Duong T; Maeder, Marcel; Burns, Robert C; Puxty, Graeme

2014-04-15

To reduce CO2 emission into the atmosphere, particularly from coal-fired power stations, post combustion capture (PCC) using amine-based solvents to chemically absorb CO2 has been extensively developed. From an infrastructure viewpoint, the faster the absorption of CO2, the smaller the absorber required. The use of catalysts for this process has been broadly studied. In this manuscript, a study of the catalytic efficiencies of inorganic oxoanions such as arsenite, arsenate, phosphite, phosphate, and borate is described. The kinetics of the accelerated CO2 absorption at 25 °C was investigated using stopped-flow spectrophotometry. The catalytic rate constants of these anions for the reaction of CO2 with H2O were determined to be 137.7(3), 30.3(7), 69(2), 32.7(9), and 13.66(7) M(-1)s(-1), respectively. A new mechanism for the catalytic reaction of oxoanions with CO2 has also been proposed. The applicability of these catalysts to PCC was further studied by simulation of the absorption process under PCC conditions using their experimental catalytic rate constants. Arsenite and phosphite were confirmed to be the best catalysts for CO2 capture. However, considering the toxicological effect of arsenic and the oxidative instability of phosphite, phosphate would be the most promising inorganic catalyst for PCC process from the series of inorganic oxoanions studied.

Gas-phase and particulate products from the atmospheric degradation of the organothiophosphorus insecticide chlorpyrifos-methyl.

PubMed

Borrás, Esther; Tortajada-Genaro, Luis Antonio; Ródenas, Milagros; Vera, Teresa; Coscollá, Clara; Yusá, Vicent; Muñoz, Amalia

2015-11-01

The phosphorothioate structure is highly present in several organophosphorus pesticides. However, there is insufficient information about its degradation process after the release to the atmosphere and the secondary pollutants formed. Herein, the atmospheric reaction of chlorpyrifos-methyl (o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate), is described for semi-urban or rural locations. The photo-oxidation under low NOx conditions (5-55 ppbV) was reproduced in a large outdoor simulation chamber, observing a rapid degradation (lifetime<3.5 h). The formation of gaseous products and particulate matter (aerosol yield 2-8%) was monitored. The chemical composition of minor products (gaseous and particulate) was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate, dimethyl 3,5,6-trichloropyridin-2-yl phosphate, o-methyl o-(3,5,6-trichloropyridin-2-yl) hydrogen phosphorothioate, 3,5,6-trichloropyridin-2-yl dihydrogen phosphate, 3,5,6-trichloropyridin-2-ol, and 3,5,6-trichloropyridine-2,4-diol. An atmospheric degradation mechanism has been proposed based on an oxidation started with OH-nucleophilic attack to P=S bond. The results have been extrapolated to other organothiophosphorus molecules, such as malathion, parathion, diazinon and methidathion, among many others, to estimate their photo-oxidative degradation and the expected products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Conformation-dependent DNA attraction.

PubMed

Li, Weifeng; Nordenskiöld, Lars; Zhou, Ruhong; Mu, Yuguang

2014-06-21

Understanding how DNA molecules interact with other biomolecules is related to how they utilize their functions and is therefore critical for understanding their structure-function relationships. For a long time, the existence of Z-form DNA (a left-handed double helical version of DNA, instead of the common right-handed B-form) has puzzled the scientists, and the definitive biological significance of Z-DNA has not yet been clarified. In this study, the effects of DNA conformation in DNA-DNA interactions are explored by molecular dynamics simulations. Using umbrella sampling, we find that for both B- and Z-form DNA, surrounding Mg(2+) ions always exert themselves to screen the Coulomb repulsion between DNA phosphates, resulting in very weak attractive force. On the contrary, a tight and stable bound state is discovered for Z-DNA in the presence of Mg(2+) or Na(+), benefiting from their hydrophobic nature. Based on the contact surface and a dewetting process analysis, a two-stage binding process of Z-DNA is outlined: two Z-DNA first attract each other through charge screening and Mg(2+) bridges to phosphate groups in the same way as that of B-DNA, after which hydrophobic contacts of the deoxyribose groups are formed via a dewetting effect, resulting in stable attraction between two Z-DNA molecules. The highlighted hydrophobic nature of Z-DNA interaction from the current study may help to understand the biological functions of Z-DNA in gene transcription.

Reaction Mechanism of Isopentenyl Phosphate Kinase: A QM/MM Study.

