D-Ribulose 5-Phosphate 3-Epimerase: Functional and Structural Relationships to Members of the Ribulose-Phosphate Binding (beta/alpha)8-Barrel Superfamily

Energy Technology Data Exchange (ETDEWEB)

Akana,J.; Federov, A.; Federov, E.; Novak, W.; Babbitt, P.; Almo, S.; Gerlt, J.

2006-01-01

The 'ribulose phosphate binding' superfamily defined by the Structural Classification of Proteins (SCOP) database is considered the result of divergent evolution from a common ({beta}/{alpha}){sub 8}-barrel ancestor. The superfamily includes D-ribulose 5-phosphate 3-epimerase (RPE), orotidine 5'-monophosphate decarboxylase (OMPDC), and 3-keto-L-gulonate 6-phosphate decarboxylase (KGPDC), members of the OMPDC suprafamily, as well as enzymes involved in histidine and tryptophan biosynthesis that utilize phosphorylated metabolites as substrates. We now report studies of the functional and structural relationships of RPE to the members of the superfamily. As suggested by the results of crystallographic studies of the RPEs from rice and Plasmodium falciparum, the RPE from Streptococcus pyogenes is activated by Zn{sup 2+} which binds with a stoichiometry of one ion per polypeptide. Although wild type RPE has a high affinity for Zn{sup 2+} and inactive apoenzyme cannot be prepared, the affinity for Zn{sup 2+} is decreased by alanine substitutions for the two histidine residues that coordinate the Zn{sup 2+} ion (H34A and H67A); these mutant proteins can be prepared in an inactive, metal-free form and activated by exogenous Zn{sup 2+}. The crystal structure of the RPE was solved at 1.8 Angstroms resolution in the presence of D-xylitol 5-phosphate, an inert analogue of the D-xylulose 5-phosphate substrate. This structure suggests that the 2,3-enediolate intermediate in the 1,1-proton transfer reaction is stabilized by bidentate coordination to the Zn{sup 2+} that also is liganded to His 34, Asp 36, His 67, and Asp 176; the carboxylate groups of the Asp residues are positioned also to function as the acid/base catalysts. Although the conformation of the bound analogue resembles those of ligands bound in the active sites of OMPDC and KGPDC, the identities of the active site residues that coordinate the essential Zn{sup 2+} and participate as acid/base catalysts

Evaluation of intestinal phosphate binding to improve the safety profile of oral sodium phosphate bowel cleansing.

Directory of Open Access Journals (Sweden)

Stef Robijn

Full Text Available Prior to colonoscopy, bowel cleansing is performed for which frequently oral sodium phosphate (OSP is used. OSP results in significant hyperphosphatemia and cases of acute kidney injury (AKI referred to as acute phosphate nephropathy (APN; characterized by nephrocalcinosis are reported after OSP use, which led to a US-FDA warning. To improve the safety profile of OSP, it was evaluated whether the side-effects of OSP could be prevented with intestinal phosphate binders. Hereto a Wistar rat model of APN was developed. OSP administration (2 times 1.2 g phosphate by gavage with a 12h time interval induced bowel cleansing (severe diarrhea and significant hyperphosphatemia (21.79 ± 5.07 mg/dl 6h after the second OSP dose versus 8.44 ± 0.97 mg/dl at baseline. Concomitantly, serum PTH levels increased fivefold and FGF-23 levels showed a threefold increase, while serum calcium levels significantly decreased from 11.29 ± 0.53 mg/dl at baseline to 8.68 ± 0.79 mg/dl after OSP. OSP administration induced weaker NaPi-2a staining along the apical proximal tubular membrane. APN was induced: serum creatinine increased (1.5 times baseline and nephrocalcinosis developed (increased renal calcium and phosphate content and calcium phosphate deposits on Von Kossa stained kidney sections. Intestinal phosphate binding (lanthanum carbonate or aluminum hydroxide was not able to attenuate the OSP induced side-effects. In conclusion, a clinically relevant rat model of APN was developed. Animals showed increased serum phosphate levels similar to those reported in humans and developed APN. No evidence was found for an improved safety profile of OSP by using intestinal phosphate binders.

Further investigations on the inorganic phosphate binding site of beef heart mitochondrial F1-ATPase

International Nuclear Information System (INIS)

Pougeois, R.; Lauquin, G.J.

1985-01-01

The possibility that 4-azido-2-nitrophenyl phosphate (ANPP), a photoreactive derivative of inorganic phosphate (P /sub i/ ), could mimic ATP was investigated. ANPP was hydrolyzed in the dark by sarcoplasmic reticulum Ca 2+ -ATPase in the presence of Ca 2+ but not in the presence of ethylene glycol bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid. ANPP was not hydrolyzed by purified mitochondrial F1-ATPase; however, ADP and ATP protected F1-ATPase against ANPP photoinactivation. On the other hand, the trinitrophenyl nucleotide analogues (TNP-ADP, TNP-ATP, and TNP-AMP-PNP), which bind specifically at the two catalytic sites of F1-ATPase, abolished P /sub i/ binding on F1-ATPase; they do not protect F1-ATPase against ANPP photoinactivation. Furthermore, ANPP-photoinactivated F1-ATPase binds the TNP analogues in the same way as the native enzyme. The Pi binding site of F1-ATPase, which is shown to be photolabeled by ANPP, does not appear to be at the gamma-phosphate position of the catalytic sites

Vitamin B12 Phosphate Conjugation and Its Effect on Binding to the Human B12 -Binding Proteins Intrinsic Factor and Haptocorrin

DEFF Research Database (Denmark)

Ó Proinsias, Keith; Ociepa, Michał; Pluta, Katarzyna

2016-01-01

The binding of vitamin B12 derivatives to human B12 transporter proteins is strongly influenced by the type and site of modification of the cobalamin original structure. We have prepared the first cobalamin derivative modified at the phosphate moiety. The reaction conditions were fully optimized...... and its limitations examined. The resulting derivatives, particularly those bearing terminal alkyne and azide groups, were isolated and used in copper-catalyzed alkyne-azide cycloaddition reactions (CuAAC). Their sensitivity towards light revealed their potential as photocleavable molecules. The binding...... abilities of selected derivatives were examined and compared with cyanocobalamin. The interaction of the alkylated derivatives with haptocorrin was less affected than the interaction with intrinsic factor. Furthermore, the configuration of the phosphate moiety was irrelevant to the binding process....

Kinetics of solid-phase in ion exchange on tin hydrogen phosphate

International Nuclear Information System (INIS)

Kislitsyn, M.N.; Ketsko, V.A.; Yaroslavtsev, A.B.

2004-01-01

Solid state reactions in mixture of tin hydrogen phosphate and alkali metal (M=Na, K, Cs) chlorides have been studied both in the mode of polythermal heating and at a fixed temperature, using data of X-ray phase and thermogravimetric analyses. In the range 400-750 Deg C solid state ion exchange reactions occur in the systems studied and yield mono-- and dialkali phosphates MHSn(PO 4 ) 2 and M 2 Sn(PO 4 ) 2 . Counter diffusion coefficients for alkali metal cations and protons in the matrices of compositions MHSn(PO 4 ) 2 and M 2 Sn(PO 4 ) 2 have been determined [ru

Critical role of γ-phosphate in structural transition of Na,K-ATPase upon ATP binding

Science.gov (United States)

Petrushanko, Irina Yu.; Mitkevich, Vladimir A.; Anashkina, Anastasia A.; Klimanova, Elizaveta A.; Dergousova, Elena A.; Lopina, Olga D.; Makarov, Alexander A.

2014-06-01

Active transport of sodium and potassium ions by Na,K-ATPase is accompanied by the enzyme conformational transition between E1 and E2 states. ATP and ADP bind to Na,K-ATPase in the E1 conformation with similar affinity but the properties of enzyme in complexes with these nucleotides are different. We have studied thermodynamics of Na,K-ATPase binding with adenine nucleotides at different temperatures using isothermal titration calorimetry. Our data indicate that β-phosphate is involved in complex formation by increasing the affinity of adenine nucleotides to Na,K-ATPase by an order of magnitude, while γ-phosphate does not affect it. ATP binding to Na,K-ATPase in contrast to ADP binding generates a structural transition in the enzyme, which is consistent with the movement of a significant portion of the surface area to a solvent-protected state. We propose that ATP binding leads to convergence of the nucleotide-binding and phosphorylation domains transferring the enzyme from the ``E1-open'' to ``E1-closed'' conformation ready for phosphorylation.

Phosphate binding therapy in dialysis patients: focus on lanthanum carbonate

Directory of Open Access Journals (Sweden)

Ismail A Mohammed

2008-11-01

carbonate, dialysis, phosphate binding

Binding of reactive organophosphate by oximes via hydrogen bond

Indian Academy of Sciences (India)

In this contribution, the ability of simple oximes to bind a well-known nerve agent simulant (dimethylmethylphosphonate, DMMP) via hydrogen bond is reported. UV/Vis measurements indicate the formation of 1:1 complexes. 1H-, 31P-NMR titrations and T-ROESY experiments confirm that oximes bind the organophosphate ...

Tritium gettering from air with hydrogen uranyl phosphate. Revision 1

International Nuclear Information System (INIS)

Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, R.T.

1985-01-01

Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m 3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

Measurement of binding of adenine nucleotides and phosphate to cytosolic proteins in permeabilized rat-liver cells

NARCIS (Netherlands)

Gankema, H. S.; Groen, A. K.; Wanders, R. J.; Tager, J. M.

1983-01-01

1. A method is described for measuring the binding of metabolites to cytosolic proteins in situ in isolated rat-liver cells treated with filipin to render the plasma membrane permeable to compounds of low molecular weight. 2. There is no binding of ATP or inorganic phosphate to cytosolic proteins,

Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

International Nuclear Information System (INIS)

Ordonez R, E.; Fernandez V, S.M.; Drot, R.; Simoni, E.

2005-01-01

The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10 -4 and 10 -5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO 4 . The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

Investigation on molecular interaction of amino acids in aqueous disodium hydrogen phosphate solutions with reference to volumetric and compressibility measurements

International Nuclear Information System (INIS)

Kumar, Harsh; Singla, Meenu; Jindal, Rajeev

2014-01-01

Highlights: • Densities and speeds of sound of amino acids in aqueous disodium hydrogen phosphate. • Partial molar volumes and compressibility of transfer. • Positive values of transfer volume indicates interactions between ions of amino acids and TSC. • Ion–hydrophilic and hydrophilic–hydrophilic interactions are present. • Pair-wise interactions are dominant in the mixtures. -- Abstract: The interactions of amino acids glycine (Gly), L-alanine (Ala), and L-valine (Val) with disodium hydrogen phosphate (DSHP) as a function of temperature have been investigated by combination of volumetric and acoustic measurements. Densities (ρ) and speeds of sound (u) of amino acids in aqueous solutions of disodium hydrogen phosphate have been measured at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K and atmospheric pressure. The apparent molar volume (V ϕ ), the partial molar volume (V ϕ 0 ) and standard partial molar volumes of transfer (ΔV ϕ 0 ) for amino acids from water to aqueous disodium hydrogen phosphate solutions have been calculated from density data. Partial molar adiabatic compressibility (κ ϕ,s ) and partial molar adiabatic compressibility of transfer (Δκ ϕ,S 0 ) have been calculated from speed of sound data. The pair (V AB , κ AB ) and triplet (V ABB , κ ABB ) interaction coefficient have been calculated from both the properties. The results have been explained based on competing patterns of interactions of co-solvents and the solute

Insights into phosphate cooperativity and influence of substrate modifications on binding and catalysis of hexameric purine nucleoside phosphorylases.

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Priscila O de Giuseppe

Full Text Available The hexameric purine nucleoside phosphorylase from Bacillus subtilis (BsPNP233 displays great potential to produce nucleoside analogues in industry and can be exploited in the development of new anti-tumor gene therapies. In order to provide structural basis for enzyme and substrates rational optimization, aiming at those applications, the present work shows a thorough and detailed structural description of the binding mode of substrates and nucleoside analogues to the active site of the hexameric BsPNP233. Here we report the crystal structure of BsPNP233 in the apo form and in complex with 11 ligands, including clinically relevant compounds. The crystal structure of six ligands (adenine, 2'deoxyguanosine, aciclovir, ganciclovir, 8-bromoguanosine, 6-chloroguanosine in complex with a hexameric PNP are presented for the first time. Our data showed that free bases adopt alternative conformations in the BsPNP233 active site and indicated that binding of the co-substrate (2'deoxyribose 1-phosphate might contribute for stabilizing the bases in a favorable orientation for catalysis. The BsPNP233-adenosine complex revealed that a hydrogen bond between the 5' hydroxyl group of adenosine and Arg(43* side chain contributes for the ribosyl radical to adopt an unusual C3'-endo conformation. The structures with 6-chloroguanosine and 8-bromoguanosine pointed out that the Cl(6 and Br(8 substrate modifications seem to be detrimental for catalysis and can be explored in the design of inhibitors for hexameric PNPs from pathogens. Our data also corroborated the competitive inhibition mechanism of hexameric PNPs by tubercidin and suggested that the acyclic nucleoside ganciclovir is a better inhibitor for hexameric PNPs than aciclovir. Furthermore, comparative structural analyses indicated that the replacement of Ser(90 by a threonine in the B. cereus hexameric adenosine phosphorylase (Thr(91 is responsible for the lack of negative cooperativity of phosphate binding

Assessment of phosphate binding by sevelamer carbonate powder for oral suspension mixed in foods.

Science.gov (United States)

Hanus, Martin; Zhorov, Eugene; Brommage, Deborah; Plone, Melissa; Holmes-Farley, Stephen Randall

2012-01-01

This study investigated mixing sevelamer carbonate powder with foods and beverages other than water. Food samples, including applesauce, oatmeal, chicken, protein powder, scrambled eggs, ginger ale, and diet ginger ale, were subjected to an in vitro assay, and the difference in the amount of phosphate bound between samples pre-exposed to foods and samples where the drug was exposed to foods concurrently was determined Under these assay conditions, pre-exposure to sevelamer carbonate powder had no effect on the ability to bind phosphate. Clinical testing is needed to further evaluate this finding.

Calcium Alginate and Salt/Phosphate as Binding Agents in Restructured Lamb

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Triana Setyawardani

2001-01-01

Full Text Available A study on restructurization of lamb meat using several binding agents were conducted. Objectives of the study were evaluate effectivity of Ca–alginate, salt and phosphate as binding agent and their effect on physical properties of the restructured meat stored at -20⁰C for up to 12 weeks. Three binding agents were added to the restructured products, which include NaCl 0.3 %/ NTPP 0.3 %; alginate 0.5 %/Ca-lactate 0.5%; NaCl 0.3 % / NTPP 0.5 %/alginate 0.5% and no binding agent as a control. The products were evaluated at 0, 4, 8 and 12 weeks of storage. The result showed that treatment with alginate 0.5%/Ca-lactate 0.5% had the least purge loss value of 4.3±0.2%. The least cooking losses of 30.2±3.79% and the highest shear force 61.6±13.77 N. (Animal Production 3(1: 20-25 (2001Key Words: Alginate/Ca-lactate, purge loss, cooking losses, shear force.

Calcium Alginate and Salt/Phosphate as Binding Agents in Restructured Lamb

Directory of Open Access Journals (Sweden)

Triana Setyawardani

2001-01-01

Full Text Available A study on  restructurization of lamb meat using several binding agents were conducted. Objectives of the study were evaluate  effectivity of Ca–alginate, salt and phosphate as binding agent and their effect on physical properties of the restructured meat stored at -20⁰C for up to 12 weeks. Three binding agents were added to the restructured products, which include NaCl 0.3 %/ NTPP 0.3 %; alginate 0.5 %/Ca-lactate 0.5%; NaCl 0.3 % / NTPP 0.5 %/alginate 0.5% and no binding agent as a control. The products were evaluated at 0, 4, 8 and 12 weeks of storage. The result showed that treatment with alginate 0.5%/Ca-lactate 0.5% had the least purge loss value of 4.3±0.2%. The least cooking losses of 30.2±3.79% and the highest shear force 61.6±13.77 N. (Animal Production 3(1: 20-25 (2001 Key Words: Alginate/Ca-lactate, purge loss, cooking losses, shear  force.

Binding and uptake of {sup 125}iodine-labelled, oxidized low density lipoprotein by macrophages: Comparison of the effects of {alpha}-tocopherol, probucol, pyridoxal-5`-phosphate and magnesium-pyridoxal-5`-phosphate-glutamate

Energy Technology Data Exchange (ETDEWEB)

Selmer, D. [Technische Univ. Muenchen, Freising-Weihenstephan (Germany). Lehrstuhl fuer Phytopathologie; Senekowitsch-Schmidtke, R. [Technische Univ. Muenchen (Germany). Nuklearmedizinische Klinik; Schneider, W. [Steigerwald Arzneimittel, Darmstadt (Germany); Elstner, E.F. [Technische Univ. Muenchen, Freising-Weihenstephan (Germany). Lehrstuhl fuer Phytopathologie

1997-01-01

Specific and unspecific binding and uptake (internalization) by macrophages of {sup 125}iodine-labelled, copper-oxidized human low density lipoprotein is differently influenced by the anti-oxidants {alpha}-tocopherol ({alpha}-Toc), probucol (Prob), pyridoxal-5`-phosphate (PP) and the magnesium-pyridoxal-5`-phosphate glutamate complex (MPPG). Binding as well as internalization, mediated by the so-called `scavenger receptor` is lower in the presence of MPPG whereas both specific binding and internalization are enhanced. The comparison of the effects in vitro allows a rating of the potentially anti-atherogenic and thus protective effects of the tested substances as follows: MPPG>PP>{alpha}-Toc>Prob. (orig.)

Glucose-6-phosphate mediates activation of the carbohydrate responsive binding protein (ChREBP)

International Nuclear Information System (INIS)

Li, Ming V.; Chen, Weiqin; Harmancey, Romain N.; Nuotio-Antar, Alli M.; Imamura, Minako; Saha, Pradip; Taegtmeyer, Heinrich; Chan, Lawrence

2010-01-01

Carbohydrate response element binding protein (ChREBP) is a Mondo family transcription factor that activates a number of glycolytic and lipogenic genes in response to glucose stimulation. We have previously reported that high glucose can activate the transcriptional activity of ChREBP independent of the protein phosphatase 2A (PP2A)-mediated increase in nuclear entry and DNA binding. Here, we found that formation of glucose-6-phosphate (G-6-P) is essential for glucose activation of ChREBP. The glucose response of GAL4-ChREBP is attenuated by D-mannoheptulose, a potent hexokinase inhibitor, as well as over-expression of glucose-6-phosphatase (G6Pase); kinetics of activation of GAL4-ChREBP can be modified by exogenously expressed GCK. Further metabolism of G-6-P through the two major glucose metabolic pathways, glycolysis and pentose-phosphate pathway, is not required for activation of ChREBP; over-expression of glucose-6-phosphate dehydrogenase (G6PD) diminishes, whereas RNAi knockdown of the enzyme enhances, the glucose response of GAL4-ChREBP, respectively. Moreover, the glucose analogue 2-deoxyglucose (2-DG), which is phosphorylated by hexokinase, but not further metabolized, effectively upregulates the transcription activity of ChREBP. In addition, over-expression of phosphofructokinase (PFK) 1 and 2, synergistically diminishes the glucose response of GAL4-ChREBP. These multiple lines of evidence support the conclusion that G-6-P mediates the activation of ChREBP.

τ - hydrogen phosphate of zirconia in sodium salt form and some of its properties

International Nuclear Information System (INIS)

Fernandez V, S.M.; Ordonez R, E.

2004-01-01

It is reported the obtaining and characterization in the sodium salt form of the τ-hydrogen phosphate of zirconium in sodium form, this compound it was synthesized, for a new technique developed in the laboratory of Dept. of Chemistry of the ININ. The characterization was carried out for XRD, IR, Sem and EDS the thermal gravimetric analysis is also reported. (Author)

Dissolution of uranium dioxide in supercritical carbon dioxide modified with tri-n-butyl phosphate-hydrogen peroxide

International Nuclear Information System (INIS)

Kanekar, A.S.; Pathak, P.N.; Mohapatra, P.K.; Manchanda, V.K.

2009-01-01

Direct dissolution of uranium dioxide in supercritical carbon dioxide modified with tri-n-butyl phosphate (TBP) has been attempted. The effects of TBP concentration and pressure on the extraction of uranium have been studied. Addition of hydrogen peroxide in the modifier enhances the dissolution/extraction of uranium. (author)

Functional consequences of piceatannol binding to glyceraldehyde-3-phosphate dehydrogenase.

Science.gov (United States)

Gerszon, Joanna; Serafin, Eligiusz; Buczkowski, Adam; Michlewska, Sylwia; Bielnicki, Jakub Antoni; Rodacka, Aleksandra

2018-01-01

Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) is one of the key redox-sensitive proteins whose activity is largely affected by oxidative modifications at its highly reactive cysteine residue in the enzyme's active site (Cys149). Prolonged exposure to oxidative stress may cause, inter alia, the formation of intermolecular disulfide bonds leading to accumulation of GAPDH aggregates and ultimately to cell death. Recently these anomalies have been linked with the pathogenesis of Alzheimer's disease. Novel evidences indicate that low molecular compounds may be effective inhibitors potentially preventing the GAPDH translocation to the nucleus, and inhibiting or slowing down its aggregation and oligomerization. Therefore, we decided to establish the ability of naturally occurring compound, piceatannol, to interact with GAPDH and to reveal its effect on functional properties and selected parameters of the dehydrogenase structure. The obtained data revealed that piceatannol binds to GAPDH. The ITC analysis indicated that one molecule of the tetrameric enzyme may bind up to 8 molecules of polyphenol (7.3 ± 0.9). Potential binding sites of piceatannol to the GAPDH molecule were analyzed using the Ligand Fit algorithm. Conducted analysis detected 11 ligand binding positions. We indicated that piceatannol decreases GAPDH activity. Detailed analysis allowed us to presume that this effect is due to piceatannol ability to assemble a covalent binding with nucleophilic cysteine residue (Cys149) which is directly involved in the catalytic reaction. Consequently, our studies strongly indicate that piceatannol would be an exceptional inhibitor thanks to its ability to break the aforementioned pathologic disulfide linkage, and therefore to inhibit GAPDH aggregation. We demonstrated that by binding with GAPDH piceatannol blocks cysteine residue and counteracts its oxidative modifications, that induce oligomerization and GAPDH aggregation.

Crystal Structure and Substrate Specificity of D-Galactose-6-Phosphate Isomerase Complexed with Substrates

Science.gov (United States)

Lee, Jung-Kul; Pan, Cheol-Ho

2013-01-01

D-Galactose-6-phosphate isomerase from Lactobacillus rhamnosus (LacAB; EC 5.3.1.26), which is encoded by the tagatose-6-phosphate pathway gene cluster (lacABCD), catalyzes the isomerization of D-galactose-6-phosphate to D-tagatose-6-phosphate during lactose catabolism and is used to produce rare sugars as low-calorie natural sweeteners. The crystal structures of LacAB and its complex with D-tagatose-6-phosphate revealed that LacAB is a homotetramer of LacA and LacB subunits, with a structure similar to that of ribose-5-phosphate isomerase (Rpi). Structurally, LacAB belongs to the RpiB/LacAB superfamily, having a Rossmann-like αβα sandwich fold as has been identified in pentose phosphate isomerase and hexose phosphate isomerase. In contrast to other family members, the LacB subunit also has a unique α7 helix in its C-terminus. One active site is distinctly located at the interface between LacA and LacB, whereas two active sites are present in RpiB. In the structure of the product complex, the phosphate group of D-tagatose-6-phosphate is bound to three arginine residues, including Arg-39, producing a different substrate orientation than that in RpiB, where the substrate binds at Asp-43. Due to the proximity of the Arg-134 residue and backbone Cα of the α6 helix in LacA to the last Asp-172 residue of LacB with a hydrogen bond, a six-carbon sugar-phosphate can bind in the larger pocket of LacAB, compared with RpiB. His-96 in the active site is important for ring opening and substrate orientation, and Cys-65 is essential for the isomerization activity of the enzyme. Two rare sugar substrates, D-psicose and D-ribulose, show optimal binding in the LacAB-substrate complex. These findings were supported by the results of LacA activity assays. PMID:24015281

Crystal structure and substrate specificity of D-galactose-6-phosphate isomerase complexed with substrates.

Directory of Open Access Journals (Sweden)

Woo-Suk Jung

Full Text Available D-Galactose-6-phosphate isomerase from Lactobacillus rhamnosus (LacAB; EC 5.3.1.26, which is encoded by the tagatose-6-phosphate pathway gene cluster (lacABCD, catalyzes the isomerization of D-galactose-6-phosphate to D-tagatose-6-phosphate during lactose catabolism and is used to produce rare sugars as low-calorie natural sweeteners. The crystal structures of LacAB and its complex with D-tagatose-6-phosphate revealed that LacAB is a homotetramer of LacA and LacB subunits, with a structure similar to that of ribose-5-phosphate isomerase (Rpi. Structurally, LacAB belongs to the RpiB/LacAB superfamily, having a Rossmann-like αβα sandwich fold as has been identified in pentose phosphate isomerase and hexose phosphate isomerase. In contrast to other family members, the LacB subunit also has a unique α7 helix in its C-terminus. One active site is distinctly located at the interface between LacA and LacB, whereas two active sites are present in RpiB. In the structure of the product complex, the phosphate group of D-tagatose-6-phosphate is bound to three arginine residues, including Arg-39, producing a different substrate orientation than that in RpiB, where the substrate binds at Asp-43. Due to the proximity of the Arg-134 residue and backbone Cα of the α6 helix in LacA to the last Asp-172 residue of LacB with a hydrogen bond, a six-carbon sugar-phosphate can bind in the larger pocket of LacAB, compared with RpiB. His-96 in the active site is important for ring opening and substrate orientation, and Cys-65 is essential for the isomerization activity of the enzyme. Two rare sugar substrates, D-psicose and D-ribulose, show optimal binding in the LacAB-substrate complex. These findings were supported by the results of LacA activity assays.