PubMed

McClory, James; Timson, David J; Singh, Warispreet; Zhang, Jian; Huang, Meilan

2017-12-14

Isopentenyl phosphate kinase (IPK) catalyzes the Mg 2+ -ATP dependent phosphorylation reactions to produce isopentenyl diphosphate, an important precursor in the synthesis of isopentenols. However, the position of the divalent metal ion in the crystal structures of IPK in complex with ATP and its native substrate IP has not been definitively resolved, and as a result ambiguity surrounds the catalytic mechanism of IP, limiting its exploitation as a biofuel and in drug design. Here we report the catalytically competent structure in complex with the metal ion Mg 2+ and elucidate the phosphorylation reaction mechanism using molecular dynamic simulations and density functional theory-based quantum mechanics/molecular mechanics calculations (B97d/AMBER99). Comparing the substrate-bound and substrate-free IPK complexes, we observed that substrate binding results in significant conformational change of three residues Lys204, Glu207, and Lys211 located on the αG helix to form a strong salt bridge network with Asp145, which in turn tethers the invariant Ser142 via H-bond interaction. The conformational change shuts the subtrate entrance channel formed between the αG and αE helices. Further, we demonstrate the phosphorylation reaction occurs with a reaction barrier of 17.58 kcal/mol, which is in agreement with the previous experimental kinetic data. We found that a highly conserved Gly8 on a glycine-rich loop, together with Lys14, stabilizes the transition state.

Dehydroacetic Acid Derivatives Bearing Amide or Urea Moieties as Effective Anion Receptors.

PubMed

Bregović, Nikola; Cindro, Nikola; Bertoša, Branimir; Barišić, Dajana; Frkanec, Leo; Užarević, Krunoslav; Tomišić, Vladislav

2017-08-01

Derivatives of dehydroacetic acid comprising amide or urea subunits have been synthesized and their anion-binding properties investigated. Among a series of halides and oxyanions, the studied compounds selectively bind acetate and dihydrogen phosphate in acetonitrile and dimethyl sulfoxide. The corresponding complexation processes were characterized by means of 1 H NMR titrations, which revealed a 1:1 complex stoichiometry in most cases, with the exception of dihydrogen phosphate, which formed 2:1 (anion/ligand) complexes in acetonitrile. The complex stability constants were determined and are discussed with respect to the structural properties of the receptors, the hydrogen-bond-forming potential of the anions, and the characteristics of the solvents used. Based on the spectroscopic data and results of Monte Carlo simulations, the amide or urea groups were affirmed as the primary binding sites in all cases. The results of the computational methods indicate that an array of both inter- and intramolecular hydrogen bonds can form in the studied systems, and these were shown to play an important role in defining the overall stability of the complexes. Solubility measurements were carried out in both solvents and the thermodynamics of transfer from acetonitrile to dimethyl sulfoxide were characterized on a quantitative level. This has afforded a detailed insight into the impact of the medium on the complexation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A possible mechanism of metabolic regulation in Gibberella fujikuroi using a mixed carbon source of glucose and corn oil inferred from analysis of the kinetics data obtained in a stirrer tank bioreactor.

PubMed

Rios-Iribe, Erika Y; Hernández-Calderón, Oscar M; Reyes-Moreno, C; Contreras-Andrade, I; Flores-Cotera, Luis B; Escamilla-Silva, Eleazar M

2013-01-01

A nonstructured model was used to study the dynamics of gibberellic acid production in a stirred tank bioreactor. Experimental data were obtained from submerged batch cultures of Gibberella fujikuroi (CDBB H-984) grown in varying ratios of glucose-corn oil as the carbon source. The nitrogen depletion effect was included in mathematical model by considering the specific kinetic constants as a linear function of the normalized nitrogen consumption rate. The kinetics of biomass growth and consumption of phosphate and nitrogen were based on the logistic model. The traditional first-order kinetic model was used to describe the specific consumption of glucose and corn oil. The nitrogen effect was solely included in the phosphate and corn oil consumption and biomass growth. The model fit was satisfactory, revealing the dependence of the kinetics with respect to the nitrogen assimilation rate. Through simulations, it was possible to make diagrams of specific growth rate and specific rate of substrate consumptions, which was a powerful tool for understanding the metabolic interactions that occurred during the various stages of fermentation process. This kinetic analysis provided the proposal of a possible mechanism of regulation on growth, substrate consumptions, and production of gibberellic acid (GA3 ) in G. fujikuroi. © 2013 American Institute of Chemical Engineers.

Preparation of candidate reference materials for the determination of phosphorus containing flame retardants in styrene-based polymers.