Functional consequences of piceatannol binding to glyceraldehyde-3-phosphate dehydrogenase.

Directory of Open Access Journals (Sweden)

Joanna Gerszon

Full Text Available Glyceraldehyde-3-phosphate dehydrogenase (GAPDH is one of the key redox-sensitive proteins whose activity is largely affected by oxidative modifications at its highly reactive cysteine residue in the enzyme's active site (Cys149. Prolonged exposure to oxidative stress may cause, inter alia, the formation of intermolecular disulfide bonds leading to accumulation of GAPDH aggregates and ultimately to cell death. Recently these anomalies have been linked with the pathogenesis of Alzheimer's disease. Novel evidences indicate that low molecular compounds may be effective inhibitors potentially preventing the GAPDH translocation to the nucleus, and inhibiting or slowing down its aggregation and oligomerization. Therefore, we decided to establish the ability of naturally occurring compound, piceatannol, to interact with GAPDH and to reveal its effect on functional properties and selected parameters of the dehydrogenase structure. The obtained data revealed that piceatannol binds to GAPDH. The ITC analysis indicated that one molecule of the tetrameric enzyme may bind up to 8 molecules of polyphenol (7.3 ± 0.9. Potential binding sites of piceatannol to the GAPDH molecule were analyzed using the Ligand Fit algorithm. Conducted analysis detected 11 ligand binding positions. We indicated that piceatannol decreases GAPDH activity. Detailed analysis allowed us to presume that this effect is due to piceatannol ability to assemble a covalent binding with nucleophilic cysteine residue (Cys149 which is directly involved in the catalytic reaction. Consequently, our studies strongly indicate that piceatannol would be an exceptional inhibitor thanks to its ability to break the aforementioned pathologic disulfide linkage, and therefore to inhibit GAPDH aggregation. We demonstrated that by binding with GAPDH piceatannol blocks cysteine residue and counteracts its oxidative modifications, that induce oligomerization and GAPDH aggregation.

Comparison of S. cerevisiae F-BAR domain structures reveals a conserved inositol phosphate binding site

Science.gov (United States)

Moravcevic, Katarina; Alvarado, Diego; Schmitz, Karl R.; Kenniston, Jon A.; Mendrola, Jeannine M.; Ferguson, Kathryn M.; Lemmon, Mark A.

2015-01-01

SUMMARY F-BAR domains control membrane interactions in endocytosis, cytokinesis, and cell signaling. Although generally thought to bind curved membranes containing negatively charged phospholipids, numerous functional studies argue that differences in lipid-binding selectivities of F-BAR domains are functionally important. Here, we compare membrane-binding properties of the S. cerevisiae F-BAR domains in vitro and in vivo. Whereas some F-BAR domains (such as Bzz1p and Hof1p F-BARs) bind equally well to all phospholipids, the F-BAR domain from the RhoGAP Rgd1p preferentially binds phosphoinositides. We determined X-ray crystal structures of F-BAR domains from Hof1p and Rgd1p, the latter bound to an inositol phosphate. The structures explain phospholipid-binding selectivity differences, and reveal an F-BAR phosphoinositide binding site that is fully conserved in a mammalian RhoGAP called Gmip, and is partly retained in certain other F-BAR domains. Our findings reveal previously unappreciated determinants of F-BAR domain lipid-binding specificity, and provide a basis for its prediction from sequence. PMID:25620000

"Fabrication of arbitrarily shaped carbonate apatite foam based on the interlocking process of dicalcium hydrogen phosphate dihydrate".

Science.gov (United States)

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 .

Tunable GLUT-Hexose Binding and Transport via Modulation of Hexose C-3 Hydrogen-Bonding Capabilities.

Science.gov (United States)

Kumar Kondapi, Venkata Pavan; Soueidan, Olivier-Mohamad; Cheeseman, Christopher I; West, Frederick G

2017-06-12

The importance of the hydrogen bonding interactions in the GLUT-hexose binding process (GLUT=hexose transporter) has been demonstrated by studying the binding of structurally modified d-fructose analogues to GLUTs, and in one case its transport into cells. The presence of a hydrogen bond donor at the C-3 position of 2,5-anhydro-d-mannitol derivatives is essential for effective binding to GLUT5 and transport into tumor cells. Surprisingly, installation of a group that can function only as a hydrogen bond acceptor at C-3 resulted in selective recognition by GLUT1 rather than GLUT5. A fluorescently labelled analogue clearly showed GLUT-mediated transport and low efflux properties of the probe. This study reveals that a single positional modification of a 2,5-anhydro-d-mannitol derivative is sufficient to switch its binding preference from GLUT5 to GLUT1, and uncovers general scaffolds that are suitable for the potential selective delivery of molecular payloads into tumor cells via GLUT transport machinery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rheb Protein Binds CAD (Carbamoyl-phosphate Synthetase 2, Aspartate Transcarbamoylase, and Dihydroorotase) Protein in a GTP- and Effector Domain-dependent Manner and Influences Its Cellular Localization and Carbamoyl-phosphate Synthetase (CPSase) Activity*

Science.gov (United States)

Sato, Tatsuhiro; Akasu, Hitomi; Shimono, Wataru; Matsu, Chisa; Fujiwara, Yuki; Shibagaki, Yoshio; Heard, Jeffrey J.; Tamanoi, Fuyuhiko; Hattori, Seisuke

2015-01-01

Rheb small GTPases, which consist of Rheb1 and Rheb2 (also known as RhebL1) in mammalian cells, are unique members of the Ras superfamily and play central roles in regulating protein synthesis and cell growth by activating mTOR. To gain further insight into the function of Rheb, we carried out a search for Rheb-binding proteins and found that Rheb binds to CAD protein (carbamoyl-phosphate synthetase 2, aspartate transcarbamoylase, and dihydroorotase), a multifunctional enzyme required for the de novo synthesis of pyrimidine nucleotides. CAD binding is more pronounced with Rheb2 than with Rheb1. Rheb binds CAD in a GTP- and effector domain-dependent manner. The region of CAD where Rheb binds is located at the C-terminal region of the carbamoyl-phosphate synthetase domain and not in the dihydroorotase and aspartate transcarbamoylase domains. Rheb stimulated carbamoyl-phosphate synthetase activity of CAD in vitro. In addition, an elevated level of intracellular UTP pyrimidine nucleotide was observed in Tsc2-deficient cells, which was attenuated by knocking down of Rheb. Immunostaining analysis showed that expression of Rheb leads to increased accumulation of CAD on lysosomes. Both a farnesyltransferase inhibitor that blocks membrane association of Rheb and knockdown of Rheb mislocalized CAD. These results establish CAD as a downstream effector of Rheb and suggest a possible role of Rheb in regulating de novo pyrimidine nucleotide synthesis. PMID:25422319

Rheb protein binds CAD (carbamoyl-phosphate synthetase 2, aspartate transcarbamoylase, and dihydroorotase) protein in a GTP- and effector domain-dependent manner and influences its cellular localization and carbamoyl-phosphate synthetase (CPSase) activity.

Science.gov (United States)

Sato, Tatsuhiro; Akasu, Hitomi; Shimono, Wataru; Matsu, Chisa; Fujiwara, Yuki; Shibagaki, Yoshio; Heard, Jeffrey J; Tamanoi, Fuyuhiko; Hattori, Seisuke

2015-01-09

Rheb small GTPases, which consist of Rheb1 and Rheb2 (also known as RhebL1) in mammalian cells, are unique members of the Ras superfamily and play central roles in regulating protein synthesis and cell growth by activating mTOR. To gain further insight into the function of Rheb, we carried out a search for Rheb-binding proteins and found that Rheb binds to CAD protein (carbamoyl-phosphate synthetase 2, aspartate transcarbamoylase, and dihydroorotase), a multifunctional enzyme required for the de novo synthesis of pyrimidine nucleotides. CAD binding is more pronounced with Rheb2 than with Rheb1. Rheb binds CAD in a GTP- and effector domain-dependent manner. The region of CAD where Rheb binds is located at the C-terminal region of the carbamoyl-phosphate synthetase domain and not in the dihydroorotase and aspartate transcarbamoylase domains. Rheb stimulated carbamoyl-phosphate synthetase activity of CAD in vitro. In addition, an elevated level of intracellular UTP pyrimidine nucleotide was observed in Tsc2-deficient cells, which was attenuated by knocking down of Rheb. Immunostaining analysis showed that expression of Rheb leads to increased accumulation of CAD on lysosomes. Both a farnesyltransferase inhibitor that blocks membrane association of Rheb and knockdown of Rheb mislocalized CAD. These results establish CAD as a downstream effector of Rheb and suggest a possible role of Rheb in regulating de novo pyrimidine nucleotide synthesis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Solid solutions of hydrogen uranyl phosphate and hydrogen uranyl arsenate. A family of luminescent, lamellar hosts

International Nuclear Information System (INIS)

Dorhout, P.K.; Rosenthal, G.L.; Ellis, A.B.

1988-01-01

Hydrogen uranyl phosphate, HUO 2 PO 4 x 4H 2 O (HUP), and hydrogen uranyl arsenate, HUO 2 AsO 4 x 4H 2 O (HUAs), form solid solutions of composition HUO 2 (PO 4 ) 1-x (AsO 4 )x (HUPAs), representing a family of lamellar, luminescent solids that can serve as hosts for intercalation chemistry. The solids are prepared by aqueous precipitation reactions from uranyl nitrate and mixtures of phosphoric and arsenic acids; thermogravimetric analysis indicates that the phases are tetrahydrates, like HUP and HUAs. Powder x-ray diffraction data reveal the HUPAs solids to be single phases whose lattice constants increase with X, in rough accord with Vegard's law Spectral shifts observed for the HUPAs samples. Emission from the solids is efficient (quantum yields of ∼ 0.2) and long-lived (lifetimes of ∼ 150 μs), although the measured values are uniformly smaller than those of HUP and HUAs; unimolecular radiative and nonradiative rate constants for excited-state decay of ∼ 1500 and 5000 s -1 , respectively, have been calculated for the compounds. 18 refs., 5 figs., 2 tabs

Structural Diversity Within the Mononuclear and Binuclear Active Sites of N-Acetyl-D-Glucosamine-6-Phosphate Deacetylase

Energy Technology Data Exchange (ETDEWEB)

Hall,R.; Brown, S.; Fedorov, A.; Fedorov, E.; Xu, C.; Babbitt, P.; Almo, S.; Raushel, F.

2007-01-01

NagA catalyzes the hydrolysis of N-acetyl-D-glucosamine-6-phosphate to D-glucosamine-6-phosphate and acetate. X-ray crystal structures of NagA from Escherichia coli were determined to establish the number and ligation scheme for the binding of zinc to the active site and to elucidate the molecular interactions between the protein and substrate. The three-dimensional structures of the apo-NagA, Zn-NagA, and the D273N mutant enzyme in the presence of a tight-binding N-methylhydroxyphosphinyl-D-glucosamine-6-phosphate inhibitor were determined. The structure of the Zn-NagA confirms that this enzyme binds a single divalent cation at the beta-position in the active site via ligation to Glu-131, His-195, and His-216. A water molecule completes the ligation shell, which is also in position to be hydrogen bonded to Asp-273. In the structure of NagA bound to the tight binding inhibitor that mimics the tetrahedral intermediate, the methyl phosphonate moiety has displaced the hydrolytic water molecule and is directly coordinated to the zinc within the active site. The side chain of Asp-273 is positioned to activate the hydrolytic water molecule via general base catalysis and to deliver this proton to the amino group upon cleavage of the amide bond of the substrate. His-143 is positioned to help polarize the carbonyl group of the substrate in conjunction with Lewis acid catalysis by the bound zinc. The inhibitor is bound in the {alpha}-configuration at the anomeric carbon through a hydrogen bonding interaction of the hydroxyl group at C-1 with the side chain of His-251. The phosphate group of the inhibitor attached to the hydroxyl at C-6 is ion paired with Arg-227 from the adjacent subunit. NagA from Thermotoga maritima was shown to require a single divalent cation for full catalytic activity.

Solid-state reaction kinetics of neodymium doped magnesium hydrogen phosphate system

Science.gov (United States)

Gupta, Rashmi; Slathia, Goldy; Bamzai, K. K.

2018-05-01

Neodymium doped magnesium hydrogen phosphate (NdMHP) crystals were grown by using gel encapsulation technique. Structural characterization of the grown crystals has been carried out by single crystal X-ray diffraction (XRD) and it revealed that NdMHP crystals crystallize in orthorhombic crystal system with space group Pbca. Kinetics of the decomposition of the grown crystals has been studied by non-isothermal analysis. The estimation of decomposition temperatures and weight loss has been made from the thermogravimetric/differential thermo analytical (TG/DTA) in conjuncture with DSC studies. The various steps involved in the thermal decomposition of the material have been analysed using Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova equations for evaluating various kinetic parameters.

Kinetics and thermodynamics of the binding of riboflavin, riboflavin 5'-phosphate and riboflavin 3',5'-bisphosphate by apoflavodoxins.

OpenAIRE

Pueyo, J J; Curley, G P; Mayhew, S G

1996-01-01

The reactions of excess apoflavodoxin from Desulfovibrio vulgaris, Anabaena variabilis and Azotobacter vinelandii with ribo- flavin 5«-phosphate (FMN), riboflavin 3«,5«-bisphosphate and riboflavin are pseudo-first-order. The rates increase with decreasing pH in the range pH 5-8, and, in general, they increase with increasing ionic strength to approach a maximum at an ionic strength greater than 0.4 M. The rate of FMN binding in phosphate at high pH increases to a maximum ...

Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

Energy Technology Data Exchange (ETDEWEB)

Novo, Joao Batista Marques [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil)]. E-mail: jbmnovo@quimica.ufpr.br; Batista, Fabio Roberto [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Cunha, Carlos Jorge da [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Dias, Lauro Camargo Jr. [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Teixeira Pessine, Francisco Benedito [Instituto de Quimica, Universidade Estadual de Campinas, CP 6154, 13084-971 Campinas-SP (Brazil)

2007-05-15

Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), {alpha}-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times.

Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

International Nuclear Information System (INIS)

Novo, Joao Batista Marques; Batista, Fabio Roberto; Cunha, Carlos Jorge da; Dias, Lauro Camargo Jr.; Teixeira Pessine, Francisco Benedito

2007-01-01

Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), α-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times

Biasing hydrogen bond donating host systems towards chemical warfare agent recognition.

Science.gov (United States)

Hiscock, Jennifer R; Wells, Neil J; Ede, Jayne A; Gale, Philip A; Sambrook, Mark R

2016-10-12

A series of neutral ditopic and negatively charged, monotopic host molecules have been evaluated for their ability to bind chloride and dihydrogen phosphate anions, and neutral organophosphorus species dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PMP) and the chemical warfare agent (CWA) pinacolyl methylphosphonofluoridate (GD, soman) in organic solvent via hydrogen bonding. Urea, thiourea and boronic acid groups are shown to bind anions and neutral guests through the formation of hydrogen bonds, with the urea and thiourea groups typically exhibiting higher affinity interactions. The introduction of a negative charge on the host structure is shown to decrease anion affinity, whilst still allowing for high stability host-GD complex formation. Importantly, the affinity of the host for the neutral CWA GD is greater than for anionic guests, thus demonstrating the potential for selectivity reversal based on charge repulsion.

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

Science.gov (United States)

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.

Solvent Extraction and QSPR of Catecholamines with a Bis(2-ethlhexyl) Hydrogen Phosphate

Energy Technology Data Exchange (ETDEWEB)

Yoshizuka, Kazuharu.; Fujimoto, Yuko.; Ota, Keisuke.; Inoue, Katsutoshi. [Saga University, Saga (Japan). Dept. of Applied Chemistry

1999-02-01

In order to develop an effective separation recess for catecholamine (CA), a basic investigation on solvent extraction of dopamine (DA), adrenaline (Ad) and noradrenaline (NA) from hydrochloric acid solution and their stripping is conducted at 30 degree C employing bis(2-ethylhexyl) hydrogen phosphate (D2EHPA) in chloroform, n-hexane and toluene as the organic diluents. From the dependencies of the distribution ratios on the concentrations of reactant species, i.e. CA, hydrogen ion and D2EHPA, it is elucidated that CA (RNH{sub 2}) is extracted with D2EHPA (HR`) according to the ion exchange mechanism, as the complex type, RNH{sub 3}R` (HR`){sub 3}, and the equilibrium constants (K{sub ex,CA}) for the extraction reactions are also evaluated. The quantitative structure property relationship (QSPR) of K{sub ex,CA} values for each organic diluent is discussed using molecular modeling with semi-empirical molecular orbital calculations considering the solvent effect. (author)

Concerted regulation of npc2 binding to endosomal/lysosomal membranes by bis(monoacylglycero)phosphate and sphingomyelin

DEFF Research Database (Denmark)

Enkavi, Giray; Mikkolainen, Heikki; Güngör, Burçin

2017-01-01

remained elusive. Here, based on an extensive set of atomistic simulations and free energy calculations, we clarify the mechanism and energetics of npc2-membrane binding and characterize the roles of physiologically relevant key lipids associated with the binding process. Our results capture in atomistic......Niemann-Pick Protein C2 (npc2) is a small soluble protein critical for cholesterol transport within and from the lysosome and the late endosome. Intriguingly, npc2-mediated cholesterol transport has been shown to be modulated by lipids, yet the molecular mechanism of npc2-membrane interactions has......). This mode is associated with cholesterol uptake and release. On the other hand, the second mode (Supine) places the cholesterol binding pocket away from the membrane surface, but has overall higher membrane binding affinity. We determined that bis(monoacylglycero)phosphate (bmp) is specifically required...

Binding of Diphtheria Toxin to Phospholipids in Liposomes

Science.gov (United States)

Alving, Carl R.; Iglewski, Barbara H.; Urban, Katharine A.; Moss, Joel; Richards, Roberta L.; Sadoff, Jerald C.

1980-04-01

Diphtheria toxin bound to the phosphate portion of some, but not all, phospholipids in liposomes. Liposomes consisting of dimyristoyl phosphatidylcholine and cholesterol did not bind toxin. Addition of 20 mol% (compared to dimyristoyl phosphatidylcholine) of dipalmitoyl phosphatidic acid, dicetyl phosphate, phosphatidylinositol phosphate, cardiolipin, or phosphatidylserine in the liposomes resulted in substantial binding of toxin. Inclusion of phosphatidylinositol in dimyristol phosphatidylcholine / cholesterol liposomes did not result in toxin binding. The calcium salt of dipalmitoyl phosphatidic acid was more effective than the sodium salt, and the highest level of binding occurred with liposomes consisting only of dipalmitoyl phosphatidic acid (calcium salt) and cholesterol. Binding of toxin to liposomes was dependent on pH, and the pattern of pH dependence varied with liposomes having different compositions. Incubation of diphtheria toxin with liposomes containing dicetyl phosphate resulted in maximal binding at pH 3.6, whereas binding to liposomes containing phosphatidylinositol phosphate was maximal above pH 7. Toxin did not bind to liposomes containing 20 mol% of a free fatty acid (palmitic acid) or a sulfated lipid (3-sulfogalactosylceramide). Toxin binding to dicetyl phosphate or phosphatidylinositol phosphate was inhibited by UTP, ATP, phosphocholine, or p-nitrophenyl phosphate, but not by uracil. We conclude that (a) diphtheria toxin binds specifically to the phosphate portion of certain phospholipids, (b) binding to phospholipids in liposomes is dependent on pH, but is not due only to electrostatic interaction, and (c) binding may be strongly influenced by the composition of adjacent phospholipids that do not bind toxin. We propose that a minor membrane phospholipid (such as phosphatidylinositol phosphate or phosphatidic acid), or that some other phosphorylated membrane molecule (such as a phosphoprotein) may be important in the initial binding of

Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

Science.gov (United States)

Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

2014-02-15

The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Influence of intramolecular hydrogen bonds on the binding potential of methylated β-cyclodextrin derivatives

Directory of Open Access Journals (Sweden)

Gerhard Wenz

2012-11-01

Full Text Available Various heptasubstituted derivatives of β-cyclodextrin (β-CD bearing 1, 2 and 3 methyl substituents per glucose unit were synthesized by regioselective methods. Binding free energies and binding enthalpies of these hosts towards 4-tert-butylbenzoate and adamantane-1-carboxylate were determined by isothermal titration microcalorimetry (ITC. It was found that methyl substituents at the secondary positions of β-CD lead to a tremendous reduction of the binding potential, while methylation at the primary positions significantly improved binding. Stabilizing intramolecular hydrogen bonds between the glucose units were made responsible for the high binding potentials of those β-CD derivatives that possess secondary hydroxy groups.

Calcium carbonate phosphate binding ion exchange filtration and accelerated denitrification improve public health standards and combat eutrophication in aquatic ecosystems.

Science.gov (United States)

Yanamadala, Vijay

2005-01-01

Hektoen agar. Initial analyses suggest a strong correlation between phosphate concentrations and bacterial populations; a 66% decrease in phosphate resulted in a 35% reduction in bacterial populations and a 45% reduction in enteropathogenic populations. Likewise, a strong correlation was shown between calcium carbonate concentrations and bacterial reduction greater than that which can be attributed to the phosphate reduction alone. This was followed by the construction of various phosphate binding calcium carbonate filters, which used the ion exchange principle, including a spring loading filter, PVC pipe filter, and a galvanized filter. All were tested with the aid of Stoke's law formulation. The experiment was extremely successful in designing a working phosphate-binding and ammonia-reducing filter, and a large-scale agitator-clarifier filter system is currently being planned for construction in Madrona Marsh; this filter will reduce phosphate and ammonia levels substantially in the following years, bringing ecological, economical, and health-related improvements to the overall ecosystem and habitat.

Tritium gettering from air with hydrogen uranyl phosphate

International Nuclear Information System (INIS)

Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, T.T.

1985-08-01

The managers of all tritium facilities now worry about their emissions into the atmosphere. The only method for cleaning tritium out of air is to catalyze the formation of tritiated water which is adsorbed, along with the overwhelming bulk of naturally occurring water vapor, on a zeolite molecular sieve. This method generally costs several million dollars for a small system, because of the necessary steel ducting, compressors and holding tanks. We have long had the dream of finding another getter that might be cheaper to use and would, hopefully, not make tritiated water (HTO). In a previous paper, we discovered that hydrogen uranyl phosphate (HUP, with the formula HUO 2 PO 4 x 4H 2 O) getters 1 ppM of tritium gas out of moist air. This makes HUP the first known ''direct'' tritium getter to work in air. However, the tritium enters a hydroxyl network within the HUP, so that it is effectively still in ''water'' form within the HUP. Worse yet, we found up to 10% tritiated water formed during the previous gettering experiments. HUP is unusual in possessing the exceptionally low vapor pressure of 0.6 torr water vapor at 298 0 K. This allows HUP to be used in fairly dry environments. 14 refs., 3 figs., 2 tabs

Oxysterol-binding Protein Activation at Endoplasmic Reticulum-Golgi Contact Sites Reorganizes Phosphatidylinositol 4-Phosphate Pools*

OpenAIRE

Goto, Asako; Charman, Mark; Ridgway, Neale D.

2015-01-01

Oxysterol-binding protein (OSBP) exchanges cholesterol and phosphatidylinositol 4-phosphate (PI-4P) at contact sites between the endoplasmic reticulum (ER) and the trans-Golgi/trans-Golgi network. 25-Hydroxycholesterol (25OH) competitively inhibits this exchange reaction in vitro and causes the constitutive localization of OSBP at the ER/Golgi interface and PI-4P-dependent recruitment of ceramide transfer protein (CERT) for sphingomyelin synthesis. We used PI-4P probes and mass analysis to de...

Interaction between calcium and phosphate adsorption on goethite

NARCIS (Netherlands)

Rietra, R.P.J.J.; Hiemstra, T.; Riemsdijk, van W.H.

2001-01-01

Quantitatively, little is known about the ion interaction processes that are responsible for the binding of phosphate in soil, water, and sediment, which determine the bioavailability and mobility of phosphate. Studies have shown that metal hydroxides are often responsible for the binding of PO4 in

Interaction of bovine gallbladder mucin and calcium-binding protein: effects on calcium phosphate precipitation.

Science.gov (United States)

Afdhal, N H; Ostrow, J D; Koehler, R; Niu, N; Groen, A K; Veis, A; Nunes, D P; Offner, G D

1995-11-01

Gallstones consist of calcium salts and cholesterol crystals, arrayed on a matrix of gallbladder mucin (GBM), and regulatory proteins like calcium-binding protein (CBP). To determine if interactions between CBP and GBM follow a biomineralization scheme, their mutual binding and effects on CaHPO4 precipitation were studied. Binding of CBP to GBM was assessed by inhibition of the fluorescence of the complex of GBM with bis-1,8-anilinonaphthalene sulfonic acid (bis-ANS). The effects of the proteins on precipitation of CaHPO4 were assessed by nephelometry and gravimetry. Precipitates were analyzed for calcium, phosphate, and protein. CBP and bis-ANS competitively displaced each other from 30 binding sites on mucin, with a 1:1 stoichiometry and similar affinity. The rate of precipitation of CaHPO4 was retarded by mucin and CBP. Precipitate mass was unaffected by GBM alone but decreased with the addition of CBP. Complexing CBP with GBM abolished or moderated this latter effect, altered precipitate morphology, and changed the stoichiometric ratios of Ca to PO4 in the precipitates from 1:1 to 3:2. Mucin and CBP were incorporated into the precipitates. These studies suggest that the formation of calcium-containing gallstones is a biomineralization process regulated by both GBM and CBP.

A new crystal modification of diammonium hydrogen phosphate, (NH42(HPO4

Directory of Open Access Journals (Sweden)

Bernhard Spingler

2010-04-01

Full Text Available The addition of hexafluoridophosphate salts (ammonium, silver, thallium or potassium is usually used to precipitate complex cations from aqueous solutions. It has long been known that PF6− is sensitive towards hydrolysis under acidic conditions [Gebala & Jones (1969. J. Inorg. Nucl. Chem. 31, 771–776; Plakhotnyk et al. (2005. J. Fluorine Chem. 126, 27–31]. During the course of our investigation into coinage metal complexes of diphosphine ligands, we used ammonium hexafluoridophosphate in order to crystallize [Ag(diphosphine2]PF6 complexes. From these solutions we always obtained needle-like crystals which turned out to be the title compound, 2NH4+·HPO42−. It was received as the hydrolysis product of NH4PF6. The crystals are a new modification of diammonium hydrogen phosphate. In contrast to the previously published polymorph [Khan et al. (1972. Acta Cryst. B28, 2065–2069], Z′ of the title compound is 2. In the new modification of the title compound, there are eight molecules of (NH42(HPO4 in the unit cell. The structure consists of PO3OH and NH4 tetrahedra, held together by O—H...O and N—H...O hydrogen bonds.

Gadolinium-hydrogen ion exchange of zirconium phosphate

Science.gov (United States)

Liu, D. C.; Power, J. L.

1972-01-01

The Gd(+3)/H(+) ion exchange on a commercial zirconium phosphate ion exchanger was investigated in chloride, sulfate, and phosphate solutions of Gd(+3) at gadolinium concentrations of 0.001 to 1 millimole per cc and in the pH range of 0 to 3.5. Relatively low Gd(+3) capacities, in the range of 0.01 to 0.1 millimole per g of ion exchanger were found at room temperature. A significant difference in Gd(+3) sorption was observed, depending on whether the ion exchanger was converted from initial conditions of greater or lesser Gd(+3) sorption than the specific final conditions. Correlations were found between decrease in Gd(+3) capacity and loss of exchanger phosphate groups due to hydrolysis during washing and between increase in capacity and treatment with H3PO4. Fitting of the experimental data to ideal ion exchange equilibrium expressions indicated that each Gd(+3) ion is sorbed on only one site of the ion exchanger. The selectivity quotient was determined to be 2.5 + or - 0.4 at room temperature on gadolinium desorption in chloride solutions.

Nitrite-cured color and phosphate-mediated water binding of pork muscle proteins as affected by calcium in the curing solution.

Science.gov (United States)

Zhao, Jing; Xiong, Youling L

2012-07-01

Calcium is a mineral naturally present in water and may be included into meat products during processing thereby influencing meat quality. Phosphates improve myofibril swelling and meat water-holding capacity (WHC) but can be sensitive to calcium precipitation. In this study, pork shoulder meat was used to investigate the impact of calcium at 0, 250, and 500 ppm and phosphate type [sodium pyrophosphate (PP), tripolyphosphate (TPP), and hexametaphopshate (HMP)] at 10 mM on nitrite-cured protein extract color at various pH levels (5.5, 6.0, and 6.5) and crude myofibril WHC at pH 6.0. Neither calcium nor phosphates present in the curing brines significantly affected the cured color. Increasing the pH tended to promote the formation of metmyoglobin instead of nitrosylmyoglobin. The ability of PP to enhance myofibril WHC was hampered (P meat products. Although not affecting nitrite-cured color, calcium hampers the efficacy of phosphates to promote water binding by muscle proteins, underscoring the importance of water quality for brine-enhanced meat products. © 2012 Institute of Food Technologists®

Effects of mutagenesis of aspartic acid residues in the putative phosphoribosyl diphosphate binding site of Escherichia coli phosphoribosyl diphosphate synthetase on metal ion specificity and ribose-5-phosphate binding

DEFF Research Database (Denmark)

Willemoës, Martin; Nilsson, Dan; Hove-Jensen, Bjarne

1996-01-01

The three conserved aspartic acid residues of the 5-phospho-d-ribosyl a-1-diphosphate binding site (213-GRDCVLVDDMIDTGGT-228) of Escherichia coli phosphoribosyl diphosphate synthetase were studied by analysis of the mutant enzymes D220E, D220F, D221A, D224A, and D224S. The mutant enzymes showed...... enzymes were dependent on the metal ion present, suggesting a function of the investigated aspartic acid residues both in the binding of ribose 5-phosphate, possibly via a divalent metal ion, and in the interaction with a divalent metal ion during catalysis....

Synthesis, Characterization and Applications of Ethyl Cellulose-Based Polymeric Calcium(II) Hydrogen Phosphate Composite

Science.gov (United States)

Mohammad, Faruq; Arfin, Tanvir; Al-Lohedan, Hamad A.

2018-03-01

The present report deals with the synthesis, characterization and testing of an ethyl cellulose-calcium(II) hydrogen phosphate (EC-CaHPO4) composite, where a sol-gel synthesis method was applied for the preparation of the composite so as to test its efficacy towards the electrochemical, biological, and adsorption related applications. The physical properties of the composite were characterized by using scanning electron microscopy (SEM), ultraviolet- visible (UV-Vis) spectroscopy, and fourier transform-infrared (FTIR) spectroscopy. On testing, the mechanical properties indicated that the composite is highly stable due to the cross-linked rigid framework and the enhanced interactions offered by the EC polymer supported for its binding very effectively. In addition, the conductivity of EC-CaHPO4 is completely governed by the transport mechanism where the electrolyte concentration has preference towards the adsorption of ions and the variations in the conductivity significantly affected the material's performance. We observed an increasing order of KCl > NaCl for the conductivity when 1:1 electrolytes were applied. Further, the material was tested for its usefulness towards the purification of industrial waste waters by removing harmful metal ions from the samples collected near the Aligarh city, India where the data indicates that the material has highest affinity towards Pb2+, Cu2+, Ni2+ and Fe3+ metal ions. Finally, the biological efficiency of the material was confirmed by means of testing the antibacterial activity against two gram positive (staphylococcus aureus and Bacillus thuringiensis) and two gram negative bacteriums (Pseudomonas aeruginosa and Patoea dispersa). Thus, from the cumulative study of outcomes, it indicates that the EC-CaHPO4 composite found to serve as a potential smart biomaterial due to its efficiency in many different applications that includes the electrical conductivity, adsorption capability, and antimicrobial activity.

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

Science.gov (United States)

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-03-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

Enhanced resistance in Theobroma cacao against oomycete and fungal pathogens by secretion of phosphatidylinositol-3-phosphate-binding proteins.

Science.gov (United States)

Helliwell, Emily E; Vega-Arreguín, Julio; Shi, Zi; Bailey, Bryan; Xiao, Shunyuan; Maximova, Siela N; Tyler, Brett M; Guiltinan, Mark J

2016-03-01

The internalization of some oomycete and fungal pathogen effectors into host plant cells has been reported to be blocked by proteins that bind to the effectors' cell entry receptor, phosphatidylinositol-3-phosphate (PI3P). This finding suggested a novel strategy for disease control by engineering plants to secrete PI3P-binding proteins. In this study, we tested this strategy using the chocolate tree Theobroma cacao. Transient expression and secretion of four different PI3P-binding proteins in detached leaves of T. cacao greatly reduced infection by two oomycete pathogens, Phytophthora tropicalis and Phytophthora palmivora, which cause black pod disease. Lesion size and pathogen growth were reduced by up to 85%. Resistance was not conferred by proteins lacking a secretory leader, by proteins with mutations in their PI3P-binding site, or by a secreted PI4P-binding protein. Stably transformed, transgenic T. cacao plants expressing two different PI3P-binding proteins showed substantially enhanced resistance to both P. tropicalis and P. palmivora, as well as to the fungal pathogen Colletotrichum theobromicola. These results demonstrate that secretion of PI3P-binding proteins is an effective way to increase disease resistance in T. cacao, and potentially in other plants, against a broad spectrum of pathogens. © 2015 Society for Experimental Biology, Association of Applied Biologists and John Wiley & Sons Ltd.

Hydrogen-bonding patterns involving a cyclic phosphate

Indian Academy of Sciences (India)

Administrator

Phosphates, which always have electronegative oxygen atoms, bear no exception in their involvement in ... water makes the study of structural patterns due to H-bonding much too complicated. We ... H-bonding features found in all the above.

Takifugu rubripes cation independent mannose 6-phosphate receptor: Cloning, expression and functional characterization of the IGF-II binding domain.

Science.gov (United States)

A, Ajith Kumar; Nadimpalli, Siva Kumar

2018-07-01

Mannose 6-phosphate/IGF-II receptor mediated lysosomal clearance of insulin-like growth factor-II is significantly associated with the evolution of placental mammals. The protein is also referred to as the IGF-II receptor. Earlier studies suggested relatively low binding affinity between the receptor and ligand in prototherian and metatherian mammals. In the present study, we cloned the IGF-II binding domain of the early vertebrate fugu fish and expressed it in bacteria. A 72000Da truncated receptor containing the IGF-II binding domain was obtained. Analysis of this protein (covering domains 11-13 of the CIMPR) for its affinity to fish and human IGF-II by ligand blot assays and ELISA showed that the expressed receptor can specifically bind to both fish and human IGF-II. Additionally, a peptide-specific antibody raised against the region of the IGF-II binding domain also was able to recognize the IGF-II binding regions of mammalian and non-mammalian cation independent MPR protein. These interactions were further characterized by Surface Plasma resonance support that the receptor binds to fish IGF-II, with a dissociation constant of 548nM. Preliminary analysis suggests that the binding mechanism as well as the affinity of the fish and human receptor for IGF-II may have varied according to different evolutionary pressures. Copyright © 2018. Published by Elsevier B.V.

Reactions of the melatonin metabolite N(1)-acetyl-5-methoxykynuramine with carbamoyl phosphate and related compounds.

Science.gov (United States)

Kuesel, Jana T; Hardeland, Rüdiger; Pfoertner, Henrike; Aeckerle, Nelia

2010-01-01

N-[2-(6-methoxyquinazolin-4-yl)-ethyl] acetamide (MQA) is a compound formed from the melatonin metabolite N(1)-acetyl-5-methoxykynuramine (AMK). We followed MQA production in reaction systems containing various putative reaction partners, in the absence and presence of hydrogen peroxide and/or copper(II). Although MQA may be formally described as a condensation product of either N(1)-acetyl-N(2)-formyl-5-methoxykynuramine (AFMK) with ammonia, or AMK with formamide, none of these combinations led to substantial quantities of MQA. However, MQA formation was observed in mixtures containing AMK, hydrogen peroxide, hydrogen carbonate and ammonia, or AMK, hydrogen peroxide, copper(II) and potentially carbamoylating agents, such as potassium cyanate or, more efficiently, carbamoyl phosphate. In the presence of hydrogen peroxide, copper(II) and carbamoyl phosphate, MQA was the major product obtained from AMK, but the omission of copper(II) mainly led to another metabolite, 3-acetamidomethyl-6-methoxycinnolinone (AMMC). This was caused by nitric oxide (NO) generated under oxidative conditions from carbamoyl phosphate, as shown by an NO spin trap. MQA formation with carbamoyl phosphate was not due to the possible decomposition product, formamide. The reaction of AMK with carbamoyl phosphate under oxidative conditions, in which inorganic phosphate and water are released and which differs from the typical process of carbamoylation via isocyanate, may be considered as a new physiological route of MQA formation.

Characterization of the allosteric binding pocket of human liver fructose-1,6-bisphosphatase by protein crystallography and inhibitor activity studies.

Science.gov (United States)

Iversen, L F; Brzozowski, M; Hastrup, S; Hubbard, R; Kastrup, J S; Larsen, I K; Naerum, L; Nørskov-Lauridsen, L; Rasmussen, P B; Thim, L; Wiberg, F C; Lundgren, K

1997-05-01

The structures of three complexes of human fructose-1,6-bisphosphatase (FB) with the allosteric inhibitor AMP and two AMP analogues have been determined and all fully refined. The data used for structure determination were collected at cryogenic temperature (110 K), and with the use of synchrotron radiation. The structures reveal a common mode of binding for AMP and formycine monophosphate (FMP). 5-Amino-4-carboxamido-1 beta-D-5-phosphate-ribofuranosyl-1H-imidazole (AICAR-P) shows an unexpected mode of binding to FB, different from that of the other two ligands. The imidazole ring of AICAR-P is rotated 180 degrees compared to the AMP and FMP bases. This rotation results in a slightly different hydrogen bonding pattern and minor changes in the water structure in the binding pocket. Common features of binding are seen for the ribose and phosphate moieties of all three compounds. Although binding in a different mode, AICAR-P is still capable of making all the important interactions with the residues building the allosteric binding pocket. The IC50 values of AMP, FMP, and AICAR-P were determined to be 1.7, 1.4, and 20.9 microM, respectively. Thus, the approximately 10 times lower potency of AICAR-P is difficult to explain solely from the variations observed in the binding pocket. Only one water molecule in the allosteric binding pocket was found to be conserved in all four subunits in all three structures. This water molecule coordinates to a phosphate oxygen atom and the N7 atom of the AMP molecule, and to similarly situated atoms in the FMP and AICAR-P complexes. This implies an important role of the conserved water molecule in binding of the ligand.

Solid-state reaction kinetics and optical studies of cadmium doped magnesium hydrogen phosphate crystals

Science.gov (United States)

Verma, Madhu; Gupta, Rashmi; Singh, Harjinder; Bamzai, K. K.

2018-04-01

The growth of cadmium doped magnesium hydrogen phosphate was successfully carried out by using room temperature solution technique i.e., gel encapsulation technique. Grown crystals were confirmed by single crystal X-ray diffraction (XRD). The structure of the grown crystal belongs to orthorhombic crystal system and crystallizes in centrosymmetric space group. Kinetics of the decomposition of the grown crystals were studied by non-isothermal analysis. Thermo gravimetric / differential thermo analytical (TG/DTA) studies revealed that the grown crystal is stable upto 119 °C. The various steps involved in the thermal decomposition of the material have been analysed using Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova equations for evaluating various kinetic parameters. The optical studies shows that the grown crystals possess wide transmittance in the visible region and significant optical band gap of 5.5ev with cut off wavelength of 260 nm.

Direct observation of grafting interlayer phosphate in Mg/Al layered double hydroxides

International Nuclear Information System (INIS)

Shimamura, Akihiro; Kanezaki, Eiji; Jones, Mark I.; Metson, James B.

2012-01-01

The grafting of interlayer phosphate in synthetic Mg/Al layered double hydroxides with interlayer hydrogen phosphate (LDH-HPO 4 ) has been studied by XRD, TG/DTA, FT-IR, XPS and XANES. The basal spacing of crystalline LDH-HPO 4 decreases in two stages with increasing temperature, from 1.06 nm to 0.82 nm at 333 K in the first transition, and to 0.722 nm at 453 K in the second. The first stage occurs due to the loss of interlayer water and rearrangement of the interlayer HPO 4 2− . In the second transition, the interlayer phosphate is grafted to the layer by the formation of direct bonding to metal cations in the layer, accompanied by a change in polytype of the crystalline structure. The grafted phosphate becomes immobilized and cannot be removed by anion-exchange with 1-octanesulfonate. The LDH is amorphous at 743 K but decomposes to Mg 3 (PO 4 ) 2 , AlPO 4 , MgO and MgAl 2 O 4 after heated to 1273 K. - Graphical abstract: The cross section of the synthetic Mg, Al layered double hydroxides in Phase 1, with interlayer hydrogen phosphate Phase 2, and with grafted phosphate, Phase 3. Highlights: ► The grafting of hydrogen phosphate intercalated Mg/Al-LDH has been studied. ► The basal spacing of crystalline LDH-HPO 4 decreases in two stages with increasing temperature. ► The first decrease is due to loss of interlayer water, the second is attributed to phosphate grafting. ► The grafted interlayer phosphate becomes immobilized and cannot be removed by anion-exchange.

Donor assists acceptor binding and catalysis of human α1,6-fucosyltransferase.

Science.gov (United States)

Kötzler, Miriam P; Blank, Simon; Bantleon, Frank I; Wienke, Martin; Spillner, Edzard; Meyer, Bernd

2013-08-16

α1,6-Core-fucosyltransferase (FUT8) is a vital enzyme in mammalian physiological and pathophysiological processes such as tumorigenesis and progress of, among others, non-small cell lung cancer and colon carcinoma. It was also shown that therapeutic antibodies have a dramatically higher efficacy if the α1,6-fucosyl residue is absent. However, specific and potent inhibitors for FUT8 and related enzymes are lacking. Hence, it is crucial to elucidate the structural basis of acceptor binding and the catalytic mechanism. We present here the first structural model of FUT8 in complex with its acceptor and donor molecules. An unusually large acceptor, i.e., a hexasaccharide from the core of N-glycans, is required as minimal structure. Acceptor substrate binding of FUT8 is being dissected experimentally by STD NMR and SPR and theoretically by molecular dynamics simulations. The acceptor binding site forms an unusually large and shallow binding site. Binding of the acceptor to the enzyme is much faster and stronger if the donor is present. This is due to strong hydrogen bonding between O6 of the proximal N-acetylglucosamine and an oxygen atom of the β-phosphate of GDP-fucose. Therefore, we propose an ordered Bi Bi mechanism for FUT8 where the donor molecule binds first. No specific amino acid is present that could act as base during catalysis. Our results indicate a donor-assisted mechanism, where an oxygen of the β-phosphate deprotonates the acceptor. Knowledge of the mechanism of FUT8 is now being used for rational design of targeted inhibitors to address metastasis and prognosis of carcinomas.

Towards Phosphate Detection in Hydroponics Using Molecularly Imprinted Polymer Sensors.

Science.gov (United States)

Storer, Christopher S; Coldrick, Zachary; Tate, Daniel J; Donoghue, Jack Marsden; Grieve, Bruce

2018-02-10

An interdigitated electrode sensor was designed and microfabricated for measuring the changes in the capacitance of three phosphate selective molecularly imprinted polymer (MIP) formulations, in order to provide hydroponics users with a portable nutrient sensing tool. The MIPs investigated were synthesised using different combinations of the functional monomers methacrylic acid (MAA) and N -allylthiourea, against the template molecules diphenyl phosphate, triethyl phosphate, and trimethyl phosphate. A cross-interference study between phosphate, nitrate, and sulfate was carried out for the MIP materials using an inductance, capacitance, and resistance (LCR) meter. Capacitance measurements were taken by applying an alternating current (AC) with a potential difference of 1 V root mean square (RMS) at a frequency of 1 kHz. The cross-interference study demonstrated a strong binding preference to phosphate over the other nutrient salts tested for each formulation. The size of template molecule and length of the functional monomer side groups also determined that a short chain functional monomer in combination with a template containing large R-groups produced the optimal binding site conditions when synthesising a phosphate selective MIP.

Structure of conjugated polyketone reductase from Candida parapsilosis IFO 0708 reveals conformational changes for substrate recognition upon NADPH binding.

Science.gov (United States)

Qin, Hui-Min; Yamamura, Akihiro; Miyakawa, Takuya; Kataoka, Michihiko; Nagai, Takahiro; Kitamura, Nahoko; Urano, Nobuyuki; Maruoka, Shintaro; Ohtsuka, Jun; Nagata, Koji; Shimizu, Sakayu; Tanokura, Masaru

2014-01-01

Conjugated polyketone reductase C2 (CPR-C2) from Candida parapsilosis IFO 0708, identified as a nicotinamide adenine dinucleotide phosphate (NADPH)-dependent ketopantoyl lactone reductase, belongs to the aldo-keto reductase superfamily. This enzyme reduces ketopantoyl lactone to D-pantoyl lactone in a strictly stereospecific manner. To elucidate the structural basis of the substrate specificity, we determined the crystal structures of the apo CPR-C2 and CPR-C2/NADPH complex at 1.70 and 1.80 Å resolutions, respectively. CPR-C2 adopted a triose-phosphate isomerase barrel fold at the core of the structure. Binding with the cofactor NADPH induced conformational changes in which Thr27 and Lys28 moved 15 and 5.0 Å, respectively, in the close vicinity of the adenosine 2'-phosphate group of NADPH to form hydrogen bonds. Based on the comparison of the CPR-C2/NADPH structure with 3-α-hydroxysteroid dehydrogenase and mutation analyses, we constructed substrate binding models with ketopantoyl lactone, which provided insight into the substrate specificity by the cofactor-induced structure. The results will be useful for the rational design of CPR-C2 mutants targeted for use in the industrial manufacture of ketopantoyl lactone.

Preparation of calcium phosphate paste

International Nuclear Information System (INIS)

Mohd Reusmaazran Yusof; Norzita Yaacob; Idris Besar; Che Seman Mahmood; Rusnah Mustafa

2010-01-01

Calcium phosphate paste were prepared by mixing between calcium sodium potassium phosphate, Ca 2 NaK (PO 4 ) 2 (CSPP) and monocalcium phosphate monohydrate, Ca(H 2 PO 4 ) 2 .H 2 O (MCPM). CSPP were obtained by reaction between calcium hydrogen phosphate (CaHPO 4 ), potassium carbonate (K 2 CO 3 ) and sodium carbonate (Na 2 CO 3 ) in solid state sintering process followed by quenching in air at 1000 degree Celsius. The paste was aging in simulated body fluid (SBF) for 0.5, 1, 3, 6, 12, 24, 48 hrs, 3, 7 and 14 days. The morphological investigation indicated the formation of apatite crystal were first growth after 24 hours. The obvious growth of apatite crystal was shown at 3 days. The obvious growth of apatite crystal was shown in 7 and 14 days indicated the prediction of paste would have rapid reaction with bone after implantation. (author)

Structure of selected basic zinc/copper (II) phosphate minerals based upon near-infrared spectroscopy--implications for hydrogen bonding.

Science.gov (United States)

Frost, Ray L; Reddy, B Jagannadha; Palmer, Sara J; Keeffe, Eloise C

2011-03-01

The NIR spectra of reichenbachite, scholzite and parascholzite have been studied at 298 K. The spectra of the minerals are different, in line with composition and crystal structural variations. Cation substitution effects are significant in their electronic spectra and three distinctly different electronic transition bands are observed in the near-infrared spectra at high wavenumbers in the 12,000-7600 cm(-1) spectral region. Reichenbachite electronic spectrum is characterised by Cu(II) transition bands at 9755 and 7520 cm(-1). A broad spectral feature observed for ferrous ion in the 12,000-9000 cm(-1) region both in scholzite and parascholzite. Some what similarities in the vibrational spectra of the three phosphate minerals are observed particularly in the OH stretching region. The observation of strong band at 5090 cm(-1) indicates strong hydrogen bonding in the structure of the dimorphs, scholzite and parascholzite. The three phosphates exhibit overlapping bands in the 4800-4000 cm(-1) region resulting from the combinations of vibrational modes of (PO(4))(3-) units. Copyright © 2010 Elsevier B.V. All rights reserved.

Mannobiose Binding Induces Changes in Hydrogen Bonding and Protonation States of Acidic Residues in Concanavalin A As Revealed by Neutron Crystallography

Energy Technology Data Exchange (ETDEWEB)

Gerlits, Oksana O. [UT/ORNL; Coates, Leighton [Biology; Woods, Robert J. [Complex; Kovalevsky, Andrey [Biology

2017-08-30

Plant lectins are carbohydrate-binding proteins with various biomedical applications. Concanavalin A (Con A) holds promise in treating cancerous tumors. To better understand the Con A carbohydrate binding specificity, we obtained a room-temperature neutron structure of this legume lectin in complex with a disaccharide Manα1–2Man, mannobiose. The neutron structure afforded direct visualization of the hydrogen bonding between the protein and ligand, showing that the ligand is able to alter both protonation states and interactions for residues located close to and distant from the binding site. An unprecedented low-barrier hydrogen bond was observed forming between the carboxylic side chains of Asp28 and Glu8, with the D atom positioned equidistant from the oxygen atoms having an O···D···O angle of 101.5°.