PubMed

Roth, Thomas; Urpi Bertran, Raquel; Latza, Andreas; Andörfer-Lang, Katrin; Hügelschäffer, Claudia; Pöhlein, Manfred; Puchta, Ralph; Placht, Christian; Maid, Harald; Bauer, Walter; van Eldik, Rudi

2015-04-01

Candidate reference materials (RM) for the analysis of phosphorus-based flame retardants in styrene-based polymers were prepared using a self-made mini-extruder. Due to legal requirements of the current restriction for the use of certain hazardous substances in electrical and electronic equipment, focus now is placed on phosphorus-based flame retardants instead of the brominated kind. Newly developed analytical methods for the first-mentioned substances also require RMs similar to industrial samples for validation and verification purposes. Hence, the prepared candidate RMs contained resorcinol-bis-(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), triphenyl phosphate and triphenyl phosphine oxide as phosphorus-based flame retardants. Blends of polycarbonate and acrylonitrile-co-butadiene-co-styrene as well as blends of high-impact polystyrene and polyphenylene oxide were chosen as carrier polymers. Homogeneity and thermal stability of the candidate RMs were investigated. Results showed that the candidate RMs were comparable to the available industrial materials. Measurements by ICP/OES, FTIR and NMR confirmed the expected concentrations of the flame retardants and proved that analyte loss and degradation, respectively, was below the uncertainty of measurement during the extrusion process. Thus, the candidate RMs were found to be suitable for laboratory use.

Phosphate release coupled to rotary motion of F1-ATPase

PubMed Central

Okazaki, Kei-ichi; Hummer, Gerhard

2013-01-01

F1-ATPase, the catalytic domain of ATP synthase, synthesizes most of the ATP in living organisms. Running in reverse powered by ATP hydrolysis, this hexameric ring-shaped molecular motor formed by three αβ-dimers creates torque on its central γ-subunit. This reverse operation enables detailed explorations of the mechanochemical coupling mechanisms in experiment and simulation. Here, we use molecular dynamics simulations to construct a first atomistic conformation of the intermediate state following the 40° substep of rotary motion, and to study the timing and molecular mechanism of inorganic phosphate (Pi) release coupled to the rotation. In response to torque-driven rotation of the γ-subunit in the hydrolysis direction, the nucleotide-free αβE interface forming the “empty” E site loosens and singly charged Pi readily escapes to the P loop. By contrast, the interface stays closed with doubly charged Pi. The γ-rotation tightens the ATP-bound αβTP interface, as required for hydrolysis. The calculated rate for the outward release of doubly charged Pi from the αβE interface 120° after ATP hydrolysis closely matches the ∼1-ms functional timescale. Conversely, Pi release from the ADP-bound αβDP interface postulated in earlier models would occur through a kinetically infeasible inward-directed pathway. Our simulations help reconcile conflicting interpretations of single-molecule experiments and crystallographic studies by clarifying the timing of Pi exit, its pathway and kinetics, associated changes in Pi protonation, and changes of the F1-ATPase structure in the 40° substep. Important elements of the molecular mechanism of Pi release emerging from our simulations appear to be conserved in myosin despite the different functional motions. PMID:24062450

Spinach chloroplast 0-acetylserine (thiol)-lyase exhibits two catalytically non-equivalent pyridoxal-5'-phosphate-containing active sites.

PubMed

Rolland, N; Ruffet, M L; Job, D; Douce, R; Droux, M

1996-02-15

A synthetic gene encoding the mature spinach- chloroplast O-acetylserine (thiol)-lyase was constructed and expressed in an Escherichia coli strain carrying the T7 RNA polymerase system. The pure recombinant protein was obtained at high yield (6 mg/l cell culture) using a new purification procedure that includes affinity chromatography on Green A agarose. Its specific activity was of the order of 1000 U/mg, and its physical properties were similar to those previously reported for the natural enzyme isolated from spinach chloroplasts. In particular the recombinant enzyme, as for the natural enzyme, behaved as a homodimer composed of two identical subunits each of Mr 35000. From steady-state kinetic studies using sulfide or 5-thio(2-nitrobenzoate) (Nbs) as alternative nucleophilic co-substrates, the enzyme exhibited positive kinetic co-operativity with respect to O-acetylserine [Ser(Ac)] in the presence of sulfide and a negative kinetic co-operativity in the presence of Nbs. Binding of Ser(Ac) to the enzyme was also investigated by absorbance and fluorescence measurements to obtain insight into the role of pyridoxal 5'-phosphate and of the single tryptophan residue (Trp176) present in the enzyme molecule. Addition of Ser(Ac) to the enzyme provoked the disappearance of the 409-nm absorbance band of the pyridoxal 5'-phosphate Schiff base and the appearance of two new absorbance bands, the one located between 320 nm and 360 nm and the other centered at 470 nm. Also, the fluorescence emission of the pyridoxal 5'-phosphate Schiff base was quenched upon addition of Ser(Ac) to the enzyme. These changes were most presumably due to the formation of a Schiff base intermediate between alpha-aminoacrylate and the pyridoxal 5'-phosphate cofactor. The fluorescence emission of Trp176 was also quenched upon Ser(Ac) binding to the enzyme. Quantitative analysis of the absorbance and fluorescence equilibrium data disclosed a co-operative behavior in Ser(Ac) binding, in agreement with the steady-state kinetic results. Fluorescence quenching experiments with the acrylamide and iodide revealed that the indole ring of Trp176 was largely exposed and located within the pyridoxal 5'-phosphate active site. These results are consistent with the finding that the native enzyme is composed of two identical subunits. Yet, presumably due to subunit-subunit interactions, the enzyme exhibits two non-equivalent pyridoxal-5'-phosphate-containing active sites.