Optimizing the Binding Energy of Hydrogen on Nanostructured Carbon Materials through Structure Control and Chemical Doping

Energy Technology Data Exchange (ETDEWEB)

Jie Liu

2011-02-01

The DOE Hydrogen Sorption Center of Excellence (HSCoE) was formed in 2005 to develop materials for hydrogen storage systems to be used in light-duty vehicles. The HSCoE and two related centers of excellence were created as follow-on activities to the DOE Office of Energy Efficiency and Renewable Energy’s (EERE’s) Hydrogen Storage Grand Challenge Solicitation issued in FY 2003. The Hydrogen Sorption Center of Excellence (HSCoE) focuses on developing high-capacity sorbents with the goal to operate at temperatures and pressures approaching ambient and be efficiently and quickly charged in the tank with minimal energy requirements and penalties to the hydrogen fuel infrastructure. The work was directed at overcoming barriers to achieving DOE system goals and identifying pathways to meet the hydrogen storage system targets. To ensure that the development activities were performed as efficiently as possible, the HSCoE formed complementary, focused development clusters based on the following four sorption-based hydrogen storage mechanisms: 1. Physisorption on high specific surface area and nominally single element materials 2. Enhanced H2 binding in Substituted/heterogeneous materials 3. Strong and/or multiple H2 binding from coordinated but electronically unsatruated metal centers 4. Weak Chemisorption/Spillover. As a member of the team, our group at Duke studied the synthesis of various carbon-based materials, including carbon nanotubes and microporous carbon materials with controlled porosity. We worked closely with other team members to study the effect of pore size on the binding energy of hydrogen to the carbon –based materials. Our initial project focus was on the synthesis and purification of small diameter, single-walled carbon nanotubes (SWNTs) with well-controlled diameters for the study of their hydrogen storage properties as a function of diameters. We developed a chemical vapor deposition method that synthesized gram quantities of carbon nanotubes with

Determination of the stability of the uranyl ion sipped in {tau}-hydrogen phosphate of zirconium in sodic form; Determinacion de la estabilidad del ion uranilo sorbido en {tau}-hidrogenofosfato de zirconio en forma sodica

Energy Technology Data Exchange (ETDEWEB)

Ordonez R, E.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Drot, R.; Simoni, E. [Universite de Paris-Sud-XI, Institut de Physique Nucleaire d' Orsay, Groupe de radiochimie, Bat. 100, 91406 Orsay (France)]. e-mail: edo@nuclear.inin.mx

2005-07-01

The stability of the uranyl sipped in the zirconium {tau}-hydrogen phosphate in sodic form ({tau}-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10{sup -4} and 10{sup -5} of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO{sub 4}. The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the {tau}-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

Simulations of hydrogen sorption in rht-MOF-1: identifying the binding sites through explicit polarization and quantum rotation calculations

KAUST Repository

Pham, Tony

2014-01-01

Grand canonical Monte Carlo (GCMC) simulations of hydrogen sorption were performed in rht-MOF-1, a metal-organic framework (MOF) that consists of isophthalate groups joined by copper paddlewheel clusters and Cu3O trimers through tetrazolate moeities. This is a charged rht-MOF that contains extra-framework nitrate counterions within the material. For the simulations performed herein, excellent agreement with experiment was achieved for the simulated hydrogen sorption isotherms and calculated isosteric heat of adsorption, Qst, values only when using a polarizable potential. Thermodynamic agreement is demonstrated via comparing to experimental isotherms and binding sites are revealed by combining simulation and inelastic neutron scattering (INS) data. Simulations involving explicit many-body polarization interactions assisted in the determination of the binding sites in rht-MOF-1 through the distribution of the induced dipoles that led to strong adsorbate interactions. Four distinct hydrogen sorption sites were determined from the polarization distribution: the nitrate ions located in the corners of the truncated tetrahedral cages, the Cu2+ ions of the paddlewheels that project into the truncated tetrahedral and truncated octahedral cages (Cu1 ions), the Cu2+ ions of the Cu3O trimers (Cu3 ions), and the sides of the paddlewheels in the cuboctahedral cage. The simulations revealed that the initial sorption sites for hydrogen in rht-MOF-1 are the nitrate ions; this site corresponds to the high initial Qst value for hydrogen (9.5 kJ mol-1) in the MOF. The radial distribution functions, g(r), about the Cu2+ ions at various loadings revealed that the Cu1 ions are the preferred open-metal sorption sites for hydrogen at low loading, while the Cu3 ions become occupied at higher loadings. The validation of the aforementioned sorption sites in rht-MOF-1 was confirmed by calculating the two-dimensional quantum rotational levels about each site and comparing the levels to the

The Effect of 3% Phosphate Ascorbyl Gel on Bond Strength of Composite Resin to Enamel treated with 35% Hydrogen Peroxide.

Science.gov (United States)

de Castro, Milena de Fátima Schalcher; Silva, Alice Carvalho; Franco, Marcela Mayana Pereira; Silva, Ana Paula Brito; Bramante, Fausto da Silva; da Silva, Monica Barros; Lima, Darlon Martins; Pereira, Adriana de Fátima Vasconcelos

2015-05-01

To evaluate the effect of 3% phosphate ascorbyl gel (PA) in different times onto the microshear bond strength of composite resin (CR) to bovine enamel treated with 35% hydrogen peroxide (HP). Thirty enamel blocks of bovine incisors were made and divided into 5 groups (n = 6) with three specimens per group (n = 18), according to treatment: G1= No bleaching + CR; G2 = HP + CR after 15d; G3 = HP + CR after 24 hours; G4 = HP + PA (15 min) + CR after 24 hours; G5 = HP + PA (2 hours) + CR after 24 hours. The resin cylinders were made by Tygon matrices. Microshear bond strength test was performed using universal testing machine with a 50N load at a speed of 0.5 mm/min. Fracture modes were assessed by a stereomicroscope 40 ×. Microshear bond strength values were submitted to the analysis of variance (ANOVA) one-way and Tukey test (p 0.05). Failure modes were categorized into adhesive (90%) and mixed (10%). The use of 3% phosphate ascorbyl gel for 15 minutes was able to improve bond strength of composite resin to bleached bovine enamel, but when 3% phosphate ascorbyl gel was applied during 40 minutes it negatively interfered in the adhesion of the resin to bleached bovine enamel.

Structure of octaheme cytochrome c nitrite reductase from Thioalkalivibrio nitratireducens in a complex with phosphate

Energy Technology Data Exchange (ETDEWEB)

Trofimov, A. A.; Polyakov, K. M., E-mail: kostya@eimb.relarn.ru [Russian Academy of Sciences, Engelhardt Institute of Molecular Biology (Russian Federation); Boiko, K. M.; Filimonenkov, A. A. [Russian Academy of Sciences, Bach Institute of Biochemistry (Russian Federation); Dorovatovskii, P. V. [Kurchatov Center for Synchrotron Radiation and Nanotechnology (Russian Federation); Tikhonova, T. V.; Popov, V. O. [Russian Academy of Sciences, Bach Institute of Biochemistry (Russian Federation); Koval' chuk, M. V. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

2010-01-15

Octaheme cytochrome c nitrite reductase from Thioalkalivibrio nitratireducens (TvNiR) catalyzes the reduction of nitrite and hydroxylamine to ammonia. The structures of the free enzyme and of the enzyme in complexes with the substrate (nitrite ion) and the inhibitor (azide ion) have been solved previously. In this study we report the structures of the oxidized complex of TvNiR with phosphate and of this complex reduced by europium(II) chloride (1.8- and 2.0-A resolution, the R factors are 15.9 and 16.7%, respectively) and the structure of the enzyme in the complex with cyanide (1.76-A resolution, the R factor is 16.5%), which was prepared by soaking a crystal of the oxidized phosphate complex of TvNiR. In the active site of the enzyme, the phosphate ion binds to the iron ion of the catalytic heme and to the side chains of the catalytic residues Arg131, Tyr303, and His361. The cyanide ion is coordinated to the heme-iron ion and is hydrogen bonded to the residue His361. In the structure of reduced TvNiR, the phosphate ion is bound in the same manner as in the structure of oxidized TvNiR, and the nine{sub c}oordinated europium ion is located on the surface of one of the crystallographically independent monomers of the enzyme.

Structure of octaheme cytochrome c nitrite reductase from Thioalkalivibrio nitratireducens in a complex with phosphate

International Nuclear Information System (INIS)

Trofimov, A. A.; Polyakov, K. M.; Boiko, K. M.; Filimonenkov, A. A.; Dorovatovskii, P. V.; Tikhonova, T. V.; Popov, V. O.; Koval'chuk, M. V.

2010-01-01

Octaheme cytochrome c nitrite reductase from Thioalkalivibrio nitratireducens (TvNiR) catalyzes the reduction of nitrite and hydroxylamine to ammonia. The structures of the free enzyme and of the enzyme in complexes with the substrate (nitrite ion) and the inhibitor (azide ion) have been solved previously. In this study we report the structures of the oxidized complex of TvNiR with phosphate and of this complex reduced by europium(II) chloride (1.8- and 2.0-A resolution, the R factors are 15.9 and 16.7%, respectively) and the structure of the enzyme in the complex with cyanide (1.76-A resolution, the R factor is 16.5%), which was prepared by soaking a crystal of the oxidized phosphate complex of TvNiR. In the active site of the enzyme, the phosphate ion binds to the iron ion of the catalytic heme and to the side chains of the catalytic residues Arg131, Tyr303, and His361. The cyanide ion is coordinated to the heme-iron ion and is hydrogen bonded to the residue His361. In the structure of reduced TvNiR, the phosphate ion is bound in the same manner as in the structure of oxidized TvNiR, and the nine c oordinated europium ion is located on the surface of one of the crystallographically independent monomers of the enzyme.

Studies on various properties of pure and Li-doped Barium Hydrogen Phosphate (BHP) single crystals

Energy Technology Data Exchange (ETDEWEB)

Nallamuthu, D. [Department of Physics, Aditanar College of Arts and Science, Tiruchendur 628216, Tamil Nadu (India); Selvarajan, P., E-mail: pselvarajanphy@yahoo.co.i [Department of Physics, Aditanar College of Arts and Science, Tiruchendur 628216, Tamil Nadu (India); Freeda, T.H. [Physics Research Centre, S.T. Hindu College, Nagercoil 629002 (India)

2010-12-15

Single crystals of pure and Li-doped barium hydrogen phosphate (BHP) were grown by solution method with gel technique. Various properties of the harvested crystals were studied by carrying out single crystal and powder XRD, FTIR, TG/DTA, microhardness and dielectric studies. Atomic absorption study was carried out for Li-doped BHP crystal to check the presence of Li dopants. Unit cell dimensions and diffracting planes of the grown crystals have been identified from XRD studies. Functional groups of the title compounds have been identified from FTIR studies. Density of the grown crystals was calculated using the XRD data. Thermal stability of the samples was checked by TG/DTA studies. Mechanical and dielectric characterizations of the harvested pure and Li-doped BHP crystals reveal the mechanical strength and ferroelectric transition. The observed results are reported and discussed.

Reagentless phosphate ion sensor system for environmental monitoring

Energy Technology Data Exchange (ETDEWEB)

Suzuki, M.; Kurata, H.; Inoue, Y.; Shin, H. [Kyushu Institute of Technology, Fukuoka (Japan). Faculty of computer Science and Systems; Kubo, I. [Soka University, Tokyo (Japan). Faculty of Engineering; Nakamura, H.; Ikebukuro, K.; Karube, I. [The University of Tokyo, Tokyo (Japan). Research Center for Advanced Science and Technology

1998-06-05

Phosphate ion sensor system using an electrochemical detector was developed by the use of recombinant pyruvate oxidase (PyOD) from Lactobacillus plantarum, which needs no addition of thiamine pyrophosphate and flavin adenine dinucleotide for reaction. This system could detect 2 nM hydrogen peroxide. Response time for phosphate ion was 80 s and total measurement time for one sample was 3 min. Citrate buffer solution (pH 6.3) was most suitable for the measurement and optimum flow rate was 0.6 ml/min. Under these optimum conditions minimum detection limit of phosphate ion was 15 nM, which was enough for the determination of phosphate ion in dam-lake. 6 refs., 5 figs., 1 tab.

Research and engineering assessment of biological solubilization of phosphate

Energy Technology Data Exchange (ETDEWEB)

Rogers, R.D.; McIlwain, M.E.; Losinski, S.J.; Taylor, D.D.

1993-03-01

This research and engineering assessment examined a microbial phosphate solubilization process as a method of recovering phosphate from phosphorus containing ore compared to the existing wet acid and electric arc methods. A total of 860 microbial isolates, collected from a range of natural environments were tested for their ability to solubilize phosphate from rock phosphate. A bacterium (Pseudomonas cepacia) was selected for extensive characterization and evaluation of the mechanism of phosphate solubilization and of process engineering parameters necessary to recover phosphate from rock phosphate. These studies found that concentration of hydrogen ion and production of organic acids arising from oxidation of the carbon source facilitated microbial solubilization of both pure chemical insoluble phosphate compounds and phosphate rock. Genetic studies found that phosphate solubilization was linked to an enzyme system (glucose dehydrogenase). Process-related studies found that a critical solids density of 1% by weight (ore to liquid) was necessary for optimal solubilization. An engineering analysis evaluated the cost and energy requirements for a 2 million ton per year sized plant, whose size was selected to be comparable to existing wet acid plants.

Hydrogen bond based smart polymer for highly selective and tunable capture of multiply phosphorylated peptides.

Science.gov (United States)

Qing, Guangyan; Lu, Qi; Li, Xiuling; Liu, Jing; Ye, Mingliang; Liang, Xinmiao; Sun, Taolei

2017-09-06

Multisite phosphorylation is an important and common mechanism for finely regulating protein functions and subsequent cellular responses. However, this study is largely restricted by the difficulty to capture low-abundance multiply phosphorylated peptides (MPPs) from complex biosamples owing to the limitation of enrichment materials and their interactions with phosphates. Here we show that smart polymer can serve as an ideal platform to resolve this challenge. Driven by specific but tunable hydrogen bonding interactions, the smart polymer displays differential complexation with MPPs, singly phosphorylated and non-modified peptides. Importantly, MPP binding can be modulated conveniently and precisely by solution conditions, resulting in highly controllable MPP adsorption on material surface. This facilitates excellent performance in MPP enrichment and separation from model proteins and real biosamples. High enrichment selectivity and coverage, extraordinary adsorption capacities and recovery towards MPPs, as well as high discovery rates of unique phosphorylation sites, suggest its great potential in phosphoproteomics studies.Capture of low-abundance multiply phosphorylated peptides (MPPs) is difficult due to limitation of enrichment materials and their interactions with phosphates. Here the authors show, a smart polymer driven by specific but tunable hydrogen bonding interactions can differentially complex with MPPs, singly phosphorylated and non-modified peptides.

Ophthalmic acid accumulation in an Escherichia coli mutant lacking the conserved pyridoxal 5′-phosphate-binding protein YggS

OpenAIRE

Ito, Tomokazu; Yamauchi, Ayako; Hemmi, Hisashi; Yoshimura, Tohru

2016-01-01

Escherichia coli YggS is a highly conserved pyridoxal 5′-phosphate (PLP)-binding protein whose biochemical function is currently unknown. A previous study with a yggS-deficient E. coli strain (ΔyggS) demonstrated that YggS controls l-Ile- and l-Val-metabolism by modulating 2-ketobutyrate (2-KB), l-2-aminobutyrate (l-2-AB), and/or coenzyme A (CoA) availability in a PLP-dependent fashion. In this study, we found that ΔyggS accumulates an unknown metabolite as judged by amino acid analyses. LC/M...

Lactose Binding Induces Opposing Dynamics Changes in Human Galectins Revealed by NMR-Based Hydrogen-Deuterium Exchange.

Science.gov (United States)

Chien, Chih-Ta Henry; Ho, Meng-Ru; Lin, Chung-Hung; Hsu, Shang-Te Danny

2017-08-16

Galectins are β-galactoside-binding proteins implicated in a myriad of biological functions. Despite their highly conserved carbohydrate binding motifs with essentially identical structures, their affinities for lactose, a common galectin inhibitor, vary significantly. Here, we aimed to examine the molecular basis of differential lactose affinities amongst galectins using solution-based techniques. Consistent dissociation constants of lactose binding were derived from nuclear magnetic resonance (NMR) spectroscopy, intrinsic tryptophan fluorescence, isothermal titration calorimetry and bio-layer interferometry for human galectin-1 (hGal1), galectin-7 (hGal7), and the N-terminal and C-terminal domains of galectin-8 (hGal8 NTD and hGal8 CTD , respectively). Furthermore, the dissociation rates of lactose binding were extracted from NMR lineshape analyses. Structural mapping of chemical shift perturbations revealed long-range perturbations upon lactose binding for hGal1 and hGal8 NTD . We further demonstrated using the NMR-based hydrogen-deuterium exchange (HDX) that lactose binding increases the exchange rates of residues located on the opposite side of the ligand-binding pocket for hGal1 and hGal8 NTD , indicative of allostery. Additionally, lactose binding induces significant stabilisation of hGal8 CTD across the entire domain. Our results suggested that lactose binding reduced the internal dynamics of hGal8 CTD on a very slow timescale (minutes and slower) at the expense of reduced binding affinity due to the unfavourable loss of conformational entropy.

Preparation and Characterization of Apatitic Biphasic Calcium Phosphate

International Nuclear Information System (INIS)

Thin Thin Nwe; Kyaw Naing; Khin Mar Tun; Nyunt Wynn

2005-09-01

The apatitic biphasic calcium phosphate (ABcp) consisting of hydroxyapatite (HA) and -tricalcium phosphate ( -Tcp) has been prepared by precipitation technique using slaked lime and orthophosphoric acid. The X-ray diffraction analysis of the product I (hydroxyapatite) revealed that ABcp was partially crystalline state. However, on heating at 800 C for 8 hrs, XRD pattern indicated a perfectly crystalline form of ABcp. This observation was supported by FT-IR measurement. The change in morphology regarding in the functional nature was infered by the shift in the FT-IR frequency. The optimization of the apatitic biphasic calcium phosphate was done by the variation of disodium hydrogen phosphate concentration, setting time, hardening time as well as compressive strength. The perpared cement may be used as an artificial substitution bone

Structural Isosteres of Phosphate Groups in the Protein Data Bank.

Science.gov (United States)

Zhang, Yuezhou; Borrel, Alexandre; Ghemtio, Leo; Regad, Leslie; Boije Af Gennäs, Gustav; Camproux, Anne-Claude; Yli-Kauhaluoma, Jari; Xhaard, Henri

2017-03-27

We developed a computational workflow to mine the Protein Data Bank for isosteric replacements that exist in different binding site environments but have not necessarily been identified and exploited in compound design. Taking phosphate groups as examples, the workflow was used to construct 157 data sets, each composed of a reference protein complexed with AMP, ADP, ATP, or pyrophosphate as well other ligands. Phosphate binding sites appear to have a high hydration content and large size, resulting in U-shaped bioactive conformations recurrently found across unrelated protein families. A total of 16 413 replacements were extracted, filtered for a significant structural overlap on phosphate groups, and sorted according to their SMILES codes. In addition to the classical isosteres of phosphate, such as carboxylate, sulfone, or sulfonamide, unexpected replacements that do not conserve charge or polarity, such as aryl, aliphatic, or positively charged groups, were found.

Effects of neutral sodium hydrogen phosphate on setting reaction and mechanical strength of hydroxyapatite putty.

Science.gov (United States)

Ishikawa, K; Miyamoto, Y; Takechi, M; Ueyama, Y; Suzuki, K; Nagayama, M; Matsumura, T

1999-03-05

The setting reaction and mechanical strength in terms of diametral tensile strength (DTS) of hydroxyapatite (HAP) putty made of tetracalcium phosphate, dicalcium phosphate anhydrous, and neutral sodium hydrogen phosphate (Na1.8H1.2PO4) solution containing 8 wt % sodium alginate were evaluated as a function of the Na1.8H1.2PO4 concentration. In one condition, HAP putty was placed in an incubator kept at 37 degrees C and 100% relative humidity. In the other condition, immediately after mixing HAP putty was immersed in serum kept at 37 degrees C. Longer setting times and lower DTS values were observed when HAP putty was immersed in serum regardless of the Na1.8H1.2PO4 concentration. The setting times of the HAP putty in both conditions became shorter with an increase in the Na1. 8H1.2PO4 concentration, reaching approximately 7-13 min when the Na1. 8H1.2PO4 concentration was 0.6 mol/L or higher. The DTS value of HAP putty was relatively constant (10 MPa) regardless of the Na1.8H1. 2PO4 concentration (0.2-1.0 mol/L) when HAP putty was kept in an incubator. In contrast, when HAP putty was immersed in serum, the DTS value was dependent on the Na1.8H1.2PO4 concentration. It increased with the Na1.8H1.2PO4 concentration and reached approximately 5 MPa when the Na1.8H1.2PO4 concentration was 0.6 mol/L, after which it showed a relatively constant DTS value. We therefore would recommend a HAP putty that uses 0.6 mol/L Na1.8H1. 2PO4 since at that concentration the putty's setting time (approximately 10 min) is proper for clinical use and it shows good DTS value (approximately 5 MPa) even when it is immersed in serum immediately after mixing. Copyright 1999 John Wiley & Sons, Inc.

A study of phosphate absorption by magnesium iron hydroxycarbonate.

Science.gov (United States)

Du, Yi; Rees, Nicholas; O'Hare, Dermot

2009-10-21

A study of the mechanism of phosphate adsorption by magnesium iron hydroxycarbonate, [Mg(2.25)Fe(0.75)(OH)(6)](CO(3))(0.37).0.65H(2)O over a range of pH has been carried out. The efficiency of the phosphate removal from aqueous solution has been investigated between pH 3-9 and the resulting solid phases have been studied by elemental analysis, XRD, FT-IR, Raman, HRTEM, EDX and solid-state MAS (31)P NMR. The analytical and spectroscopic data suggest that phosphate removal from solution occurs not by anion intercalation of the relevant phosphorous oxyanion (H(2)PO(4)(-) or HPO(4)(2-)) into the LDH but by the precipitation of either an insoluble iron hydrogen phosphate hydrate and/or a magnesium phosphate hydrate.

31P NMR study of the interaction of inorganic phosphate with bovine copper-zinc superoxide dismutase

International Nuclear Information System (INIS)

de Freitas, D.M.; Luchinat, C.; Banci, L.; Bertini, I.; Valentine, J.S.

1987-01-01

Paramagnetic effect of 31 P phosphate resonances caused by Cu(II) ions in native and phenylglyoxal-modified bovine Cu,Zn-superoxide dismutase have been used to monitor the interaction of phosphate with these proteins. T 2 values are found to be 70 times smaller than T 1 , indicating that some mechanisms, as yet undefined, contribute to the line width. Using T 1 measurements, it was determined that the affinity constants for phosphate binding to the native protein are 20 +/- 4 and 34 +/- 3 M -1 at pH 8.0 and 7.0 respectively, and that the Cu(II)-phosphate distance 5.3 A. At pH 6.3, two binding sites are observed, one at a distance >7 A with an affinity constant >100 M -1 and another at approximately 5 A with an affinity constant of 10 M -1 . Modification of the protein with phenylglyoxal causes the affinity of phosphate for the same sites to decrease by a factor of 3 at pH 6.3. These results indicate that phosphate does not bind directly to Cu(II) but to a site close by. It was concluded that the site of phosphate binding is Arg-141, which in known from X-ray structural evidence to be located approximately 5 Angstrom form the copper center. 26 references, 4 figures

{tau} - hydrogen phosphate of zirconia in sodium salt form and some of its properties; {tau} - hidrogenofosfato de zirconio en forma sodica y algunas de sus propiedades

Energy Technology Data Exchange (ETDEWEB)

Fernandez V, S.M.; Ordonez R, E. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

2004-07-01

It is reported the obtaining and characterization in the sodium salt form of the {tau}-hydrogen phosphate of zirconium in sodium form, this compound it was synthesized, for a new technique developed in the laboratory of Dept. of Chemistry of the ININ. The characterization was carried out for XRD, IR, Sem and EDS the thermal gravimetric analysis is also reported. (Author)

Characterization of the sterol and phosphatidylinositol 4-phosphate binding properties of Golgi-associated OSBP-related protein 9 (ORP9.

Directory of Open Access Journals (Sweden)

Xinwei Liu

Full Text Available Oxysterol binding protein (OSBP and OSBP-related proteins (ORPS have a conserved lipid-binding fold that accommodates cholesterol, oxysterols and/or phospholipids. The diversity of OSBP/ORPs and their potential ligands has complicated the analysis of transfer and signalling properties of this mammalian gene family. In this study we explored the use of the fluorescent sterol cholestatrienol (CTL to measure sterol binding by ORP9 and competition by other putative ligands. Relative to cholesterol, CTL and dehydroergosterol (DHE were poor ligands for OSBP. In contrast, both long (ORP9L and short (ORP9S variants of ORP9 rapidly extracted CTL, and to a lesser extent DHE, from liposomes. ORP9L and ORP9S also extracted [32P]phosphatidylinositol 4-phosphate (PI-4P from liposomes, which was inhibited by mutating two conserved histidine residues (HH488,489AA at the entrance to the binding pocket but not by a mutation in the lid region that inhibited cholesterol binding. Results of direct binding and competition assays showed that phosphatidylserine was poorly extracted from liposomes by ORP9 compared to CTL and PI-4P. ORP9L and PI-4P did not co-localize in the trans-Golgi/TGN of HeLa cells, and siRNA silencing of ORP9L expression did not affect PI-4P distribution in the Golgi apparatus. However, transient overexpression of ORP9L or ORP9S in CHO cells, but not the corresponding PI-4P binding mutants, prevented immunostaining of Golgi-associated PI-4P. The apparent sequestration of Golgi PI-4P by ORP9S was identified as a possible mechanism for its growth inhibitory effects. These studies identify ORP9 as a dual sterol/PI-4P binding protein that could regulate PI-4P in the Golgi apparatus.

Characterization of the sterol and phosphatidylinositol 4-phosphate binding properties of Golgi-associated OSBP-related protein 9 (ORP9).

Science.gov (United States)

Liu, Xinwei; Ridgway, Neale D

2014-01-01

Oxysterol binding protein (OSBP) and OSBP-related proteins (ORPS) have a conserved lipid-binding fold that accommodates cholesterol, oxysterols and/or phospholipids. The diversity of OSBP/ORPs and their potential ligands has complicated the analysis of transfer and signalling properties of this mammalian gene family. In this study we explored the use of the fluorescent sterol cholestatrienol (CTL) to measure sterol binding by ORP9 and competition by other putative ligands. Relative to cholesterol, CTL and dehydroergosterol (DHE) were poor ligands for OSBP. In contrast, both long (ORP9L) and short (ORP9S) variants of ORP9 rapidly extracted CTL, and to a lesser extent DHE, from liposomes. ORP9L and ORP9S also extracted [32P]phosphatidylinositol 4-phosphate (PI-4P) from liposomes, which was inhibited by mutating two conserved histidine residues (HH488,489AA) at the entrance to the binding pocket but not by a mutation in the lid region that inhibited cholesterol binding. Results of direct binding and competition assays showed that phosphatidylserine was poorly extracted from liposomes by ORP9 compared to CTL and PI-4P. ORP9L and PI-4P did not co-localize in the trans-Golgi/TGN of HeLa cells, and siRNA silencing of ORP9L expression did not affect PI-4P distribution in the Golgi apparatus. However, transient overexpression of ORP9L or ORP9S in CHO cells, but not the corresponding PI-4P binding mutants, prevented immunostaining of Golgi-associated PI-4P. The apparent sequestration of Golgi PI-4P by ORP9S was identified as a possible mechanism for its growth inhibitory effects. These studies identify ORP9 as a dual sterol/PI-4P binding protein that could regulate PI-4P in the Golgi apparatus.