Functionalized Nano and Micro Structured Composite Coatings

DTIC Science & Technology

2011-06-01

created. Contact angles for water, hexadecane and warfare simulants (tributyl phosphate (TBP), methyl salicylate (MS) and 2-chloroethyl ethyl sulfide... methyl salicylate PAA-POEGMA polyacrylic acid-co-poly(oligoethylene glycol methacrylate) PBMA poly(butyl methacrylate) PD-TDES commercial mixture of...polymerized radically (according to a procedure published elsewhere1) to give PGMA, Mn = 300,000 kDa, PDI = 2. The polymerization was carried out in methyl

Phosphate Adsorption using Modified Iron Oxide-based Sorbents in Lake Water: Kinetics, Equilibrium, and Column Tests

EPA Science Inventory

Adsorption behavior of Bayoxide ® E33 (E33) and three E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese (E33/Mn) and silver (E33/AgI and E33/AgII) nanoparticles. Adso...

Molecular bases of diseases characterized by hypophosphatemia and phosphaturia: new understanding.

PubMed

Ozono, Keiichi; Michigami, Toshimi; Namba, Noriyuki; Nakajima, Shigeo; Yamamoto, Takehisa

2006-01-01

Serum phosphate levels are regulated in both calcium-dependent and -independent fashions. Active vitamin D increases while PTH decreases serum phosphate levels in association with the elevation of serum calcium. On the other hand, a calcium-independent phosphaturic factor, historically called phosphatonin is believed to exert a physiological function based on findings in hereditary and tumor-induced diseases characterized by hypophosphatemia with normocalcemia. Among them, autosomal dominant hypophosphatemic rickets (ADHR) has contributed greatly to its elucidation because the gene responsible for ADHR encodes fibroblast growth factor 23 (FGF23) that has been found to have a phosphaturic effect. In addition, FGF23 has been proved to be involved in most cases of oncogenic osteomalacia and X-linked hypophosphatemic rickets that are also characterized by hypophosphatemia and normocalcemia. Moreover, familial tumoral calcinosis, which represents the metabolic mirror image of hypophosphatemic conditions, is caused by a loss-of-function mutation in the FGF23 gene in some patients. Very recently, hereditary hypophosphatemic rickets with hypercalciuria has been found to be caused by mutations in the SLC34A1 gene which encodes a type of sodium phosphate cotransporter. These findings may provide new strategies for treating patients with abnormal phosphate metabolism.

Phosphate Detection through a Cost-Effective Carbon Black Nanoparticle-Modified Screen-Printed Electrode Embedded in a Continuous Flow System.

PubMed

Talarico, Daria; Cinti, Stefano; Arduini, Fabiana; Amine, Aziz; Moscone, Danila; Palleschi, Giuseppe

2015-07-07

An automatable flow system for the continuous and long-term monitoring of the phosphate level has been developed using an amperometric detection method based on the use of a miniaturized sensor. This method is based on the monitoring of an electroactive complex obtained by the reaction between phosphate and molybdate that is consequently reduced at the electrode surface. The use of a screen-printed electrode modified with carbon black nanoparticles (CBNPs) leads to the quantification of the complex at low potential, because CBNPs are capable of electrocatalitically enhancing the phosphomolybdate complex reduction at +125 mV versus Ag/AgCl without fouling problems. The developed system also incorporates reagents and waste storage and is connected to a portable potentiostat for rapid detection and quantification of phosphate. Main analytical parameters, such as working potential, reagent concentration, type of cell, and flow rate, were evaluated and optimized. This system was characterized by a low detection limit (6 μM). Interference studies were carried out. Good recovery percentages comprised between 89 and 131.5% were achieved in different water sources, highlighting its suitability for field measurements.

Nanocube-based hematite photoanode produced in the presence of Na2HPO4 for efficient solar water splitting

NASA Astrophysics Data System (ADS)

Liu, Kan; Wang, Hongyan; Wu, Quanping; Zhao, Jun; Sun, Zhe; Xue, Song

2015-06-01

A thin film of α-Fe2O3 on FTO substrate has been synthesized from hydrothermal process in an aqueous solution of FeCl3 and Na2HPO4. A nanocube structure of α-Fe2O3 is observed within the formed hematite films and coated with phosphate ions on the surface. For comparison, another phosphate modified hematite film has been prepared by soaking the bare hematite film in Na2HPO4 solution. A negative electrostatic field can be built up on the surface of both phosphate modified hematite which will promote charge separation and extraction of photoexcited holes to the electrode surface. It is found that different types of phosphate complex exist in the hematite films, which has been determined by the isoelectric point (IEP) of the hematite films, and consequently influences the formation and strength of the electrostatic field. The effects of phosphate ions on the morphology, surface characteristics and the photoelectrochemical properties of the hematite thin films are investigated and the mechanism is proposed.

Severe hypophosphataemia after intravenous iron administration.

PubMed

Blazevic, A; Hunze, J; Boots, J M M

2014-01-01

Currently, in many centres, intravenous administration of iron is becoming increasingly popular because of higher efficacy and decreased side effects, mainly gastrointestinal, compared with oral iron therapy. Studies of intravenous ferric carboxymaltose administration in the postpartum setting and in patients with non-dialysis-dependent chronic kidney disease revealed a decrease in serum phosphate levels that was generally asymptomatic and transient. Here, we report four cases of severe and symptomatic hypophosphataemia after intravenous iron administration. All patients received this as therapy for iron deficiency anaemia due to heavy menstrual bleeding. In most cases, a pre-existent disorder in the phosphate homeostasis existed, such as a secondary (cases 3 and 4) or tertiary hyperparathyroidism (case 1). However, in the second case there were no risk factors for a dysregulation of the phosphate homeostasis. Based on these findings, we conclude that severe and symptomatic hypophosphatemia can occur as a side effect of intravenous iron administration and can persist for months after administration. Especially patients with low phosphate levels prior to therapy due to concomitant disorders in phosphate homeostasis (e.g. hyperparathyroidism, vitamin D deficiency) are at risk.

Influence of lead on stabilization/solidification by ordinary Portland cement and magnesium phosphate cement.

PubMed

Wang, Yan-Shuai; Dai, Jian-Guo; Wang, Lei; Tsang, Daniel C W; Poon, Chi Sun

2018-01-01

Inorganic binder-based stabilization/solidification (S/S) of Pb-contaminated soil is a commonly used remediation approach. This paper investigates the influences of soluble Pb species on the hydration process of two types of inorganic binders: ordinary Portland cement (OPC) and magnesium potassium phosphate cement (MKPC). The environmental leachability, compressive strength, and setting time of the cement products are assessed as the primary performance indicators. The mechanisms of Pb involved in the hydration process are analyzed through X-ray diffraction (XRD), hydration heat evolution, and thermogravimetric analyses. Results show that the presence of Pb imposes adverse impact on the compressive strength (decreased by 30.4%) and the final setting time (prolonged by 334.7%) of OPC, but it exerts much less influence on those of MKPC. The reduced strength and delayed setting are attributed to the retarded hydration reaction rate of OPC during the induction period. These results suggest that the OPC-based S/S of soluble Pb mainly depends on physical encapsulation by calcium-silicate-hydrate (CSH) gels. In contrast, in case of MKPC-based S/S process, chemical stabilization with residual phosphate (pyromorphite and lead phosphate precipitation) and physical fixation of cementitious struvite-K are the major mechanisms. Therefore, MKPC is a more efficient and chemically stable inorganic binder for the Pb S/S process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of phosphate in water using one-step synthesized zirconium-loaded reduced graphene oxide

NASA Astrophysics Data System (ADS)

Luo, Xin; Wang, Xiurong; Bao, Shaopan; Liu, Xiawei; Zhang, Weicheng; Fang, Tao

2016-12-01

In this account, a one-step green hydrothermal method for zirconium-loaded reduced graphene oxide (RGO-Zr) adsorbent was developed in pure water. It is based on the formation of initially strong-coupling RGO-Zr nanocomposites followed by in situ reduction of GO to RGO during the hydrothermal treatment. The phosphate adsorption performance of the as-prepared nanocomposites was investigated in aqueous environment under various conditions. The characterization results of RGO-Zr nanocomposites showed that ZrO2 was successfully integrated onto the RGO sheets in amorphous. The data from equilibrium phosphate adsorption on RGO-Zr revealed that the adsorption kinetics followed a pseudo-second-order kinetic model, where the adsorption isotherm fitted the Langmuir isotherm model with a maximum adsorption capacity of 27.71 mg P/g at pH 5 and 298 K. The improved phosphate adsorption on RGO-Zr was caused by the dispersion of ZrO2 on the RGO surface. Furthermore, the phosphate adsorption was found insensitive to the increase in pH while it was sensitive to the increase in temperature. The coexisting anions of SO42-, F-, Cl-, NO3- and CO32- affected the phosphate adsorption in a different way. Results suggest that the present RGO-Zr adsorbent has the potential for controlling phosphorus pollution in water.

Multifunctional properties of phosphate-solubilizing microorganisms grown on agro-industrial wastes in fermentation and soil conditions.