Studies of layered uranium(VI) compounds. I. High proton conductivity in polycrystalline hydrogen uranyl phosphate tetrahydrate

International Nuclear Information System (INIS)

Howe, A.T.; Shilton, M.G.

1979-01-01

Hydrogen uranyl phosphate tetrahydrate HUO 2 PO 4 .4H 2 O has a high proton conductivity. The ac conductivity was 0.4 ohm -1 m -1 at 290 0 K measured parallel to the faces of sintered disks of the compound. The activation energy was found to be 31 +- 3 kJ mole -1 . The values of conductivity were between 3 and 10 times lower when measured perpendicular to the disk faces due to preferred orientation of the plate-like crystals. Both the powder and sintered disks are stable in air and insoluble in phosphoric acid solution of pH 2.5. Experiments are described which enable possible grain boundary contributions to the conductivity to be determined in such hydrates. The extrinsic grain boundary contribution to the conductivity was found to be small from experiments in which the pH in a solution cell was varied. The abnormally high bulk H + conductivity thus inferred is attributed primarily to the high concentration of H + , which exists as H 3 O + in the interlamellar hydrogen-bounded network. A Grotthus-type mechanism of conduction is proposed which involves intermolecular transfer steps (hopping) and intramolecular transfer steps, in comparable numbers, the former facilitated by the high concentration of H 3 O + ions in the structure, and the latter most likely facilitated by the high concentration of H-bond vacancies. 8 figures, 1 table

Steric Effects on the Binding of Phosphate and Polyphosphate Anions by Zinc(II) and Copper(II) Dinuclear Complexes of m-Xylyl-bis-cyclen.

Science.gov (United States)

Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita

2018-05-11

The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.

Are Polyphosphates or Phosphate Esters Prebiotic Reagents?

Science.gov (United States)

Keefe, Anthony D.; Miller, Stanley L.

1995-01-01

It is widely held that there was a phosphate compound in prebiotic chemistry that played the role of adenosine triphosphate and that the first living organisms had ribose-phosphate in the backbone of their genetic material. However, there are no known efficient prebiotic synthesis of high-energy phosphates or phosphate esters. We review the occurrence of phosphates in nature, the efficiency of the volcanic synthesis of P4O10, the efficiency of polyphosphate synthesis by heating phosphate minerals under geological conditions, and the use of high-energy organic compounds such as cyanamide or hydrogen cyanide. These are shown to be inefficient processes especially when the hydrolysis of the polyphosphates is taken into account. For example, if a whole atmosphere of methane or carbon monoxide were converted to cyanide which somehow synthesized polyphosphates quantitatively, the polyphosphate concentration in the ocean would still have been insignificant. We also attempted to find more efficient high-energy polymerizing agents by spark discharge syntheses, but without success. There may still be undiscovered robust prebiotic syntheses of polyphosphates, or mechanisms for concentrating them, but we conclude that phosphate esters may not have been constituents of the first genetic material. Phosphoanhydrides are also unlikely as prebiotic energy sources.

Binding of Divalent Magnesium by Escherichia coli Phosphoribosyl Diphosphate Synthetase

DEFF Research Database (Denmark)

Willemoës, Martin; Hove-Jensen, Bjarne

1997-01-01

The mechanism of binding of the substrates MgATP and ribose 5-phosphate as well as Mg2+ to the enzyme 5-phospho-d-ribosyl a-1-diphosphate synthetase from Escherichia coli has been analyzed. By use of the competive inhibitors of ATP and ribose 5-phosphate binding, a,ß-methylene ATP and (+)-1-a,2-a...

Oxysterol-binding Protein Activation at Endoplasmic Reticulum-Golgi Contact Sites Reorganizes Phosphatidylinositol 4-Phosphate Pools*

Science.gov (United States)

Goto, Asako; Charman, Mark; Ridgway, Neale D.

2016-01-01

Oxysterol-binding protein (OSBP) exchanges cholesterol and phosphatidylinositol 4-phosphate (PI-4P) at contact sites between the endoplasmic reticulum (ER) and the trans-Golgi/trans-Golgi network. 25-Hydroxycholesterol (25OH) competitively inhibits this exchange reaction in vitro and causes the constitutive localization of OSBP at the ER/Golgi interface and PI-4P-dependent recruitment of ceramide transfer protein (CERT) for sphingomyelin synthesis. We used PI-4P probes and mass analysis to determine how OSBP controls the availability of PI-4P for this metabolic pathway. Treatment of fibroblasts or Chinese hamster ovary (CHO) cells with 25OH caused a 50–70% reduction in Golgi-associated immunoreactive PI-4P that correlated with Golgi localization of OSBP. In contrast, 25OH caused an OSBP-dependent enrichment in Golgi PI-4P that was detected with a pleckstrin homology domain probe. The cellular mass of phosphatidylinositol monophosphates and Golgi PI-4P measured with an unbiased PI-4P probe (P4M) was unaffected by 25OH and OSBP silencing, indicating that OSBP shifts the distribution of PI-4P upon localization to ER-Golgi contact sites. The PI-4P and sterol binding activities of OSBP were both required for 25OH activation of sphingomyelin synthesis, suggesting that 25OH must be exchanged for PI-4P to be concentrated at contact sites. We propose a model wherein 25OH activation of OSBP promotes the binding and retention of PI-4P at ER-Golgi contact sites. This pool of PI-4P specifically recruits pleckstrin homology domain-containing proteins involved in lipid transfer and metabolism, such as CERT. PMID:26601944

Interaction between calcium and phosphate adsorption on goethite.

Science.gov (United States)

Rietra, R P; Hiemstra, T; van Riemsdijk, W H

2001-08-15

Quantitatively, little is known about the ion interaction processes that are responsible for the binding of phosphate in soil, water, and sediment, which determine the bioavailability and mobility of phosphate. Studies have shown that metal hydroxides are often responsible for the binding of PO4 in soils and sediments, but the binding behavior of PO4 in these systems often differs significantly from adsorption studies on metal hydroxides in laboratory. The interaction between PO4 and Ca adsorption was studied on goethite because Ca can influence the PO4 adsorption equilibria. Since adsorption interactions are very difficult to discriminate from precipitation reactions, conditions were chosen to prevent precipitation of Ca-PO4 solids. Adsorption experiments of PO4 and Ca, individually and in combination, show a strong interaction between adsorbed Ca and PO4 on goethite for conditions below the saturation index of apatite. It is shown that it is possible to predict the adsorption and interaction of PO4 and Ca on electrostatic arguments using the model parameter values derived from the single-ion systems and without invoking ternary complex formation or precipitation. The model enables the prediction of the Ca-PO4 interaction for environmentally relevant calcium and phosphate concentrations.

Factor VII and protein C are phosphatidic acid-binding proteins.

Science.gov (United States)

Tavoosi, Narjes; Smith, Stephanie A; Davis-Harrison, Rebecca L; Morrissey, James H

2013-08-20

Seven proteins in the human blood clotting cascade bind, via their GLA (γ-carboxyglutamate-rich) domains, to membranes containing exposed phosphatidylserine (PS), although with membrane binding affinities that vary by 3 orders of magnitude. Here we employed nanodiscs of defined phospholipid composition to quantify the phospholipid binding specificities of these seven clotting proteins. All bound preferentially to nanobilayers in which PS headgroups contained l-serine versus d-serine. Surprisingly, however, nanobilayers containing phosphatidic acid (PA) bound substantially more of two of these proteins, factor VIIa and activated protein C, than did equivalent bilayers containing PS. Consistent with this finding, liposomes containing PA supported higher proteolytic activity by factor VIIa and activated protein C toward their natural substrates (factors X and Va, respectively) than did PS-containing liposomes. Moreover, treating activated human platelets with phospholipase D enhanced the rates of factor X activation by factor VIIa in the presence of soluble tissue factor. We hypothesize that factor VII and protein C bind preferentially to the monoester phosphate of PA because of its accessibility and higher negative charge compared with the diester phosphates of most other phospholipids. We further found that phosphatidylinositol 4-phosphate, which contains a monoester phosphate attached to its myo-inositol headgroup, also supported enhanced enzymatic activity of factor VIIa and activated protein C. We conclude that factor VII and protein C bind preferentially to monoester phosphates, which may have implications for the function of these proteases in vivo.

Intra- versus Intermolecular Hydrogen Bonding: Solvent-Dependent Conformational Preferences of a Common Supramolecular Binding Motif from 1 H NMR and Vibrational Circular Dichroism Spectra.

Science.gov (United States)

Demarque, Daniel P; Merten, Christian

2017-12-19

When predicting binding properties of small molecules or larger supramolecular aggregates, intra- and intermolecular hydrogen bonds are often considered the most important factor. Spectroscopic techniques such as 1 H NMR spectroscopy are typically utilized to characterize such binding events, but interpretation is often qualitative and follows chemical intuition. In this study, we compare the effects of intramolecular hydrogen bonding and solvation on two chiral 2,6-pyridinediyl-dialkylamides. In comparison with 1 H NMR spectroscopy, vibrational circular dichroism (VCD) spectroscopy proved to be more sensitive to conformational changes. In fact, the change of the solvent from CDCl 3 to [D 6 ]DMSO generates mirror-image VCD spectra for the same enantiomer. Here, the common sense that the sterically less hindered group is more prone to solvation proved to be wrong according predicted VCD spectra, which clearly show that both asymmetric amide hydrogens are equally likely to be solvated, but never simultaneously. The competition between intra- and intermolecular hydrogen bonding and their importance for a correct prediction of spectral properties are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new human NHERF1 mutation decreases renal phosphate transporter NPT2a expression by a PTH-independent mechanism.

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Marie Courbebaisse

Full Text Available BACKGROUND: The sodium-hydrogen exchanger regulatory factor 1 (NHERF1 binds to the main renal phosphate transporter NPT2a and to the parathyroid hormone (PTH receptor. We have recently identified mutations in NHERF1 that decrease renal phosphate reabsorption by increasing PTH-induced cAMP production in the renal proximal tubule. METHODS: We compared relevant parameters of phosphate homeostasis in a patient with a previously undescribed mutation in NHERF1 and in control subjects. We expressed the mutant NHERF1 protein in Xenopus Oocytes and in cultured cells to study its effects on phosphate transport and PTH-induced cAMP production. RESULTS: We identified in a patient with inappropriate renal phosphate reabsorption a previously unidentified mutation (E68A located in the PDZ1 domain of NHERF1.We report the consequences of this mutation on NHERF1 function. E68A mutation did not modify cAMP production in the patient. PTH-induced cAMP synthesis and PKC activity were not altered by E68A mutation in renal cells in culture. In contrast to wild-type NHERF1, expression of the E68A mutant in Xenopus oocytes and in human cells failed to increase phosphate transport. Pull down experiments showed that E68A mutant did not interact with NPT2a, which robustly interacted with wild type NHERF1 and previously identified mutants. Biotinylation studies revealed that E68A mutant was unable to increase cell surface expression of NPT2a. CONCLUSIONS: Our results indicate that the PDZ1 domain is critical for NHERF1-NPT2a interaction in humans and for the control of NPT2a expression at the plasma membrane. Thus we have identified a new mechanism of renal phosphate loss and shown that different mutations in NHERF1 can alter renal phosphate reabsorption via distinct mechanisms.

Ultrafast phosphate hydration dynamics in bulk H2O

Science.gov (United States)

Costard, Rene; Tyborski, Tobias; Fingerhut, Benjamin P.; Elsaesser, Thomas

2015-06-01

Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H2PO4- 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 S ( PO2 - ) ) and asymmetric ( ν A S ( PO2 - ) ) PO 2- stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH)2) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay 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 S ( PO2 - ) and ν A S ( PO2 - ) transition frequencies with larger frequency excursions for ν A S ( PO2 - ) . The calculated frequency-time correlation function is in good agreement with the experiment. The ν ( PO2 - ) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H2PO4-/H2O 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.

Ancestral mutations as a tool for solubilizing proteins: The case of a hydrophobic phosphate-binding protein

Directory of Open Access Journals (Sweden)

Daniel Gonzalez

2014-01-01

Full Text Available Stable and soluble proteins are ideal candidates for functional and structural studies. Unfortunately, some proteins or enzymes can be difficult to isolate, being sometimes poorly expressed in heterologous systems, insoluble and/or unstable. Numerous methods have been developed to address these issues, from the screening of various expression systems to the modification of the target protein itself. Here we use a hydrophobic, aggregation-prone, phosphate-binding protein (HPBP as a case study. We describe a simple and fast method that selectively uses ancestral mutations to generate a soluble, stable and functional variant of the target protein, here named sHPBP. This variant is highly expressed in Escherichia coli, is easily purified and its structure was solved at much higher resolution than its wild-type progenitor (1.3 versus 1.9 Å, respectively.

Calcium-phosphate-osteopontin particles for caries control

DEFF Research Database (Denmark)

Schlafer, Sebastian; Birkedal, Henrik; Olsen, Jakob

2016-01-01

Caries is caused by acid production in biofilms on dental surfaces. Preventing caries therefore involves control of microorganisms and/or the acid produced. Here, calcium-phosphate-osteopontin particles are presented as a new approach to caries control. The particles are made by co......-precipitation and designed to bind to bacteria in biofilms, impede biofilm build-up without killing the microflora, and release phosphate ions to buffer bacterial acid production if the pH decreases below 6. Analysis of biofilm formation and pH in a five-species biofilm model for dental caries showed that treatment......H always remained above 5.5. Hence, calcium-phosphate-osteopontin particles show potential for applications in caries control....

Oxysterol-binding Protein Activation at Endoplasmic Reticulum-Golgi Contact Sites Reorganizes Phosphatidylinositol 4-Phosphate Pools.

Science.gov (United States)

Goto, Asako; Charman, Mark; Ridgway, Neale D

2016-01-15

Oxysterol-binding protein (OSBP) exchanges cholesterol and phosphatidylinositol 4-phosphate (PI-4P) at contact sites between the endoplasmic reticulum (ER) and the trans-Golgi/trans-Golgi network. 25-Hydroxycholesterol (25OH) competitively inhibits this exchange reaction in vitro and causes the constitutive localization of OSBP at the ER/Golgi interface and PI-4P-dependent recruitment of ceramide transfer protein (CERT) for sphingomyelin synthesis. We used PI-4P probes and mass analysis to determine how OSBP controls the availability of PI-4P for this metabolic pathway. Treatment of fibroblasts or Chinese hamster ovary (CHO) cells with 25OH caused a 50-70% reduction in Golgi-associated immunoreactive PI-4P that correlated with Golgi localization of OSBP. In contrast, 25OH caused an OSBP-dependent enrichment in Golgi PI-4P that was detected with a pleckstrin homology domain probe. The cellular mass of phosphatidylinositol monophosphates and Golgi PI-4P measured with an unbiased PI-4P probe (P4M) was unaffected by 25OH and OSBP silencing, indicating that OSBP shifts the distribution of PI-4P upon localization to ER-Golgi contact sites. The PI-4P and sterol binding activities of OSBP were both required for 25OH activation of sphingomyelin synthesis, suggesting that 25OH must be exchanged for PI-4P to be concentrated at contact sites. We propose a model wherein 25OH activation of OSBP promotes the binding and retention of PI-4P at ER-Golgi contact sites. This pool of PI-4P specifically recruits pleckstrin homology domain-containing proteins involved in lipid transfer and metabolism, such as CERT. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Expression profiles of glyceraldehyde-3-phosphate dehydrogenase from Clonorchis sinensis: a glycolytic enzyme with plasminogen binding capacity.

Science.gov (United States)

Hu, Yue; Zhang, Erhong; Huang, Lisi; Li, Wenfang; Liang, Pei; Wang, Xiaoyun; Xu, Jin; Huang, Yan; Yu, Xinbing

2014-12-01

Globally, 15-20 million people are infected with Clonorchis sinensis (C. sinensis) which results in clonorchiasis. In China, clonorchiasis is considered to be one of the fastest-growing food-borne parasitic diseases. That more key molecules of C. sinensis are characterized will be helpful to understand biology and pathogenesis of the carcinogenic liver fluke. Glyceraldehyde-3-phosphate dehydrogenases (GAPDHs) from many species have functions other than their catalytic role in glycolysis. In the present study, we analyzed the sequence and structure of GAPDH from C. sinensis (CsGAPDH) by using bioinformatics tools and obtained its recombinant protein by prokaryotic expression system, to learn its expression profiles and molecular property. CsGAPDH could bind to human intrahepatic biliary epithelial cell in vivo and in vitro by the method of immunofluorescence assays. CsGAPDH also disturbed in lumen of biliary tract near to the parasite in the liver of infected rat. Western blotting analysis together with immunofluorescence assay indicated that CsGAPDH was a component of excretory/secretory proteins (CsESPs) and a surface-localized protein of C. sinensis. Quantitative real-time PCR (Q-PCR) and Western blotting demonstrated that CsGAPDHs are expressed at the life stages of adult worm, metacercaria, and egg, but the expression levels were different from each other. Recombinant CsGAPDH (rCsGAPDH) was confirmed to have the capacity to catalyze the conversion of glyceraldehyde 3-phosphate to D-glycerate 1,3-bisphosphate which was inhibited by AMP in a dose-dependent manner. In addition, rCsGAPDH was able to interact with human plasminogen in a dose-dependent manner by ELISA. The interaction could be inhibited by lysine. The plasminogen binding capacity of rCsGAPDH along with the distribution of CsGAPDH in vivo and in the liver of C. sinensis-infected rat hinted that surface-localized CsGAPDH might play an important role in host invasion of the worm besides its glycolytic

Structural and Thermodynamic Insights into Chitooligosaccharide Binding to Human Cartilage Chitinase 3-like Protein 2 (CHI3L2 or YKL-39)*

Science.gov (United States)

Ranok, Araya; Wongsantichon, Jantana; Robinson, Robert C.; Suginta, Wipa

2015-01-01

Four crystal structures of human YKL-39 were solved in the absence and presence of chitooligosaccharides. The structure of YKL-39 comprises a major (β/α)8 triose-phosphate isomerase barrel domain and a small α + β insertion domain. Structural analysis demonstrates that YKL-39 interacts with chitooligosaccharides through hydrogen bonds and hydrophobic interactions. The binding of chitin fragments induces local conformational changes that facilitate tight binding. Compared with other GH-18 members, YKL-39 has the least extended chitin-binding cleft, containing five subsites for sugars, namely (−3)(−2)(−1)(+1)(+2), with Trp-360 playing a prominent role in the sugar-protein interactions at the center of the chitin-binding cleft. Evaluation of binding affinities obtained from isothermal titration calorimetry and intrinsic fluorescence spectroscopy suggests that YKL-39 binds to chitooligosaccharides with Kd values in the micromolar concentration range and that the binding energies increase with the chain length. There were no significant differences between the Kd values of chitopentaose and chitohexaose, supporting the structural evidence for the five binding subsite topology. Thermodynamic analysis indicates that binding of chitooligosaccharide to YKL-39 is mainly driven by enthalpy. PMID:25477513

ION EXCHANGE SUBSTANCES BY SAPONIFICATION OF ALLYL PHOSPHATE POLYMERS

Science.gov (United States)

Kennedy, J.

1959-04-14

An ion exchange resin having a relatively high adsorption capacity tor uranyl ion as compared with many common cations is reported. The resin comprises an alphyl-allyl hydrogen phosphate polymer, the alphyl group being either allyl or a lower alkyl group having up to 5 carbon atoins. The resin is prepared by polymerizing compounds such as alkyl-diallyl phosphate and triallyl phosphate in the presence of a free radical generating substance and then partially hydrolyzing the resulting polymer to cause partial replacement of organic radicals by cations. A preferred free radical gencrating agent is dibenzoyl peroxide. The partial hydrolysis is brought about by refluxing the polymer with concentrated aqueous NaOH for three or four hours.

Interaction between the PH and START domains of ceramide transfer protein competes with phosphatidylinositol 4-phosphate binding by the PH domain.

Science.gov (United States)

Prashek, Jennifer; Bouyain, Samuel; Fu, Mingui; Li, Yong; Berkes, Dusan; Yao, Xiaolan

2017-08-25

De novo synthesis of the sphingolipid sphingomyelin requires non-vesicular transport of ceramide from the endoplasmic reticulum to the Golgi by the multidomain protein ceramide transfer protein (CERT). CERT's N-terminal pleckstrin homology (PH) domain targets it to the Golgi by binding to phosphatidylinositol 4-phosphate (PtdIns(4)P) in the Golgi membrane, whereas its C-terminal StAR-related lipid transfer domain (START) carries out ceramide transfer. Hyperphosphorylation of a serine-rich motif immediately after the PH domain decreases both PtdIns(4)P binding and ceramide transfer by CERT. This down-regulation requires both the PH and START domains, suggesting a possible inhibitory interaction between the two domains. In this study we show that isolated PH and START domains interact with each other. The crystal structure of a PH-START complex revealed that the START domain binds to the PH domain at the same site for PtdIns(4)P-binding, suggesting that the START domain competes with PtdIns(4)P for association with the PH domain. We further report that mutations disrupting the PH-START interaction increase both PtdIns(4)P-binding affinity and ceramide transfer activity of a CERT-serine-rich phosphorylation mimic. We also found that these mutations increase the Golgi localization of CERT inside the cell, consistent with enhanced PtdIns(4)P binding of the mutant. Collectively, our structural, biochemical, and cellular investigations provide important structural insight into the regulation of CERT function and localization. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Indigo Carmine-Cu complex probe exhibiting dual colorimetric/fluorimetric sensing for selective determination of mono hydrogen phosphate ion and its logic behavior

Science.gov (United States)

Tavallali, Hossein; Deilamy-Rad, Gohar; Moaddeli, Ali; Asghari, Khadijeh

2017-08-01

A new selective probe based on copper complex of Indigo Carmine (IC-Cu2) for colorimetric, naked-eye, and fluorimetric recognition of mono hydrogen phosphate (MHP) ion in H2O/DMSO (4:1 v/v, 1.0 mmol L- 1 HEPES buffer solution pH 7.5) was developed. Detection limit of HPO42 - determination, achieved by fluorimetric and 3lorimetric method, are 0.071 and 1.46 μmol L- 1, respectively. Potential, therefore is clearly available in IC-Cu2 complex to detect HPO42 - in micromolar range via dual visible color change and fluorescence response. Present method shows high selectivity toward HPO42 - over other phosphate species and other anions and was successfully utilized for analysis of P2O5 content of a fertilizer sample. The results obtained by proposed chemosensor presented good agreement with those obtained the colorimetric reference method. INHIBIT and IMPLICATION logic gates operating at molecular level have been achieved using Cu2 + and HPO42 - as chemical inputs and UV-Vis absorbance signal as output.

Development of nanosensors for studying intracellular phosphate levels

DEFF Research Database (Denmark)

Gu, Hong

-time monitoring of Pi metabolism in living cells, providing a new tool for fluxomics (measurement of metabolic flux), analysis of pathophysiology or changes of Pi during cell activity. Transformation of plants with FLIPs had resulted in only low expression levels. As an alternative a protein transduction domain......Abstract Inorganic phosphate (Pi) is an essential macronutrient that plays a central role in metabolism and signal transduction in plants. Uptake, compartmentation and transport are important players of cellular Pi homeostasis; however, methods to determine the cellular phosphate concentration...... of a substrate-binding protein linked to two fluorescent reporter proteins. Substrate binding changes the conformation of the nanosensor and, hence, the efficiency of fluorescence resonance energy transfer (FRET) between the reporter proteins. The aim of the present project was to develop nanosensors for Pi...

Bacterial periplasmic sialic acid-binding proteins exhibit a conserved binding site

Energy Technology Data Exchange (ETDEWEB)

Gangi Setty, Thanuja [Institute for Stem Cell Biology and Regenerative Medicine, NCBS Campus, GKVK Post, Bangalore, Karnataka 560 065 (India); Cho, Christine [Carver College of Medicine, University of Iowa, Iowa City, IA 52242-1109 (United States); Govindappa, Sowmya [Institute for Stem Cell Biology and Regenerative Medicine, NCBS Campus, GKVK Post, Bangalore, Karnataka 560 065 (India); Apicella, Michael A. [Carver College of Medicine, University of Iowa, Iowa City, IA 52242-1109 (United States); Ramaswamy, S., E-mail: ramas@instem.res.in [Institute for Stem Cell Biology and Regenerative Medicine, NCBS Campus, GKVK Post, Bangalore, Karnataka 560 065 (India)

2014-07-01

Structure–function studies of sialic acid-binding proteins from F. nucleatum, P. multocida, V. cholerae and H. influenzae reveal a conserved network of hydrogen bonds involved in conformational change on ligand binding. Sialic acids are a family of related nine-carbon sugar acids that play important roles in both eukaryotes and prokaryotes. These sialic acids are incorporated/decorated onto lipooligosaccharides as terminal sugars in multiple bacteria to evade the host immune system. Many pathogenic bacteria scavenge sialic acids from their host and use them for molecular mimicry. The first step of this process is the transport of sialic acid to the cytoplasm, which often takes place using a tripartite ATP-independent transport system consisting of a periplasmic binding protein and a membrane transporter. In this paper, the structural characterization of periplasmic binding proteins from the pathogenic bacteria Fusobacterium nucleatum, Pasteurella multocida and Vibrio cholerae and their thermodynamic characterization are reported. The binding affinities of several mutations in the Neu5Ac binding site of the Haemophilus influenzae protein are also reported. The structure and the thermodynamics of the binding of sugars suggest that all of these proteins have a very well conserved binding pocket and similar binding affinities. A significant conformational change occurs when these proteins bind the sugar. While the C1 carboxylate has been identified as the primary binding site, a second conserved hydrogen-bonding network is involved in the initiation and stabilization of the conformational states.