PubMed

Vassileva, Maria; Serrano, Mercedes; Bravo, Vicente; Jurado, Encarnación; Nikolaeva, Iana; Martos, Vanessa; Vassilev, Nikolay

2010-02-01

One of the most studied approaches in solubilization of insoluble phosphates is the biological treatment of rock phosphates. In recent years, various techniques for rock phosphate solubilization have been proposed, with increasing emphasis on application of P-solubilizing microorganisms. The P-solubilizing activity is determined by the microbial biochemical ability to produce and release metabolites with metal-chelating functions. In a number of studies, we have shown that agro-industrial wastes can be efficiently used as substrates in solubilization of phosphate rocks. These processes were carried out employing various technologies including solid-state and submerged fermentations including immobilized cells. The review paper deals critically with several novel trends in exploring various properties of the above microbial/agro-wastes/rock phosphate systems. The major idea is to describe how a single P-solubilizing microorganism manifests wide range of metabolic abilities in different environments. In fermentation conditions, P-solubilizing microorganisms were found to produce various enzymes, siderophores, and plant hormones. Further introduction of the resulting biotechnological products into soil-plant systems resulted in significantly higher plant growth, enhanced soil properties, and biological (including biocontrol) activity. Application of these bio-products in bioremediation of disturbed (heavy metal contaminated and desertified) soils is based on another important part of their multifunctional properties.

Sequential injection system for simultaneous determination of sucrose and phosphate in cola drinks using paired emitter-detector diode sensor.

PubMed

Saetear, Phoonthawee; Khamtau, Kittiwut; Ratanawimarnwong, Nuanlaor; Sereenonchai, Kamonthip; Nacapricha, Duangjai

2013-10-15

This work presents the simultaneous determination of sucrose and phosphate by using sequential injection (SI) system with a low cost paired emitter-detector diode (PEDD) light sensor. The PEDD uses two 890 nm LEDs. Measurement of sucrose in Brix unit was carried out based on the detection of light refraction occurring at the liquid interface (the schlieren effect) between the sucrose solution and water. Phosphate was measured from the formation of calcium phosphate with turbidimetric detection. With careful design of the loading sequence and volume (sample--precipitating reagent--sample), simultaneous detection of sucrose and phosphate was accomplished with the single PEDD detector. At the optimized condition, linear calibrations from 1 to 7 Brix sucrose and from 50 to 200mg PO4(3-)L(-1) were obtained. Good precision at lower than 2% RSD (n=10) for both analytes with satisfactory throughput of 21 injections h(-1) was achieved. The method was successfully applied for the determination of sucrose and phosphate in cola drinks. The proposed method is readily applicable for automation and is found to be an alternative method to conventional procedures for on-line quality control process in cola drink industry. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Approach to treatment of hypophosphatemia.

PubMed

Felsenfeld, Arnold J; Levine, Barton S

2012-10-01

Hypophosphatemia can be acute or chronic. Acute hypophosphatemia with phosphate depletion is common in the hospital setting and results in significant morbidity and mortality. Chronic hypophosphatemia, often associated with genetic or acquired renal phosphate-wasting disorders, usually produces abnormal growth and rickets in children and osteomalacia in adults. Acute hypophosphatemia may be mild (phosphorus level, 2-2.5 mg/dL), moderate (1-1.9 mg/dL), or severe (<1 mg/dL) and commonly occurs in clinical settings such as refeeding, alcoholism, diabetic ketoacidosis, malnutrition/starvation, and after surgery (particularly after partial hepatectomy) and in the intensive care unit. Phosphate replacement can be given either orally, intravenously, intradialytically, or in total parenteral nutrition solutions. The rate and amount of replacement are empirically determined, and several algorithms are available. Treatment is tailored to symptoms, severity, anticipated duration of illness, and presence of comorbid conditions, such as kidney failure, volume overload, hypo- or hypercalcemia, hypo- or hyperkalemia, and acid-base status. Mild/moderate acute hypophosphatemia usually can be corrected with increased dietary phosphate or oral supplementation, but intravenous replacement generally is needed when significant comorbid conditions or severe hypophosphatemia with phosphate depletion exist. In chronic hypophosphatemia, standard treatment includes oral phosphate supplementation and active vitamin D. Future treatment for specific disorders associated with chronic hypophosphatemia may include cinacalcet, calcitonin, or dypyrimadole. Published by Elsevier Inc.

Sphingomyelinase D activity in model membranes: structural effects of in situ generation of ceramide-1-phosphate.

PubMed

Stock, Roberto P; Brewer, Jonathan; Wagner, Kerstin; Ramos-Cerrillo, Blanca; Duelund, Lars; Jernshøj, Kit Drescher; Olsen, Lars Folke; Bagatolli, Luis A