Bacterial periplasmic sialic acid-binding proteins exhibit a conserved binding site

International Nuclear Information System (INIS)

Gangi Setty, Thanuja; Cho, Christine; Govindappa, Sowmya; Apicella, Michael A.; Ramaswamy, S.

2014-01-01

Structure–function studies of sialic acid-binding proteins from F. nucleatum, P. multocida, V. cholerae and H. influenzae reveal a conserved network of hydrogen bonds involved in conformational change on ligand binding. Sialic acids are a family of related nine-carbon sugar acids that play important roles in both eukaryotes and prokaryotes. These sialic acids are incorporated/decorated onto lipooligosaccharides as terminal sugars in multiple bacteria to evade the host immune system. Many pathogenic bacteria scavenge sialic acids from their host and use them for molecular mimicry. The first step of this process is the transport of sialic acid to the cytoplasm, which often takes place using a tripartite ATP-independent transport system consisting of a periplasmic binding protein and a membrane transporter. In this paper, the structural characterization of periplasmic binding proteins from the pathogenic bacteria Fusobacterium nucleatum, Pasteurella multocida and Vibrio cholerae and their thermodynamic characterization are reported. The binding affinities of several mutations in the Neu5Ac binding site of the Haemophilus influenzae protein are also reported. The structure and the thermodynamics of the binding of sugars suggest that all of these proteins have a very well conserved binding pocket and similar binding affinities. A significant conformational change occurs when these proteins bind the sugar. While the C1 carboxylate has been identified as the primary binding site, a second conserved hydrogen-bonding network is involved in the initiation and stabilization of the conformational states

A novel analytical method for in vivo phosphate tracking (Corrigendum in FEBS Letters, 2007, 581 p. 579)

DEFF Research Database (Denmark)

Gu, H.; Lalonde, S.; Okumoto, S.

2006-01-01

Genetically-encoded fluorescence resonance energy transfer (FRET) sensors for phosphate (Pi) (FLIPPi) were engineered by fusing a predicted Synechococcus phosphate-binding protein (PiBP) to eCFP and Venus. Purified fluorescent indicator protein for inorganic phosphate (FLIPPi), in which the fluor...

Thioredoxin binding site of phosphoribulokinase overlaps the catalytic site

International Nuclear Information System (INIS)

Porter, M.A.; Hartman, F.C.

1986-01-01

The ATP-regulatory binding site of phosphoribulokinase was studied using bromoacetylethanolamine phosphate (BrAcNHEtOP). BrAcNHEtOP binds to the active-regulatory binding site of the protein. Following trypsin degradation of the labeled protein, fragments were separated by HPLC and sequenced. (DT)

Ultrafast phosphate hydration dynamics in bulk H2O

International Nuclear Information System (INIS)

Costard, Rene; Tyborski, Tobias; Fingerhut, Benjamin P.; Elsaesser, Thomas

2015-01-01

Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H 2 PO 4 − 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 S (PO 2 − )) and asymmetric (ν AS (PO 2 − )) PO 2 − stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH) 2 ) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay 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 S (PO 2 − ) and ν AS (PO 2 − ) transition frequencies with larger frequency excursions for ν AS (PO 2 − ). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO 2 − ) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H 2 PO 4 − /H 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

Phosphate-Catalyzed Hydrogen Peroxide Formation from Agar, Gellan, and κ-Carrageenan and Recovery of Microbial Cultivability via Catalase and Pyruvate.

Science.gov (United States)

Kawasaki, Kosei; Kamagata, Yoichi

2017-11-01

Previously, we reported that when agar is autoclaved with phosphate buffer, hydrogen peroxide (H 2 O 2 ) is formed in the resulting medium (PT medium), and the colony count on the medium inoculated with environmental samples becomes much lower than that on a medium in which agar and phosphate are autoclaved separately (PS medium) (T. Tanaka et al., Appl Environ Microbiol 80:7659-7666, 2014, https://doi.org/10.1128/AEM.02741-14). However, the physicochemical mechanisms underlying this observation remain largely unknown. Here, we determined the factors affecting H 2 O 2 formation in agar. The H 2 O 2 formation was pH dependent: H 2 O 2 was formed at high concentrations in an alkaline or neutral phosphate buffer but not in an acidic buffer. Ammonium ions enhanced H 2 O 2 formation, implying the involvement of the Maillard reaction catalyzed by phosphate. We found that other gelling agents (e.g., gellan and κ-carrageenan) also produced H 2 O 2 after being autoclaved with phosphate. We then examined the cultivability of microorganisms from a fresh-water sample to test whether catalase and pyruvate, known as H 2 O 2 scavengers, are effective in yielding high colony counts. The colony count on PT medium was only 5.7% of that on PS medium. Catalase treatment effectively restored the colony count of PT medium (to 106% of that on PS medium). In contrast, pyruvate was not as effective as catalase: the colony count on sodium pyruvate-supplemented PT medium was 58% of that on PS medium. Given that both catalase and pyruvate can remove H 2 O 2 from PT medium, these observations indicate that although H 2 O 2 is the main cause of reduced colony count on PT medium, other unknown growth-inhibiting substances that cannot be removed by pyruvate (but can be by catalase) may also be involved. IMPORTANCE The majority of bacteria in natural environments are recalcitrant to laboratory culture techniques. Previously, we demonstrated that one reason for this is the formation of high H 2 O

Electrochemical impedance study of copper in phosphate buffered solution

International Nuclear Information System (INIS)

Salimon, J.; Mohamad, M.; Yamin, B.M.; Kalaji, M.

2003-01-01

The processes occurring on the copper electrode surface in phosphate buffered solution were investigated using the Electrochemical Impedance Spectroscopy. The electrochemical behaviors of copper through their charge transfer resistance and double-layer capacitance at the onset of the hydrogen evolution region and the anodic passivation layer formation and diffusion of copper species at anodic potential regions are discussed. The specific adsorption of anions (hydroxide and/or H/sub 2/PO/sub 4/) occurred at potential less negative than -0.9V. Adsorbed hydrogen appeared at hydrogen evolution region at potential range of -1.5 to -1.0 V. The deposition of insoluble copper species occurred at anodic potential regions. (author)

Phosphate control in dialysis

Directory of Open Access Journals (Sweden)

Cupisti A

2013-10-01

Full Text Available Adamasco Cupisti,1 Maurizio Gallieni,2 Maria Antonietta Rizzo,2 Stefania Caria,3 Mario Meola,4 Piergiorgio Bolasco31Department of Clinical and Experimental Medicine, University of Pisa, Pisa, Italy; 2Nephrology and Dialysis Unit, San Carlo Borromeo Hospital, Milan, Italy; 3Territorial Department of Nephrology and Dialysis, ASL Cagliari, Italy; 4Sant'Anna School of Advanced Studies, University of Pisa, Pisa, ItalyAbstract: Prevention and correction of hyperphosphatemia is a major goal of chronic kidney disease–mineral and bone disorder (CKD–MBD management, achievable through avoidance of a positive phosphate balance. To this aim, optimal dialysis removal, careful use of phosphate binders, and dietary phosphate control are needed to optimize the control of phosphate balance in well-nourished patients on a standard three-times-a-week hemodialysis schedule. Using a mixed diffusive–convective hemodialysis tecniques, and increasing the number and/or the duration of dialysis tecniques are all measures able to enhance phosphorus (P mass removal through dialysis. However, dialytic removal does not equal the high P intake linked to the high dietary protein requirement of dialysis patients; hence, the use of intestinal P binders is mandatory to reduce P net intestinal absorption. Unfortunately, even a large dose of P binders is able to bind approximately 200–300 mg of P on a daily basis, so it is evident that their efficacy is limited in the case of an uncontrolled dietary P load. Hence, limitation of dietary P intake is needed to reach the goal of neutral phosphate balance in dialysis, coupled to an adequate protein intake. To this aim, patients should be informed and educated to avoid foods that are naturally rich in phosphate and also processed food with P-containing preservatives. In addition, patients should preferentially choose food with a low P-to-protein ratio. For example, patients could choose egg white or protein from a vegetable source

Binding of ATP by pertussis toxin and isolated toxin subunits

International Nuclear Information System (INIS)

Hausman, S.Z.; Manclark, C.R.; Burns, D.L.

1990-01-01

The binding of ATP to pertussis toxin and its components, the A subunit and B oligomer, was investigated. Whereas, radiolabeled ATP bound to the B oligomer and pertussis toxin, no binding to the A subunit was observed. The binding of [ 3 H]ATP to pertussis toxin and the B oligomer was inhibited by nucleotides. The relative effectiveness of the nucleotides was shown to be ATP > GTP > CTP > TTP for pertussis toxin and ATP > GTP > TTP > CTP for the B oligomer. Phosphate ions inhibited the binding of [ 3 H]ATP to pertussis toxin in a competitive manner; however, the presence of phosphate ions was essential for binding of ATP to the B oligomer. The toxin substrate, NAD, did not affect the binding of [ 3 H]ATP to pertussis toxin, although the glycoprotein fetuin significantly decreased binding. These results suggest that the binding site for ATP is located on the B oligomer and is distinct from the enzymatically active site but may be located near the eukaryotic receptor binding site

Binding of ATP by pertussis toxin and isolated toxin subunits

Energy Technology Data Exchange (ETDEWEB)

Hausman, S.Z.; Manclark, C.R.; Burns, D.L. (Center for Biologics Evaluation and Research, Bethesda, MD (USA))

1990-07-03

The binding of ATP to pertussis toxin and its components, the A subunit and B oligomer, was investigated. Whereas, radiolabeled ATP bound to the B oligomer and pertussis toxin, no binding to the A subunit was observed. The binding of ({sup 3}H)ATP to pertussis toxin and the B oligomer was inhibited by nucleotides. The relative effectiveness of the nucleotides was shown to be ATP > GTP > CTP > TTP for pertussis toxin and ATP > GTP > TTP > CTP for the B oligomer. Phosphate ions inhibited the binding of ({sup 3}H)ATP to pertussis toxin in a competitive manner; however, the presence of phosphate ions was essential for binding of ATP to the B oligomer. The toxin substrate, NAD, did not affect the binding of ({sup 3}H)ATP to pertussis toxin, although the glycoprotein fetuin significantly decreased binding. These results suggest that the binding site for ATP is located on the B oligomer and is distinct from the enzymatically active site but may be located near the eukaryotic receptor binding site.

Calcium-phosphate-osteopontin particles for caries control

DEFF Research Database (Denmark)

Schlafer, Sebastian

Oftentimes caries lesions develop in protected sites that are difficult to access by self-performed mechanical tooth cleaning. At present, there is a growing interest in chemical adjuncts to mechanical procedures of oral hygiene that aim at biofilm control rather than biofilm eradication. Calcium......-phosphate-osteopontin particles are a new promising therapeutic approach to caries control. They are designed to bind to dental biofilms and interfere with biofilm build-up, lowering the bacterial burden on the tooth surface without affecting bacterial viability in the oral cavity. Moreover, they dissolve when pH in the biofilm...... drops to 6 or below and release buffering phosphate ions that stabilize biofilm pH above the critical level for enamel dissolution. With that twofold approach, calcium-phosphate-osteopontin particles may make a relevant contribution to clinical caries control....

Hydrogen-Deuterium Exchange Mass Spectrometry Reveals Calcium Binding Properties and Allosteric Regulation of Downstream Regulatory Element Antagonist Modulator (DREAM).

Science.gov (United States)

Zhang, Jun; Li, Jing; Craig, Theodore A; Kumar, Rajiv; Gross, Michael L

2017-07-18

Downstream regulatory element antagonist modulator (DREAM) is an EF-hand Ca 2+ -binding protein that also binds to a specific DNA sequence, downstream regulatory elements (DRE), and thereby regulates transcription in a calcium-dependent fashion. DREAM binds to DRE in the absence of Ca 2+ but detaches from DRE under Ca 2+ stimulation, allowing gene expression. The Ca 2+ binding properties of DREAM and the consequences of the binding on protein structure are key to understanding the function of DREAM. Here we describe the application of hydrogen-deuterium exchange mass spectrometry (HDX-MS) and site-directed mutagenesis to investigate the Ca 2+ binding properties and the subsequent conformational changes of full-length DREAM. We demonstrate that all EF-hands undergo large conformation changes upon calcium binding even though the EF-1 hand is not capable of binding to Ca 2+ . Moreover, EF-2 is a lower-affinity site compared to EF-3 and -4 hands. Comparison of HDX profiles between wild-type DREAM and two EF-1 mutated constructs illustrates that the conformational changes in the EF-1 hand are induced by long-range structural interactions. HDX analyses also reveal a conformational change in an N-terminal leucine-charged residue-rich domain (LCD) remote from Ca 2+ -binding EF-hands. This LCD domain is responsible for the direct interaction between DREAM and cAMP response element-binding protein (CREB) and regulates the recruitment of the co-activator, CREB-binding protein. These long-range interactions strongly suggest how conformational changes transmit the Ca 2+ signal to CREB-mediated gene transcription.

Hydrogen-tritium exchange survey of allosteric effects in hemoglobin

International Nuclear Information System (INIS)

Englander, J.J.; Englander, S.W.

1987-01-01

The oxy and deoxy forms of hemoglobin display major differences in H-exchange behavior. Hydrogen-tritium exchange experiments on hemoglobin were performed in the low-resolution mode to observe the dependence of these differences on pH (Bohr effect), organic phosphates, and salt. Unlike a prior report, increasing pH was found to decrease the oxy-deoxy difference monotonically, in general accordance with the alkaline Bohr effect. A prior report that the H-exchange difference between oxy- and deoxyhemoglobin vanishes at pH 9, and thus appears to reflect the Bohr effect alone, was found to be due to the borate buffer used, which at high pH tends to abolish the oxy-deoxy difference in a limited region of the H-exchange curve. Effects on hemoglobin H exchange due to organic phosphates parallel the differential binding of these agents (inositol hexaphosphate more than diphosphoglycerate, deoxy more than oxy, at low pH more than at high pH). Added salt slows H exchange of deoxyhemoglobin and has no effect on the oxy form. These results display the sensitivity of simple H-exchange measurements for finding and characterizing effects on structure and dynamics that may occur anywhere in the protein and help to define conditions for higher resolution approaches that can localize the changes observed

Hydrogen storage by polylithiated molecules and nanostructures

NARCIS (Netherlands)

Er, S.; de Wijs, Gilles A.; Brocks, G.

2009-01-01

We study polylithiated molecules as building blocks for hydrogen storage materials, using first-principles calculations. CLi4 and OLi2 bind 12 and 10 hydrogen molecules, respectively, with an average binding energy of 0.10 and 0.13 eV, leading to gravimetric densities of 37.8 and 40.3 wt % of H2.

Steady state kinetic model for the binding of substrates and allosteric effectors to Escherichia coli phosphoribosyl-diphosphate synthase

DEFF Research Database (Denmark)

Willemoës, Martin; Hove-Jensen, Bjarne; Larsen, Sine

2000-01-01

A steady state kinetic investigation of the Pi activation of 5-phospho-D-ribosyl α-1-diphosphate synthase from Escherichia coli suggests that Pi can bind randomly to the enzyme either before or after an ordered addition of free Mg2+ and substrates. Unsaturation with ribose 5-phosphate increased...... the apparent cooperativity of Pi activation. At unsaturating Pi concentrations partial substrate inhibition by ribose 5-phosphate was observed. Together these results suggest that saturation of the enzyme with Pi directs the subsequent ordered binding of Mg2+ and substrates via a fast pathway, whereas...... saturation with ribose 5-phosphate leads to the binding of Mg2+ and substrates via a slow pathway where Pi binds to the enzyme last. The random mechanism for Pi binding was further supported by studies with competitive inhibitors of Mg2+, MgATP, and ribose 5-phosphate that all appeared noncompetitive when...

Structural basis for phosphatidylinositol-phosphate biosynthesis

Science.gov (United States)

Clarke, Oliver B.; Tomasek, David; Jorge, Carla D.; Dufrisne, Meagan Belcher; Kim, Minah; Banerjee, Surajit; Rajashankar, Kanagalaghatta R.; Shapiro, Lawrence; Hendrickson, Wayne A.; Santos, Helena; Mancia, Filippo

2015-10-01

Phosphatidylinositol is critical for intracellular signalling and anchoring of carbohydrates and proteins to outer cellular membranes. The defining step in phosphatidylinositol biosynthesis is catalysed by CDP-alcohol phosphotransferases, transmembrane enzymes that use CDP-diacylglycerol as donor substrate for this reaction, and either inositol in eukaryotes or inositol phosphate in prokaryotes as the acceptor alcohol. Here we report the structures of a related enzyme, the phosphatidylinositol-phosphate synthase from Renibacterium salmoninarum, with and without bound CDP-diacylglycerol to 3.6 and 2.5 Å resolution, respectively. These structures reveal the location of the acceptor site, and the molecular determinants of substrate specificity and catalysis. Functional characterization of the 40%-identical ortholog from Mycobacterium tuberculosis, a potential target for the development of novel anti-tuberculosis drugs, supports the proposed mechanism of substrate binding and catalysis. This work therefore provides a structural and functional framework to understand the mechanism of phosphatidylinositol-phosphate biosynthesis.

How Native and Alien Metal Cations Bind ATP: Implications for Lithium as a Therapeutic Agent

Science.gov (United States)

Dudev, Todor; Grauffel, Cédric; Lim, Carmay

2017-02-01

Adenosine triphosphate (ATP), the major energy currency of the cell, exists in solution mostly as ATP-Mg. Recent experiments suggest that Mg2+ interacts with the highly charged ATP triphosphate group and Li+ can co-bind with the native Mg2+ to form ATP-Mg-Li and modulate the neuronal purine receptor response. However, it is unclear how the negatively charged ATP triphosphate group binds Mg2+ and Li+ (i.e. which phosphate group(s) bind Mg2+/Li+) and how the ATP solution conformation depends on the type of metal cation and the metal-binding mode. Here, we reveal the preferred ATP-binding mode of Mg2+/Li+ alone and combined: Mg2+ prefers to bind ATP tridentately to each of the three phosphate groups, but Li+ prefers to bind bidentately to the terminal two phosphates. We show that the solution ATP conformation depends on the cation and its binding site/mode, but it does not change significantly when Li+ binds to Mg2+-loaded ATP. Hence, ATP-Mg-Li, like Mg2+-ATP, can fit in the ATP-binding site of the host enzyme/receptor, activating specific signaling pathways.

Growth and characterization of calcium hydrogen phosphate dihydrate crystals from single diffusion gel technique

Energy Technology Data Exchange (ETDEWEB)

Rajendran, K.; Dale Keefe, C. [Department of Chemistry, Cape Breton University, Sydney, Nova Scotia (Canada)

2010-09-15

Calcium hydrogen phosphate dihydrate (CaHPO{sub 4}.2H{sub 2}O, CHPD) a dissolved mineral in urine is known to cause renal or bladder stones in both human and animals. Growth of CHPD or brushite using sodium metasilicate gel techniques followed by light and polarizing microscopic studies revealed its structural and morphological details. Crystal identity by powder x-ray diffraction confirmed the FT-IR and FT-Raman spectroscopic techniques as alternate methods for fast analysis of brushite crystals which could form as one type of renal stones. P-O-P asymmetric stretchings in both FT-IR (987.2, 874.1 and 792 cm{sup -1}) and FT-Raman (986.3 cm{sup -1}, 1057.6 cm{sup -1} and 875.2 cm{sup -1}) were found as characteristics of brushite crystals. Differential Scanning Calorimetry (DSC) analysis revealed brushite crystallization purity using gel method by studying their endothermic peaks. This study incorporated a multidisciplinary approach in characterizing CHPD crystals grown in vitro to help formulate prevention or dissolution strategy in controlling urinary stone growth. Initial studies with 0.2 M citric acid ions as controlling agent in the nucleation of brushite crystals further support the presented approach. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Ferroelectric phase transition in hydrogen-bonded 2-aminopyridine phosphate (NC sub 4 H sub 4 NH sub 2)centre dot H sub 3 PO sub 4

CERN Document Server

Czapla, Z; Waskowska, A

2003-01-01

A new crystal of 2-aminopyridine phosphate (NC sub 4 H sub 4 NH sub 2)centre dot H sub 3 PO sub 4 has been grown and its x-ray structure and physical properties were studied. At room temperature the crystals are monoclinic, space group C2/c. The flat 2-aminopyridine cations are hydrogen bonded to the anionic [PO sub 4 ] groups. The interesting feature of the crystal structure is the three-dimensional network of hydrogen bonds including, among others, two strong, symmetrical O centre dot centre dot centre dot H, H centre dot centre dot centre dot O interactions with disordered proton locations. Symmetrically related PO sub 4 anions linked through these protons form infinite (PO sub 4) subinfinity chains along the crystal a-axis. The anomalies in the temperature dependence of the electric permittivity showed that the crystal undergoes ferroelectric phase transition at T sub c = 103.5 K. The spontaneous polarization takes place along the crystal a-axis, being parallel to the chains of the hydrogen-bonded PO sub ...

Hydrogenic-Donor Impurity Binding Energy Dependence of the Electric Field in GaAs/AlxGa1−xAs Quantum Rings

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Guangxin Wang

2013-01-01

Full Text Available Using a variational method with two-parameter trial wave function and the effective mass approximation, the binding energy of a donor impurity in GaAs/AlxGa1−xAs cylindrical quantum ring (QR subjected to an external field is calculated. It is shown that the donor impurity binding energy is highly dependent on the QR structure parameters (radial thickness and height, impurity position, and external electric field. The binding energy increases inchmeal as the QR parameters (radial thickness and height decrease until a maximum value for a central impurity and then begins to drop quickly. The applied electric field can significantly modify the spread of electronic wave function in the QR and shift electronic wave function from the donor position and then leads to binding energy changes. In addition, results for the binding energies of a hydrogenic donor impurity as functions of the impurity position and applied electric field are also presented.

Time-related Changes in pH, Buffering Capacity and Phosphate and Urea Concentration of Stimulated Saliva.

Science.gov (United States)

Vuletic, Lea; Peros, Kristina; Spalj, Stjepan; Rogic, Dunja; Alajbeg, Ivan

2014-01-01

To quantify changes in pH, buffering capacity and hydrogen carbonate, phosphate, protein and urea concentrations of stimulated saliva which occur during a 30-min measurement delay after saliva collection. The correlation between time-related chemical changes and changes of salivary pH and buffering capacity was assessed in order to explain the observed changes in salivary pH and buffering capacity. Stimulated saliva samples were collected from 30 volunteers after inducing salivation by chewing a piece of parafilm. Measurements of salivary variables were made immediately after saliva collection and again 30 min later, during which time the specimens were exposed to the atmosphere in collection cups at room temperature. Postponement of measurements resulted in a significant increase in pH and a significant decrease of buffering capacity, phosphate and urea concentration. The results suggest that the time-related pH increase could primarily be attributed to loss of dissolved carbon dioxide from saliva, and confirm the importance of hydrogen carbonate in the neutralisation of hydrogen ions, but they do not support the principle of catalysed phase-buffering for the hydrogen carbonate buffer system in saliva. A decrease in phosphate and urea concentration affects salivary buffering capacity. This study emphasises the importance of the standardisation of measurement time when measuring salivary pH, buffering capacity, phosphate and urea concentrations following the collection of saliva in order to obtain comparable results. It also provides a partial explanation of the mechanisms underlying the observed changes of pH and buffering capacity over time.

Reducing the cadmium content of crude phosphates and mineral fertilizers

Energy Technology Data Exchange (ETDEWEB)

Plessen, H von; Schimmel, G

1987-10-01

Crude sedimentary phosphates generally contain cadmium together with traces of other heavy metals. These Cd traces generally end up in fertilizers produced from the crude phosphates. Processes have therefore been developed to separate the Cd from the crude phosphate or from the crude phosphoric acids arising therefrom as intermediates. In this way, the Cd content of the crude phosphate can be reduced to less the 10% of its original value, and to 50% thereof by extractive treatment with acidic calcium nitrate solution. Older calcination processes for crude phosphate have been improved to give residual Cd contents of 10 to 50% at temperatures of 800 to 1000/sup 0/C. Cadmium can be removed almost quantitatively from crude phosphate by means of dialkyl dithiophosphoric acid esters by extraction, binding to adsorbents, or ion flotation. Cadmium can be extracted from crude acids in high yield by long-chained amines. After partial neutralization of the crude acids, precipitation as cadmium sulphide is also possible.

Structural and thermodynamic insights into chitooligosaccharide binding to human cartilage chitinase 3-like protein 2 (CHI3L2 or YKL-39).