2012-01-01

The toxicity of Loxosceles spider venom has been attributed to a rare enzyme, sphingomyelinase D, which transforms sphingomyelin to ceramide-1-phosphate. The bases of its inflammatory and dermonecrotic activity, however, remain unclear. In this work the effects of ceramide-1-phosphate on model membranes were studied both by in situ generation of this lipid using a recombinant sphingomyelinase D from the spider Loxosceles laeta and by pre-mixing it with sphingomyelin and cholesterol. The systems of choice were large unilamellar vesicles for bulk studies (enzyme kinetics, fluorescence spectroscopy and dynamic light scattering) and giant unilamellar vesicles for fluorescence microscopy examination using a variety of fluorescent probes. The influence of membrane lateral structure on the kinetics of enzyme activity and the consequences of enzyme activity on the structure of target membranes containing sphingomyelin were examined. The findings indicate that: 1) ceramide-1-phosphate (particularly lauroyl ceramide-1-phosphate) can be incorporated into sphingomyelin bilayers in a concentration-dependent manner and generates coexistence of liquid disordered/solid ordered domains, 2) the activity of sphingomyelinase D is clearly influenced by the supramolecular organization of its substrate in membranes and, 3) in situ ceramide-1-phosphate generation by enzymatic activity profoundly alters the lateral structure and morphology of the target membranes.

Structure-based functional annotation: yeast ymr099c codes for a D-hexose-6-phosphate mutarotase.

PubMed

Graille, Marc; Baltaze, Jean-Pierre; Leulliot, Nicolas; Liger, Dominique; Quevillon-Cheruel, Sophie; van Tilbeurgh, Herman

2006-10-06

Despite the generation of a large amount of sequence information over the last decade, more than 40% of well characterized enzymatic functions still lack associated protein sequences. Assigning protein sequences to documented biochemical functions is an interesting challenge. We illustrate here that structural genomics may be a reasonable approach in addressing these questions. We present the crystal structure of the Saccharomyces cerevisiae YMR099cp, a protein of unknown function. YMR099cp adopts the same fold as galactose mutarotase and shares the same catalytic machinery necessary for the interconversion of the alpha and beta anomers of galactose. The structure revealed the presence in the active site of a sulfate ion attached by an arginine clamp made by the side chain from two strictly conserved arginine residues. This sulfate is ideally positioned to mimic the phosphate group of hexose 6-phosphate. We have subsequently successfully demonstrated that YMR099cp is a hexose-6-phosphate mutarotase with broad substrate specificity. We solved high resolution structures of some substrate enzyme complexes, further confirming our functional hypothesis. The metabolic role of a hexose-6-phosphate mutarotase is discussed. This work illustrates that structural information has been crucial to assign YMR099cp to the orphan EC activity: hexose-phosphate mutarotase.

A first report of hydroxylated apatite as structural biomineral in Loasaceae – plants’ teeth against herbivores

PubMed Central

Ensikat, Hans-Jürgen; Geisler, Thorsten; Weigend, Maximilian

2016-01-01

Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix. PMID:27194462

Phosphate conversion coating reduces the degradation rate and suppresses side effects of metallic magnesium implants in an animal model.

PubMed

Rahim, Muhammad Imran; Tavares, Ana; Evertz, Florian; Kieke, Marc; Seitz, Jan-Marten; Eifler, Rainer; Weizbauer, Andreas; Willbold, Elmar; Jürgen Maier, Hans; Glasmacher, Birgit; Behrens, Peter; Hauser, Hansjörg; Mueller, Peter P

2017-08-01

Magnesium alloys have promising mechanical and biological properties for the development of degradable implants. However, rapid implant corrosion and gas accumulations in tissue impede clinical applications. With time, the implant degradation rate is reduced by a highly biocompatible, phosphate-containing corrosion layer. To circumvent initial side effects after implantation it was attempted to develop a simple in vitro procedure to generate a similarly protective phosphate corrosion layer. To this end magnesium samples were pre-incubated in phosphate solutions. The resulting coating was well adherent during routine handling procedures. It completely suppressed the initial burst of corrosion and it reduced the average in vitro magnesium degradation rate over 56 days almost two-fold. In a small animal model phosphate coatings on magnesium implants were highly biocompatible and abrogated the appearance of gas cavities in the tissue. After implantation, the phosphate coating was replaced by a layer with an elemental composition that was highly similar to the corrosion layer that had formed on plain magnesium implants. The data demonstrate that a simple pre-treatment could improve clinically relevant properties of magnesium-based implants. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1622-1635, 2017. © 2016 Wiley Periodicals, Inc.

Interaction of a dinuclear fluorescent Cd(II) complex of calix[4]arene conjugate with phosphates and its applicability in cell imaging.

PubMed

Sreenivasu Mummidivarapu, V V; Hinge, Vijaya Kumar; Rao, Chebrolu Pulla

2015-01-21

A triazole-linked hydroxyethylimino conjugate of calix[4]arene () and its cadmium complex have been synthesized and characterized, and their structures have been established. In the complex, both the Cd(2+) centers are bound by an N2O4 core, and one of it is a distorted octahedral, whereas the other is a trigonal anti-prism. The fluorescence intensity of the di-nuclear Cd(ii) complex is quenched only in the presence of phosphates and not with other anions studied owing to their binding affinities and the nature of the interaction of the phosphates with Cd(2+). These are evident even from their absorption spectra. Different phosphates exhibit changes in both their fluorescence as well as absorption spectra to varying extents, suggesting their differential interactions. Among the six phosphates, H2PO4(-) has higher fluorescence quenching even at low equivalents of this ion, whereas P2O7(4-) shows only 50% quenching even at 10 equivalents. The fluorescence quenching is considerable even at 20 ppb (0.2 μM) of H2PO4(-), whereas all other phosphates require a concentration of 50-580 ppb to exhibit the same effect on fluorescence spectra. Thus, the interaction of H2PO4(-) is more effective by ∼30 fold as compared to that of P2O7(4-). Fluorescence quenching by phosphate is due to the release of from its original cadmium complex via the formation of a ternary species followed by the capture of Cd(2+) by the phosphate, as delineated based on the combination of spectral techniques, such as absorption, emission, (1)H NMR and ESI MS. The relative interactive abilities of the six phosphates differ from each other. The removal of Cd(2+) is demonstrated to be reversible by the repeated addition of the phosphate followed by Cd(2+). The characteristics of the ternary species formed in each of these six phosphates have been computationally modeled using molecular mechanics. The computational study revealed that the coordination between cadmium and -CH2-CH2-OH breaks and new coordination is established through the phosphate oxygens, and as a result the Cd(2+) center acquires a distorted octahedral geometry. The utility of the complex was demonstrated in HeLa cells.

Effects of Microbial and Phosphate Amendments on the Bioavailability of Lead (Pb) in Shooting Range Soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brigmon, Robin; Wilson, Christina; Knox, Anna

Heavy metals including lead (Pb) are released continually into the environment as a result of industrial, recreational, and military activities. Lead ranked number two on the CERCLA Priority List of Hazardous Substances and was identified as a major hazardous chemical found on 47% of USEPA's National Priorities List sites (Hettiarachchi and Pierzynski 2004). In-situ remediation of lead (Pb) contaminated soils may be accomplished by changing the soil chemistry and structure with the application of microbial and phosphate amendments. Soil contaminated with lead bullets was collected from the surface of the berm at Savannah River Site (SRS) Small Arms Training Academymore » (SATA) in Aiken, SC. While uncontaminated soils typically have Pb levels ranging from 2 to 200 mg/kg (Berti et al. 1998), previous analysis show Pb levels of the SATA berm to reach 8,673 mg/kg. Biosurfactants are surface-active compounds naturally produced by soil bacteria that can bind metals. Biosurfactants have a wide variety of chemical structures that reduce interfacial surface tensions (Jennings and Tanner 2000) and have demonstrated efficient metal complexion (Lin 1996). Biosurfactants also have the potential to change the availability of natural organic matter (Strong-Gunderson 1995). Two types of bacteria, Alcaligenes piechaudii and Pseudomonas putida, were employed as amendments based on their ability to produce biosurfactants and survive in metal-contaminated soils. Apatites (calcium phosphate compounds) are important in the formation of Pb phosphates. Pb phosphates form rapidly when phosphate is available and are the most stable environmental form of lead in soil (Ruby et al.1998). Pyromorphites in particular remain insoluble under a wide range of environmental conditions (Zhang et al. 1998). The three apatites evaluated in the current study were North Carolina apatite (NCA), Florida apatite (FA), and biological apatite (BA). BA is ground fish bone that has few impurities such as As, Cr, or U and contains about 27% total phosphate, most of which is available. FA and NCA are two types of rock phosphates that release small amounts of phosphate over time. Total phosphate is around 30% with only 1-2% phosphate available (Knox et al. 2005). In this study, we describe the influence of combining the two microbial and three phosphate amendments on reducing lead bioavailability in shooting range soil.« less

Rational Design Synthesis and Evaluation of New Selective Inhibitors of Microbial Class II (Zinc Dependent) Fructose Bis-phosphate Aldolases

DOE Office of Scientific and Technical Information (OSTI.GOV)

R Daher; M Coincon; M Fonvielle

2011-12-31

We report the synthesis and biochemical evaluation of several selective inhibitors of class II (zinc dependent) fructose bis-phosphate aldolases (Fba). The products were designed as transition-state analogues of the catalyzed reaction, structurally related to the substrate fructose bis-phosphate (or sedoheptulose bis-phosphate) and based on an N-substituted hydroxamic acid, as a chelator of the zinc ion present in active site. The compounds synthesized were tested on class II Fbas from various pathogenic microorganisms and, by comparison, on a mammalian class I Fba. The best inhibitor shows Ki against class II Fbas from various pathogens in the nM range, with very highmore » selectivity (up to 105). Structural analyses of inhibitors in complex with aldolases rationalize and corroborate the enzymatic kinetics results. These inhibitors represent lead compounds for the preparation of new synthetic antibiotics, notably for tuberculosis prophylaxis.« less

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

PubMed Central

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-01-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron–hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries. PMID:28393912