Science.gov (United States)

Ranok, Araya; Wongsantichon, Jantana; Robinson, Robert C; Suginta, Wipa

2015-01-30

Four crystal structures of human YKL-39 were solved in the absence and presence of chitooligosaccharides. The structure of YKL-39 comprises a major (β/α)8 triose-phosphate isomerase barrel domain and a small α + β insertion domain. Structural analysis demonstrates that YKL-39 interacts with chitooligosaccharides through hydrogen bonds and hydrophobic interactions. The binding of chitin fragments induces local conformational changes that facilitate tight binding. Compared with other GH-18 members, YKL-39 has the least extended chitin-binding cleft, containing five subsites for sugars, namely (-3)(-2)(-1)(+1)(+2), with Trp-360 playing a prominent role in the sugar-protein interactions at the center of the chitin-binding cleft. Evaluation of binding affinities obtained from isothermal titration calorimetry and intrinsic fluorescence spectroscopy suggests that YKL-39 binds to chitooligosaccharides with Kd values in the micromolar concentration range and that the binding energies increase with the chain length. There were no significant differences between the Kd values of chitopentaose and chitohexaose, supporting the structural evidence for the five binding subsite topology. Thermodynamic analysis indicates that binding of chitooligosaccharide to YKL-39 is mainly driven by enthalpy. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Theory of molecular hydrogen sorption for hydrogen storage

Science.gov (United States)

Zhang, Shengbai

2011-03-01

Molecular hydrogen (H2) sorption has the advantage of fast kinetics and high reversibility. However, the binding strength is often too weak to be operative at near room temperatures. Research into such hydrogen sorption materials has branched into the study of pure van der Waals (vdW) physisorption and that of weak chemisorption (known to exist in the so-called Kubas complexes). In either case, however, theoretical tools to describe such weak interactions are underdeveloped with error bars that often exceed the strength of the interaction itself. We have used quantum-chemistry (QC) based approaches to benchmark the various available DFT methods for four classes of weak chemisorption systems [Sun et al., Phys. Rev. B 82, 073401 (2010)]. These involve complexes containing Li, Ca, Sc, and Ti with increased strength of H2 binding from predominantly vdW to mostly Kubas-like. The study reveals that most of the DFT functionals within the generalized gradient approximation underestimate the binding energy, oppose to overestimating it. The functionals that are easy to use yet yielding results reasonably close to those of accurate QC are the PBE and PW91. I will also discuss the effort of implementing vdW interaction into the currently available density functional methods [Sun, J. Chem. Phys. 129, 154102 (2008)]. The rationale is that while the true vdW is an electron-electron correlation, a DFT plus classical dispersion approach may be too simple and unnecessary within the DFT. A local pseudopotential approach has been developed to account for the core part of the polarizability of the elements. Applications to a number of benchmark systems yield good agreement with QC calculations. The application of this method and the QC methods to vdW hydrogen binding will also be discussed. Work supported by DOE/BES and DOE/EERE Hydrogen Sorption Center of Excellence under RPI subcontracts No. J30546/J90336.

Indigo Carmine-Cu complex probe exhibiting dual colorimetric/fluorimetric sensing for selective determination of mono hydrogen phosphate ion and its logic behavior.

Science.gov (United States)

Tavallali, Hossein; Deilamy-Rad, Gohar; Moaddeli, Ali; Asghari, Khadijeh

2017-08-05

A new selective probe based on copper complex of Indigo Carmine (IC-Cu 2 ) for colorimetric, naked-eye, and fluorimetric recognition of mono hydrogen phosphate (MHP) ion in H 2 O/DMSO (4:1v/v, 1.0mmolL -1 HEPES buffer solution pH7.5) was developed. Detection limit of HPO 4 2- determination, achieved by fluorimetric and 3 lorimetric method, are 0.071 and 1.46μmolL -1 , respectively. Potential, therefore is clearly available in IC-Cu 2 complex to detect HPO 4 2- in micromolar range via dual visible color change and fluorescence response. Present method shows high selectivity toward HPO 4 2- over other phosphate species and other anions and was successfully utilized for analysis of P 2 O 5 content of a fertilizer sample. The results obtained by proposed chemosensor presented good agreement with those obtained the colorimetric reference method. INHIBIT and IMPLICATION logic gates operating at molecular level have been achieved using Cu 2+ and HPO 4 2- as chemical inputs and UV-Vis absorbance signal as output. Copyright © 2017. Published by Elsevier B.V.

Theoretical Studies of Hydrogen Storage Alloys.

Energy Technology Data Exchange (ETDEWEB)

Jonsson, Hannes

2012-03-22

Theoretical calculations were carried out to search for lightweight alloys that can be used to reversibly store hydrogen in mobile applications, such as automobiles. Our primary focus was on magnesium based alloys. While MgH{sub 2} is in many respects a promising hydrogen storage material, there are two serious problems which need to be solved in order to make it useful: (i) the binding energy of the hydrogen atoms in the hydride is too large, causing the release temperature to be too high, and (ii) the diffusion of hydrogen through the hydride is so slow that loading of hydrogen into the metal takes much too long. In the first year of the project, we found that the addition of ca. 15% of aluminum decreases the binding energy to the hydrogen to the target value of 0.25 eV which corresponds to release of 1 bar hydrogen gas at 100 degrees C. Also, the addition of ca. 15% of transition metal atoms, such as Ti or V, reduces the formation energy of interstitial H-atoms making the diffusion of H-atoms through the hydride more than ten orders of magnitude faster at room temperature. In the second year of the project, several calculations of alloys of magnesium with various other transition metals were carried out and systematic trends in stability, hydrogen binding energy and diffusivity established. Some calculations of ternary alloys and their hydrides were also carried out, for example of Mg{sub 6}AlTiH{sub 16}. It was found that the binding energy reduction due to the addition of aluminum and increased diffusivity due to the addition of a transition metal are both effective at the same time. This material would in principle work well for hydrogen storage but it is, unfortunately, unstable with respect to phase separation. A search was made for a ternary alloy of this type where both the alloy and the corresponding hydride are stable. Promising results were obtained by including Zn in the alloy.

Specificity of cellular DNA-binding sites of microbial populations in a Florida reservoir

International Nuclear Information System (INIS)

Paul, J.H.; Pichard, S.L.

1989-01-01

The substrate specificity of the DNA-binding mechanism(s) of bacteria in a Florida reservoir was investigated in short- and long-term uptake studies with radiolabeled DNA and unlabeled competitors. Thymine oligonucleotides ranging in size from 2 base pairs to 19 to 24 base pairs inhibited DNA binding in 20-min incubations by 43 to 77%. Deoxynucleoside monophosphates, thymidine, and thymine had little effect on short-term DNA binding, although several of these compounds inhibited the uptake of the radiolabel from DNA in 4-h incubations. Inorganic phosphate and glucose-1-phosphate inhibited neither short- nor long-term binding of [ 3 H]- or [ 32 P]DNA, indicating that DNA was not utilized as a phosphorous source in this reservoir. RNA inhibited both short- and long-term radiolabeled DNA uptake as effectively as unlabeled DNA. Collectively these results indicate that aquatic bacteria possess a generalized nuclei acid uptake/binding mechanism specific for compounds containing phosphodiester bonds and capable of recognizing oligonucleotides as short as dinucleotides. This binding site is distinct from nucleoside-, nucleotide-, phosphomonoester-, and inorganic phosphate-binding sites. Such a nucleic acid-binding mechanism may have evolved for the utilization of extracellular DNA (and perhaps RNA), which is abundant in many marine and freshwater environments

Multi-functionalized naphthalene complexes for hydrogen storage

International Nuclear Information System (INIS)

Kalamse, Vijayanand; Wadnerkar, Nitin; Chaudhari, Ajay

2013-01-01

A density functional study of hydrogen uptake capacity of multi-functionalized naphthalene with Ti and Li metal atom has been carried out. It is observed that, the naphthalene functionalized with two Ti atoms can interact with total eight hydrogen molecules in which each Ti metal atom interacts with four hydrogen molecules. Naphthalene decorated with two Li atoms can interact with total three H 2 molecules only. First ( 19 Li) and second ( 20 Li) Li atom can interact with only one and two hydrogen molecule respectively. It is observed that, hydrogen molecules bind strongly to the C 10 H 8 Ti 2 complex than C 10 H 8 Li 2 complex. The gravimetric hydrogen uptake capacity of C 10 H 8 Ti 2 and C 10 H 8 Li 2 complex is found to be 6.72 and 3.73 wt% respectively. Moreover, after functionalizing naphthalene with four Li atoms, the uptake capacity is increased to 7.20 wt %. However, the thermochemistry result favors to Ti functionalized naphthalene complex (C 10 H 8 Ti 2 ) for hydrogen storage over Li functionalized naphthalene (both C 10 H 8 Li 2 and C 10 H 8 Li 4 ) complexes. Atom-centered density matrix propagation (ADMP) molecular dynamics simulations have been performed which showed that C 10 H 8 Li 2 and C 10 H 8 Li 4 complex cannot bind single hydrogen molecule at room temperature whereas C 10 H 8 Ti 2 can bind five hydrogen molecules. -- Highlights: ► The gravimetric H 2 uptake capacity of C 10 H 8 Ti 2 complex is 6.72 wt%. ► Uptake capacity of C 10 H 8 Li 2 and C 10 H 8 Li 4 complex is 3.73 and 7.20 wt% respectively. ► C 10 H 8 Ti is more promising material for hydrogen adsorption. ► C 10 H 8 Ti 2 can bind five hydrogen molecules as shown by ADMP-MD results.

Influence of protonation or alkylation of the phosphate group on the e. s. r. spectra and on the rate of phosphate elimination from 2-methoxyethyl phosphate 2-yl radicals. [. gamma. rays

Energy Technology Data Exchange (ETDEWEB)

Behrens, G; Koltzenburg, G; Ritter, A; Schulte-Frohlinde, D [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenchemie

1978-02-01

The e.s.r. spectra of l-yl, 2-yl and 3'-yl methoxethyl phosphate radicals derived from CH/sub 3/OCH/sub 2/CH/sub 2/-OPO/sub 3/H/sub 2/ by hydrogen abstraction have been measured in aqueous solutions and the hyperfine constants determined. The coupling constants vary strongly with protonation or alkylation of the phosphate group. The 2-yl radicals eliminate phosphate. The rate-constants for the elimination (ksub(e)) have been estimated by e.s.r. measurements and by product studies as a function of pH using /sup 60/Co ..gamma..-radiolysis. The ksub(e) values vary from approximately 0.3 s/sup -1/ for the CH/sub 3/OCHCH/sub 2/OPO/sub 3//sup - -/ radical and approximately 10/sup 3/s/sup -1/ for CH/sub 3/OCHCH/sub 2/OPO/sub 3/H/sup -/, to approximately 3 x 10/sup 6/s/sup -1/ for CH/sub 3/OCHCH/sub 2/OPO/sub 3/H/sub 2/. Alkylation of the phosphate group increased the elimination rate-constant to a similar extent as protonation. The results support a recent mechanism which described the OH-radical-induced single-strand breaks of DNA in aqueous solution starting from the C-4' radical of the sugar moiety. It is further concluded the C-4' radical of DNA eliminates the 3'-phosphate group faster than the 5'-phosphate group.

The effect of two bleaching agents on the phosphate concentration of the enamel evaluated by Raman spectroscopy: An ex vivo study

Directory of Open Access Journals (Sweden)

Sokkalingam Mothilal Venkatesan

2012-01-01

Full Text Available Aim : The aim of this ex vivo study was to evaluate the effect of in-office bleaching agents,-35% and 38% hydrogen peroxide containing bleaching agents, on the phosphate concentration of the enamel evaluated by Raman spectroscopy. Materials and Methods : Forty noncarious, craze-free human maxillary incisors, extracted for periodontal reasons, were used in this study. Baseline Raman spectra from each specimen were obtained before the application of the bleaching agent to assess the phosphate content present in the teeth. The teeth were divided into two groups: Group A - bleached with pola office bleach (35% hydrogen peroxide, potassium nitrate (light activated. Group B - bleached with opalescence Xtra bleach (38% hydrogen peroxide potassium nitrate and fluoride (chemical activated. After the bleaching procedure, the treated specimens were taken to obtain Raman spectra to assess the phosphate loss after bleaching treatment. Results : The results showed that the chemically activated bleaching agent showed less phosphate loss when compared with the light activated bleaching agent. Conclusion : Within the limitations of this study, it can be concluded that the chemically activated bleaching agent showed minimal phosphate loss when compared to light activated bleaching agent. The chemically activated bleaching agent was better than the light activated bleaching agent when values were evaluated statistically.

Dephosphorylation of microtubule-binding sites at the neurofilament-H tail domain by alkaline, acid, and protein phosphatases.

Science.gov (United States)

Hisanaga, S; Yasugawa, S; Yamakawa, T; Miyamoto, E; Ikebe, M; Uchiyama, M; Kishimoto, T

1993-06-01

The dephosphorylation-induced interaction of neurofilaments (NFs) with microtubules (MTs) was investigated by using several phosphatases. Escherichia coli alkaline and wheat germ acid phosphatases increased the electrophoretic mobility of NF-H and NF-M by dephosphorylation, and induced the binding of NF-H to MTs. The binding of NFs to MTs was observed only after the electrophoretic mobility of NF-H approached the exhaustively dephosphorylated level when alkaline phosphatase was used. The number of phosphate remaining when NF-H began to bind to MTs was estimated by measuring phosphate bound to NF-H. NF-H did not bind to MTs even when about 40 phosphates from the total of 51 had been removed by alkaline phosphatase. The removal of 6 further phosphates finally resulted in the association of NF-H with MTs. A similar finding, that the restricted phosphorylation sites in the NF-H tail domain, but not the total amount of phosphates, were important for binding to MTs, was also obtained with acid phosphatases. In contrast to alkaline and acid phosphatases, four classes of protein phosphatases (protein phosphatases 1, 2A, 2B, and 2C) were ineffective for shifting the electrophoretic mobility of NF proteins and for inducing the association of NFs to MTs.

New hydrogen titanium phosphate sulfate electrodes for Li-ion and Na-ion batteries

Science.gov (United States)

Zhao, Ran; Mieritz, Daniel; Seo, Dong-Kyun; Chan, Candace K.

2017-03-01

NASICON-type materials with general formula AxM2(PO4)3 (A = Li or Na, M = Ti, V, and Fe) are promising candidates for Li- and Na-ion batteries due to their open three-dimensional framework structure. Here we report the electrochemical properties of hydrogen titanium phosphate sulfate, H0.4Ti2(PO4)2.4(SO4)0.6 (HTPS), a new mixed polyanion material with NASICON structure. Micron-sized HTPS aggregates with crystallite grain size of ca. 23 nm are synthesized using a sol-gel synthesis in an acidic medium. The properties of the as-synthesized HTPS, ball-milled HTPS, and samples prepared as carbon composites using an in-situ glucose decomposition reaction are investigated. A capacity of 148 mAh g-1 corresponding to insertion of 2 Li+ per formula unit is observed in the ball-milled HTPS over the potential window of 1.5-3.4 V vs. Li/Li+. Lithiation at ca. 2.8 and 2.5 V is determined to occur through filling of the M1 and M2 sites, respectively. Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) are used characterize the HTPS before and after cycling. Evaluation of the HTPS in a Na-ion cell is also performed. A discharge capacity of 93 mAh g-1 with sodiation at ca. 2.9 and 2.2 V vs. Na/Na+ is observed.

Effect of non-parabolicity on the binding energy of a hydrogenic donor in quantum well with a magnetic field

International Nuclear Information System (INIS)

Jayakumar, K.; Balasubramanian, S.; Tomak, M.

1985-08-01

A hydrogenic donor in a quantum well in the presence of a magnetic field perpendicular to the barrier is considered in the effective mass approximation. The non-parabolicity of the subband is included in the Hamiltonian by an energy-dependent effective mass. The donor binding energy is calculated variationally for different well widths and the effect of non-parabolicity is discussed in the light of recent experimental results. (author)

Sublingual immunization with the phosphate-binding-protein (PstS) reduces oral colonization by Streptococcus mutans.

Science.gov (United States)

Ferreira, E L; Batista, M T; Cavalcante, R C M; Pegos, V R; Passos, H M; Silva, D A; Balan, A; Ferreira, L C S; Ferreira, R C C

2016-10-01

Bacterial ATP-binding cassette (ABC) transporters play a crucial role in the physiology and pathogenicity of different bacterial species. Components of ABC transporters have also been tested as target antigens for the development of vaccines against different bacterial species, such as those belonging to the Streptococcus genus. Streptococcus mutans is the etiological agent of dental caries, and previous studies have demonstrated that deletion of the gene encoding PstS, the substrate-binding component of the phosphate uptake system (Pst), reduced the adherence of the bacteria to abiotic surfaces. In the current study, we generated a recombinant form of the S. mutans PstS protein (rPstS) with preserved structural features, and we evaluated the induction of antibody responses in mice after sublingual mucosal immunization with a formulation containing the recombinant protein and an adjuvant derived from the heat-labile toxin from enterotoxigenic Escherichia coli strains. Mice immunized with rPstS exhibited systemic and secreted antibody responses, measured by the number of immunoglobulin A-secreting cells in draining lymph nodes. Serum antibodies raised in mice immunized with rPstS interfered with the adhesion of bacteria to the oral cavity of naive mice challenged with S. mutans. Similarly, mice actively immunized with rPstS were partially protected from oral colonization after challenge with the S. mutans NG8 strain. Therefore, our results indicate that S. mutans PstS is a potential target antigen capable of inducing specific and protective antibody responses after sublingual administration. Overall, these observations raise interesting perspectives for the development of vaccines to prevent dental caries. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Photocatalytic hydrogen evolution from aqueous solutions of organophosphorous compounds

Energy Technology Data Exchange (ETDEWEB)

Kozlova, Ekaterina A.; Vorontsov, Alexander V. [Boreskov Institute of Catalysis and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

2010-07-15

Photocatalytic hydrogen production from water solutions of dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), triethyl phosphate (TEP), and radiation protective amine WR 2721, that imitate nerve chemical warfare agents was studied for the first time. Platinized titianium dioxide Degussa P25 was used as catalyst. No significant hydrogen evolution was detected without organic electron donors - sacrificial agents. The hydrogen evolution rate was shown to grow slowly with the rise of initial DMMP concentration. The initial rate vs. DMMP concentration curve is well fitted by Langmuir-Hinshelwood (L-H) equation. The DMMP adsorption constant obtained from the L-H equation fit is markedly higher than that obtained from the Langmuir adsorption isotherm. Reactions of full destruction into inorganic products of the four organophosphorous compounds were conducted. Amounts of evolved hydrogen and carbon dioxide were completely consistent with stoichiometry of proposed reaction. There were no initial compounds and only trace of total organic carbon after the end of the reaction. Complete water purification and production of an amount of valuable hydrogen was achieved. Intermediates of DMMP oxygen-free destruction were identified by means of GC/MS. They were the same as those in the case of DMMP photocatalytic oxidation. A mechanism of hydrogen evolution that explains smaller rates of mineralization compared to photocatalytic oxidation by oxygen was proposed. (author)

External electric field effect on the binding energy of a hydrogenic donor impurity in InGaAsP/InP concentric double quantum rings

Science.gov (United States)

Hu, Min; Wang, Hailong; Gong, Qian; Wang, Shumin

2018-04-01

Within the framework of effective-mass envelope-function theory, the ground state binding energy of a hydrogenic donor impurity is calculated in the InGaAsP/InP concentric double quantum rings (CDQRs) using the plane wave method. The effects of geometry, impurity position, external electric field and alloy composition on binding energy are considered. It is shown that the peak value of the binding energy appears in two rings with large gap as the donor impurity moves along the radial direction. The binding energy reaches the peak value at the center of ring height when the donor impurity moves along the axial direction. The binding energy shows nonlinear variation with the increase of ring height. With the external electric field applied along the z-axis, the binding energy of the donor impurity located at zi ≥ 0 decreases while that located at zi < 0 increases. In addition, the binding energy decreases with increasing Ga composition, but increases with the increasing As composition.

Bulkiness or aromatic nature of tyrosine-143 of actin is important for the weak binding between F-actin and myosin-ADP-phosphate

Energy Technology Data Exchange (ETDEWEB)

Gomibuchi, Yuki [Graduate School of Science and Engineering, Teikyo University, Toyosatodai 1-1, Utsunomiya 320-8551 (Japan); Uyeda, Taro Q.P. [Biomedical Research Institute, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba Central 4, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8562 (Japan); Wakabayashi, Takeyuki, E-mail: tw007@nasu.bio.teikyo-u.ac.jp [Graduate School of Science and Engineering, Teikyo University, Toyosatodai 1-1, Utsunomiya 320-8551 (Japan); Department of Judo Therapy, Faculty of Medical Technology, Teikyo University, Toyosatodai 1-1, Utsunomiya 320-8551 (Japan)

2013-11-29

) of the replaced amino acid molecule. Because 1/K{sub app} reflects the affinity of F-actin for the myosin–ADP-phosphate intermediate (M.ADP.Pi) through the weak binding, these data suggest that the bulkiness or the aromatic nature of the tyrosin-143 is important for the initial binding of the M.ADP.Pi intermediate with F-actin but not for later processes such as the phosphate release.

Reciprocal Regulation of GlnR and PhoP in Response to Nitrogen and Phosphate Limitations in Saccharopolyspora erythraea

Science.gov (United States)

Yao, Li-li

2015-01-01

Nitrogen and phosphate source sensing, uptake, and assimilation are essential for the growth and development of microorganisms. In this study, we demonstrated that SACE_6965 encodes the phosphate regulator PhoP, which controls the transcription of genes involved in phosphate metabolism in the erythromycin-producing Saccharopolyspora erythraea. We found that PhoP and the nitrogen regulator GlnR both regulate the transcription of glnR as well as other nitrogen metabolism-related genes. Interestingly, both GlnR- and PhoP-binding sites were identified in the phoP promoter region. Unlike the nonreciprocal regulation of GlnR and PhoP observed in Streptomyces coelicolor and Streptomyces lividans, GlnR negatively controls the transcription of the phoP gene in S. erythraea. This suggests that GlnR directly affects phosphate metabolism and demonstrates that the cross talk between GlnR and PhoP is reciprocal. Although GlnR and PhoP sites in the glnR and phoP promoter regions are located in close proximity to one another (separated by only 2 to 4 bp), the binding of both regulators to their respective region was independent and noninterfering. These results indicate that two regulators could separately bind to their respective binding sites and control nitrogen and phosphate metabolism in response to environmental changes. The reciprocal cross talk observed between GlnR and PhoP serves as a foundation for understanding the regulation of complex primary and secondary metabolism in antibiotic-producing actinomycetes. PMID:26519391

Identification of human Phosphatidyl Inositol 5-Phosphate 4-Kinase as an RNA binding protein that is imported into Plasmodium falciparum.

Science.gov (United States)

Vindu, Arya; Dandewad, Vishal; Seshadri, Vasudevan

2018-04-06

Plasmodium falciparum is a causative agent for malaria and has a complex life cycle in human and mosquito hosts. Translation repression of specific set of mRNA has been reported in gametocyte stages of this parasite. A conserved element present in the 3'UTR of some of these transcripts was identified. Biochemical studies have identified components of the RNA storage and/or translation inhibitor complex but it is not yet clear how the complex is specifically recruited on the RNA targeted for translation regulation. We used the 3'UTR region of translationally regulated transcripts to identify Phosphatidyl-inositol 5-phosphate 4-kinase (PIP4K2A) as the protein that associates with these RNAs. We further show that recombinant PIP4K2A has the RNA binding activity and can associate specifically with Plasmodium 3'UTR RNAs. Immunostainings show that hPIP4K2A is imported into the Plasmodium parasite from RBC. These results identify a novel RNA binding role for PIP4K2A that may play a role in Plasmodium propagation. Copyright © 2018 Elsevier Inc. All rights reserved.

On the mechanism of ion exchange in zirconium phosphates

International Nuclear Information System (INIS)

Clearfield, A.; Kalnins, J.M.

1978-01-01

The exchange of transition metal (M 2+ ) ions from manganese through cobalt, nickel, copper to zinc with γ-zirconium phosphate was examined. By using acetate salts the hydrogen ion concentration is kept low enough to achieve high loadings. The fully loaded solids have the composition ZrM(PO 4 ) 2 .4H 2 O. Near quantitative uptakes are achieved at 100 0 C. The interlayer spacings change very little with loading indicating that γ-zirconium phosphate is able to accommodate cations and water molecules without appreciable increase in volume. The copper exchanged phase readily forms an acetylacetonate when shaken with 2,4-pentanedione. (author)

Palmitate and stearate binding to human serum albumin. Determination of relative binding constants

DEFF Research Database (Denmark)

Vorum, H; Fisker, K; Honoré, B

1997-01-01

Multiple binding equilibria of two apparently insoluble ligands, palmitate and stearate, to defatted human serum albumin were studied in a 66 mM sodium phosphate buffer (pH 7.4) at 37 degrees C, by determination of dialytic exchange rates of ligands among identical equilibrium solutions. The expe...

Selective flotation of phosphate minerals with hydroxamate collectors

Science.gov (United States)

Miller, Jan D.; Wang, Xuming; Li, Minhua

2002-01-01

A method is disclosed for separating phosphate minerals from a mineral mixture, particularly from high-dolomite containing phosphate ores. The method involves conditioning the mineral mixture by contacting in an aqueous in environment with a collector in an amount sufficient for promoting flotation of phosphate minerals. The collector is a hydroxamate compound of the formula; ##STR1## wherein R is generally hydrophobic and chosen such that the collector has solubility or dispersion properties it can be distributed in the mineral mixture, typically an alkyl, aryl, or alkylaryl group having 6 to 18 carbon atoms. M is a cation, typically hydrogen, an alkali metal or an alkaline earth metal. Preferably, the collector also comprises an alcohol of the formula, R'--OH wherein R' is generally hydrophobic and chosen such that the collector has solubility or dispersion properties so that it can be distributed in the mineral mixture, typically an alkyl, aryl, or alkylaryl group having 6 to 18 carbon atoms.

Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

Science.gov (United States)

Cortes-Concepcion, Jose A.; Anton, Donald L.

2016-04-26

A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

Effect of sodium phosphate salts on the thermodynamic properties of aqueous solutions of poly(ethylene oxide) 6000 at different temperatures

International Nuclear Information System (INIS)

Sadeghi, Rahmat; Hosseini, Rahim; Jamehbozorg, Bahman

2008-01-01

Precise density, sound velocity, water activity, and phase diagram measurements have been carried out on polyethylene oxide (PEO) in aqueous solutions of sodium di-hydrogen phosphate, di-sodium hydrogen phosphate, and tri-sodium phosphate over a range of temperatures at atmospheric pressure. The experimental density and sound velocity data are used to calculate the apparent specific volume and isentropic compressibility as a function of temperature and concentration. It was found that both of the apparent specific volume and isentropic compressibility of PEO in aqueous solutions increase by increasing temperature and charge on the anion of electrolytes. The results show that the slope of constant water activity lines increased with increasing the temperature and charge on the anion of electrolytes and the vapour pressure depression for an aqueous (PEO + sodium phosphate) system is more than the sum of those for the corresponding binary solutions. Furthermore, the effect of temperature and type of anion of salt on the salting-out effect of polyethylene oxide by sodium phosphate salts has been studied

Effect of sodium phosphate salts on the thermodynamic properties of aqueous solutions of poly(ethylene oxide) 6000 at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Sadeghi, Rahmat [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)], E-mail: rahsadeghi@yahoo.com; Hosseini, Rahim; Jamehbozorg, Bahman [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)

2008-09-15

Precise density, sound velocity, water activity, and phase diagram measurements have been carried out on polyethylene oxide (PEO) in aqueous solutions of sodium di-hydrogen phosphate, di-sodium hydrogen phosphate, and tri-sodium phosphate over a range of temperatures at atmospheric pressure. The experimental density and sound velocity data are used to calculate the apparent specific volume and isentropic compressibility as a function of temperature and concentration. It was found that both of the apparent specific volume and isentropic compressibility of PEO in aqueous solutions increase by increasing temperature and charge on the anion of electrolytes. The results show that the slope of constant water activity lines increased with increasing the temperature and charge on the anion of electrolytes and the vapour pressure depression for an aqueous (PEO + sodium phosphate) system is more than the sum of those for the corresponding binary solutions. Furthermore, the effect of temperature and type of anion of salt on the salting-out effect of polyethylene oxide by sodium phosphate salts has been studied.

THERMODINAMIC PARAMETERS ON THE SORPTION OF PHOSPHATE IONS BY MONTMORILLONITE

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Ikhsan Jaslin

2016-04-01

Full Text Available The sorption of phosphate by montmorillonite at 10, 30, and 50 oC were investigated aiming to mainly determine thermodynamic parameters for the formation of surface complexes in the adsorption of phosphate ions by montmorillonite. Data were collected by adsorption edge experiments investigating the effect of pH, adsorption isotherms enabling the effect of sorbate concentration, and acid-base titration calculating protons released or taken up by adsorption process. Data analysis was carried out using surface complexation model to fit the data collected in this study using the parameters obtained from previous study, as well as to calculate the values of ΔH and ΔS. Previous study reported that phosphate ions formed two outer-sphere surface complexes with active sites of montmorillonite through hydrogen bonding. In the first complex,  [(XH0– H2L─]─, the phosphate was held to permanent-charge X─ sites on the tetrahedral siloxane faces, and the second complex, [[(SO─(SOH]– – [H2L]─] 2─ was formed through the interaction between the phosphate and variable charge surface hydroxyl groups at the edges of montmorillonite crystals and on the octahedral alumina faces. The values of ΔH for the first and second reactions are 39.756 and 3.765x10-7 kJ mol‒1 respectively. Since both reactions have positive enthalpy values, it can be concluded that the reactions are endothermic. Large energy for the first reaction is needed by X─  sites (permanent negatively charge sites of montmorillonite to be partially desolvated, on which K+ or other surface cations are replaced by H+ ions in the surface protonated process, and are then ready to interact phosphate ions in the solution. Small values of ΔH for the second reactions indicates that hydrogen bonds formed by phosphate and SOH sites in the second reaction are easily broken out, and the phosphate can easily desorbed from the surface. The values of ΔS for the first and second reactions are

Yeast ribonuclease III uses a network of multiple hydrogen bonds for RNA binding and cleavage.

Science.gov (United States)

Lavoie, Mathieu; Abou Elela, Sherif

2008-08-19

Members of the bacterial RNase III family recognize a variety of short structured RNAs with few common features. It is not clear how this group of enzymes supports high cleavage fidelity while maintaining a broad base of substrates. Here we show that the yeast orthologue of RNase III (Rnt1p) uses a network of 2'-OH-dependent interactions to recognize substrates with different structures. We designed a series of bipartite substrates permitting the distinction between binding and cleavage defects. Each substrate was engineered to carry a single or multiple 2'- O-methyl or 2'-fluoro ribonucleotide substitutions to prevent the formation of hydrogen bonds with a specific nucleotide or group of nucleotides. Interestingly, introduction of 2'- O-methyl ribonucleotides near the cleavage site increased the rate of catalysis, indicating that 2'-OH are not required for cleavage. Substitution of nucleotides in known Rnt1p binding site with 2'- O-methyl ribonucleotides inhibited cleavage while single 2'-fluoro ribonucleotide substitutions did not. This indicates that while no single 2'-OH is essential for Rnt1p cleavage, small changes in the substrate structure are not tolerated. Strikingly, several nucleotide substitutions greatly increased the substrate dissociation constant with little or no effect on the Michaelis-Menten constant or rate of catalysis. Together, the results indicate that Rnt1p uses a network of nucleotide interactions to identify its substrate and support two distinct modes of binding. One mode is primarily mediated by the dsRNA binding domain and leads to the formation of stable RNA/protein complex, while the other requires the presence of the nuclease and N-terminal domains and leads to RNA cleavage.

sphingosine-1-phosphate transport and its role in immunology

NARCIS (Netherlands)

Reitsema, V.; Bouma, Hjalmar; Kok, Jan

2014-01-01

Sphingosine-1-phosphate (S1P) is a sphingolipid metabolite with many important functions in cellular and systemic physiology, including the immune system. As it cannot traverse the membrane, it is exported from cells by transporters. Several members of the ATP-binding cassette (ABC) transporter

Engineering Potato Starch with a Higher Phosphate Content.

Directory of Open Access Journals (Sweden)

Xuan Xu

Full Text Available Phosphate esters are responsible for valuable and unique functionalities of starch for industrial applications. Also in the cell phosphate esters play a role in starch metabolism, which so far has not been well characterized in storage starch. Laforin, a human enzyme composed of a carbohydrate-binding module and a dual-specificity phosphatase domain, is involved in the dephosphorylation of glycogen. To modify phosphate content and better understand starch (dephosphorylation in storage starch, laforin was engineered and introduced into potato (cultivar Kardal. Interestingly, expression of an (engineered laforin in potato resulted in significantly higher phosphate content of starch, and this result was confirmed in amylose-free potato genetic background (amf. Modified starches exhibited altered granule morphology and size compared to the control. About 20-30% of the transgenic lines of each series showed red-staining granules upon incubation with iodine, and contained higher phosphate content than the blue-stained starch granules. Moreover, low amylose content and altered gelatinization properties were observed in these red-stained starches. Principle component and correlation analysis disclosed a complex correlation between starch composition and starch physico-chemical properties. Ultimately, the expression level of endogenous genes involved in starch metabolism was analysed, revealing a compensatory response to the decrease of phosphate content in potato starch. This study provides a new perspective for engineering starch phosphate content in planta by making use of the compensatory mechanism in the plant itself.

Hydrogen storage behavior of one-dimensional TiBx chains

International Nuclear Information System (INIS)

Li Fen; Zhao Jijun; Chen Zhongfang

2010-01-01

We designed a series of one-dimensional TiB x (x = 2-6) chains used for hydrogen storage. Among them, TiB 5 possesses the lowest heat of formation and the highest binding energy, and is the most energetically favorable configuration. The binding energy per atom in TiB 5 is even larger than that in a Ti dimer, which suggests the preference of Ti atoms to combine with B 5 clusters rather than clustering. Each Ti atom in the TiB 5 chain can host four hydrogen molecules (corresponding to a hydrogen storage capacity of 7.3 wt%) with an average binding energy of 43.7 kJ mol -1 /H 2 . The significant charge transfer and strong Kubas σ-H 2 interaction between H 2 and Ti atoms contribute to the ideal dihydrogen binding energies.

Coordination chemistry of sugar-phosphate complexes with palladium(II), rhenium(V) and zinc(II)

Energy Technology Data Exchange (ETDEWEB)

Steinborn, Christian Martin

2013-05-21

As described before, some studies dealing with coordination chemistry of sugar phosphates are available but no analogous complexes of Zn{sup II} have been investigated yet. The primary goal of this work is, therefore, to fill this gap. In order to stay close to the active sites of enzymes such as class-II-aldolase, the simple metal fragment Zn{sup II}(dien) is used. NMR spectroscopy is used primarily as analytical method since it enables the investigation of both complex equilibria in solution and pH dependence of metal-binding sites. Since this approach is challenging due to the fast metal-ligand exchange and the absence of CIS values, it is necessary to improve the significance of NMR data collected from sugar-phosphate complexes with Zn{sup II}. Hence, further experiments are performed with molecules similar to sugar phosphates such as reducing and methylated sugars or polyols. Beside NMR spectroscopy, crystal-structure analysis will be used to get more detailed information about the binding pattern of the complexes. Additionally, sugar-phosphate complexes of Pd{sup II} are investigated. Further experiments are conducted, on the one hand, to synthesise more sugarphosphate complexes with ReVON2 fragments, and, on the other hand, to grow crystals confirming the theory about mixed sugar-core-phosphate chelation.

Sphingosine 1-phosphate stimulates hydrogen peroxide generation through activation of phospholipase C-Ca2+ system in FRTL-5 thyroid cells: possible involvement of guanosine triphosphate-binding proteins in the lipid signaling.

Science.gov (United States)

Okajima, F; Tomura, H; Sho, K; Kimura, T; Sato, K; Im, D S; Akbar, M; Kondo, Y

1997-01-01

Exogenous sphingosine 1-phosphate (S1P) stimulated hydrogen peroxide (H2O2) generation in association with an increase in intracellular Ca2+ concentration in FRTL-5 thyroid cells. S1P also induced inositol phosphate production, reflecting activation of phospholipase C (PLC) in the cells. These three S1P-induced events were inhibited partially by pertussis toxin (PTX) and markedly by U73122, a PLC inhibitor, and were conversely potentiated by N6-(L-2-phenylisopropyl)adenosine, an A1-adenosine receptor agonist. In FRTL-5 cell membranes, S1P also activated PLC in the presence of guanosine 5'-O-(3-thiotriphosphate) (GTP gamma S), but not in its absence. Guanosine 5'-O-(2-thiodiphosphate) inhibited the S1P-induced GTP gamma S-dependent activation of the enzyme. To characterize the signaling pathways, especially receptors and G proteins involved in the S1P-induced responses, cross-desensitization experiments were performed. Under the conditions where homologous desensitization occurred in S1P-, lysophosphatidic acid (LPA)-, and bradykinin-induced induction of Ca2+ mobilization, no detectable cross-desensitization of S1P and bradykinin was observed. This suggests that the primary action of S1P in its activation of the PLC-Ca2+ system was not the activation of G proteins common to S1P and bradykinin, but the activation of a putative S1P receptor. On the other hand, there was a significant cross-desensitization of S1P and LPA; however, a still significant response to S1P (50-80% of the response in the nontreated control cells) was observed depending on the lipid dose employed after a prior LPA challenge. S1P also inhibited cAMP accumulation in a PTX-sensitive manner. We conclude that S1P stimulates H2O2 generation through a PLC-Ca2+ system and also inhibits adenylyl cyclase in FRTL-5 thyroid cells. The S1P-induced responses may be mediated partly through a putative lipid receptor that is coupled to both PTX-sensitive and insensitive G proteins.

Thermodynamics of the hydrolysis reactions of α-D-galactose 1-phosphate, sn-glycerol 3-phosphate, 4-nitrophenyl phosphate, phosphocreatine, and 3-phospho-D-glycerate

International Nuclear Information System (INIS)

Goldberg, Robert N.; Lang, Brian E.; Lo, Catherine; Ross, David J.; Tewari, Yadu B.

2009-01-01

Microcalorimetry, high-performance liquid chromatography (h.p.l.c.), and an enzymatic assay have been used to conduct a thermodynamic investigation of five phosphate hydrolysis reactions: {α-D-galactose 1-phosphate(aq) + H 2 O(l) = D-galactose(aq) + orthophosphate(aq)} (1), {sn-glycerol 3-phosphate(aq) + H 2 O(l) = glycerol(aq) + orthophosphate(aq)} (2), {4-nitrophenyl phosphate(aq) + H 2 O(l) = 4-nitrophenol(aq) + orthophosphate(aq)} (3), {phosphocreatine(aq) + H 2 O(l) = creatine(aq) + orthophosphate(aq)} (4), and {3-phospho-D-glycerate(aq) + H 2 O(l) = D-glycerate(aq) + orthophosphate(aq)} (5). Calorimetrically determined enthalpies of reaction Δ r H(cal) were measured for reactions (1)-(5) and the apparent equilibrium constant K' was measured for reaction (2). The pKs and standard enthalpies of reaction Δ r H 0 for the H + and Mg 2+ binding reactions of the reactants and products in the aforementioned reactions were obtained either from the literature or by estimation. A chemical equilibrium model was then used to calculate standard equilibrium constants K and standard enthalpies of reaction Δ r H 0 for chemical reference reactions that correspond to the overall biochemical reactions that were studied experimentally. Property values from the literature and thermodynamic network calculations were used to obtain values of the equilibrium constants for the chemical reference reactions that correspond to the overall biochemical reactions (1). These values were compared with other results from the literature and also correlated with structural features. The results obtained in this study can be used in the chemical equilibrium model to calculate values of K', the standard apparent Gibbs free energy changes Δ r G '0 , the standard apparent enthalpy changes Δ r H '0 , changes in binding of the proton Δ r N(H + ), and the position of equilibrium for the overall biochemical reactions considered in this study over a reasonably wide range of temperature, pH, p

Al and Si Influences on Hydrogen Embrittlement of Carbide-Free Bainitic Steel

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Yanguo Li

2013-01-01

Full Text Available A first-principle method based on the density functional theory was applied to investigate the Al and Si influences on the hydrogen embrittlement of carbide-free bainitic steel. The hydrogen preference site, binding energy, diffusion behaviour, and electronic structure were calculated. The results showed that hydrogen preferred to be at the tetrahedral site. The binding energy of the cell with Si was the highest and it was decreased to be the worst by adding hydrogen. The diffusion barrier of hydrogen in the cell containing Al was the highest, so it was difficult for hydrogen to diffuse. Thus, hydrogen embrittlement can be reduced by Al rather than Si.

Nuclear magnetic resonance studies of the binding of nitroaromatic electron acceptors to lecithin

International Nuclear Information System (INIS)

Sidorowicz, A.

1980-01-01

It was found from the chemical shifts measurements of carbon-13 and proton resonances, that the phosphate group of lecithin forms charge-transfer complex with 2,4,6-trinitrophenol, but not with s-trinitrobenzene. The conclusion is, that hydrogen bond formed between phenolic OH proton and phosphate group of lecithin facilitates electron transfer process. (orig.)

Hydrogen storage in engineered carbon nanospaces.

Science.gov (United States)

Burress, Jacob; Kraus, Michael; Beckner, Matt; Cepel, Raina; Suppes, Galen; Wexler, Carlos; Pfeifer, Peter

2009-05-20

It is shown how appropriately engineered nanoporous carbons provide materials for reversible hydrogen storage, based on physisorption, with exceptional storage capacities (approximately 80 g H2/kg carbon, approximately 50 g H2/liter carbon, at 50 bar and 77 K). Nanopores generate high storage capacities (a) by having high surface area to volume ratios, and (b) by hosting deep potential wells through overlapping substrate potentials from opposite pore walls, giving rise to a binding energy nearly twice the binding energy in wide pores. Experimental case studies are presented with surface areas as high as 3100 m(2) g(-1), in which 40% of all surface sites reside in pores of width approximately 0.7 nm and binding energy approximately 9 kJ mol(-1), and 60% of sites in pores of width>1.0 nm and binding energy approximately 5 kJ mol(-1). The findings, including the prevalence of just two distinct binding energies, are in excellent agreement with results from molecular dynamics simulations. It is also shown, from statistical mechanical models, that one can experimentally distinguish between the situation in which molecules do (mobile adsorption) and do not (localized adsorption) move parallel to the surface, how such lateral dynamics affects the hydrogen storage capacity, and how the two situations are controlled by the vibrational frequencies of adsorbed hydrogen molecules parallel and perpendicular to the surface: in the samples presented, adsorption is mobile at 293 K, and localized at 77 K. These findings make a strong case for it being possible to significantly increase hydrogen storage capacities in nanoporous carbons by suitable engineering of the nanopore space.

Effects of Dietary Supplementation of Magnesium Hydrogen Phosphate (MgHPO as an Alternative Phosphorus Source on Growth and Feed Utilization of Juvenile Far Eastern Catfish (

Directory of Open Access Journals (Sweden)

Tae-Hyun Yoon

2014-08-01

Full Text Available The present study was conducted to investigate a supplemental effect of magnesium hydrogen phosphate (MHP, MgHPO4 as an alternative phosphorus (P source on growth and feed utilization of juvenile far eastern catfish (Silurus asotus in comparison with three conventional P additives (monocalcium phosphate (MCP, dicalcium phosphate (DCP and tricalcium phosphate [TCP] as positive controls. A basal diet as a negative control was prepared without P supplementation and four supplemental P sources were added at the level of 2%. Five groups of 450 fish having mean body weight of 11.3 g following 24 h fasting after three week adaptation period were randomly distributed into each of 15 tanks (30 fish/tank. Fish were hand-fed to apparent satiety twice a day for 8 weeks. Fish fed MHP had weight gain (WG, protein efficiency ratio and specific growth rate comparable to those fed MCP. Fish fed MHP and MCP had feed efficiency (FE significantly higher (p0.05 among treatments. Fish fed control had the lowest hematocrit, which was significantly different (p<0.05 from that of fish fed MHP. Fish fed MCP and MHP had plasma P higher (p<0.05 than fish fed the other diets. Relative efficiencies of MCP, DCP and TCP to MHP were found to be 100.5 and 101.3%, 92.0 and 91.6%, and 79.1 and 80.9% for WG and FE, respectively. P availability was determined to be 88.1%, 75.2%, 8.7%, and 90.9% for MCP, DCP, TCP, and MHP, respectively. Consequently, MHP recovered from wastewater stream showed that as an alternative P source its performance was comparative with MCP on growth and feed utilization of juvenile far eastern catfish.

Square-wave adsorptive stripping voltammetric determination of nanomolar levels of bezafibrate using a glassy carbon electrode modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film.

Science.gov (United States)

Ardila, Jorge Armando; Oliveira, Geiser Gabriel; Medeiros, Roberta Antigo; Fatibello-Filho, Orlando

2014-04-07

A highly sensitive method for bezafibrate determination using a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film based on square-wave adsorptive stripping voltammetry (SWAdSV) is proposed. The electrochemical behaviour of bezafibrate has been studied by cyclic voltammetry, showing an irreversible anodic peak at a potential of 1.09 V in 0.1 mol L(-1) phosphate buffer solution (pH 2.0). A study of the scan rate showed that the oxidation of bezafibrate is an adsorptive-controlled process, involving the transfer of two electrons and two protons per molecule. The analytical curve was linear over a bezafibrate concentration range from 50 to 910 nmol L(-1), with a detection limit of 16 nmol L(-1). This analytical method was successfully applied for benzafibrate determination in pharmaceutical formulations, with results showing good agreement with those obtained using a comparative spectrophotometric method, and has the potential for field application.

Investigation of antimony extraction from nitric acid solutions by tributyl phosphate

International Nuclear Information System (INIS)

Lakaev, V.S.; Smelov, V.S.

1988-01-01

The effect of iodide, hydrogen and pertechnetate ions on antimony extraction by tri-n-butyl phosphate (TBP) from aqueous nitric acid solutions under irradiated nuclear fuel processing is investigated at room temperature. The coefficients of antimony distribution are shown to increase at the presence of technetium ions 2-3 times and iodine ions - 100 and more times. Variation of hydrogen ion concentration does not affect antimony extraction. The schemes of the mechanism of antimony extraction at the pressence of iodide and pertechnetate ions are presented. Compositions of the formed compounds are given

Hydrogenic impurity binding energy in vertically coupled Ga1-xAlxAs quantum-dots under hydrostatic pressure and applied electric field

International Nuclear Information System (INIS)

Duque, C.M.; Barseghyan, M.G.; Duque, C.A.

2009-01-01

This work deals with a theoretical study, using a variational method and the effective mass approximation, of the ground state binding energy of a hydrogenic donor impurity in a vertically coupled multiple quantum dot structure under the effects of hydrostatic pressure and in-growth direction applied electric field. The low dimensional structure consists of three cylindrical shaped GaAs quantum dots coupled by Ga 1-x Al x As barriers. For the hydrostatic pressure has been considered the Γ-X crossover in the Ga 1-x Al x As material. As a general, the results show that: (1) the binding energy as a function of the impurity position has a similar shape to that shown by the electron wave function without the Coulomb interaction, (2) the presence of the electric field changes dramatically the binding energy profile destroying (favoring) the symmetry in the structures, and (3) depending on the impurity position the binding energy can increase or decrease with the hydrostatic pressure mainly due to increases or decreases of the carrier-wave function symmetry by changing the height of the potential barrier.

Preparation and bioactivity of micro-arc oxidized calcium phosphate coatings

International Nuclear Information System (INIS)

Pan, Y.K.; Chen, C.Z.; Wang, D.G.; Lin, Z.Q.

2013-01-01

Calcium phosphate (CaP) coatings were prepared on ZK60 magnesium alloy by micro-arc oxidation (MAO) in electrolyte containing calcium acetate monohydrate (CH 3 COO) 2 Ca·H 2 O) and disodium hydrogen phosphate dodecahydrate (Na 2 HPO 4 ·12H 2 O). Scanning electron microscope (SEM), energy-dispersive X-ray spectrometry (EDX) and X-ray diffractometer (XRD) were employed to characterize the microstructure, elemental distribution and phase composition of the CaP coatings respectively. Simulated body fluid (SBF) immersion test was used to evaluate the coating degradability and bioactivity. After 30 days of SBF immersion, the CaP coatings effectively reduce the degradation rate. The surfaces of CaP coatings are covered by a new layer formed of numerous needle-like, spherical and columned calcium phosphates. SEM, EDX and XRD results suggest that these calcium phosphates are bioactive calcium phosphate phases such as hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 , HA) and calcium pyrophosphates (Ca 2 P 2 O 7 , CPP). The formation of these calcium phosphates indicates that the CaP coatings have bioactivity. - Highlights: • Bioactive CaP coatings are successfully formed on ZK60 magnesium alloy. • CaP coatings consist of MgO, MgF 2 , CaO, CaF 2 and Ca 3 (PO 4 ) 2 . • Needle-like, spherical and columned calcium phosphates formed in SBF. • CaP coatings exhibit bioactivity and low corrosion rate

Partitioning of L-methionine in aqueous two-phase systems containing poly(propylene glycol) and sodium phosphate salts

International Nuclear Information System (INIS)

Salabat, Alireza; Sadeghi, Rahmat; Moghadam, Somayeh Tiani; Jamehbozorg, Bahman

2011-01-01

Highlights: → Thermodynamics parameters for partitioning of L-methionine in ATPS. → Investigation of different effects on partition coefficient of the amino acid. → Propose the best condition for L-methionine partitioning. - Abstract: The partitioning behavior of L-methionine has been studied in aqueous two-phase systems of (poly(propylene glycol) + sodium phosphate salts + H 2 O) at different temperatures. The salts used were sodium di-hydrogen phosphate (NaH 2 PO 4 ), di-sodium hydrogen phosphate (Na 2 HPO 4 ) and tri-sodium phosphate (Na 3 PO 4 ). The effects of tie line length, salt type, and temperature on the partition coefficient of this amino acid have been studied. In addition, thermodynamic parameters (ΔH o , ΔS o and ΔG o ) as a function of temperature were calculated. The results showed that increasing tie line length led to decreasing of the partition coefficient. We also showed that the partition coefficients of the amino acid in the systems containing Na 3 PO 4 are greater than the other two salts. Moreover, it is verified that increasing temperature led to decreasing the partition coefficient. The experimental partition coefficient data are correlated using a modified virial-type model.

Lack of conventional oxygen-linked proton and anion binding sites does not impair allosteric regulation of oxygen binding in dwarf caiman hemoglobin

Science.gov (United States)

Fago, Angela; Malte, Hans; Storz, Jay F.; Gorr, Thomas A.

2013-01-01

In contrast to other vertebrate hemoglobins (Hbs) whose high intrinsic O2 affinities are reduced by red cell allosteric effectors (mainly protons, CO2, organic phosphates, and chloride ions), crocodilian Hbs exhibit low sensitivity to organic phosphates and high sensitivity to bicarbonate (HCO3−), which is believed to augment Hb-O2 unloading during diving and postprandial alkaline tides when blood HCO3− levels and metabolic rates increase. Examination of α- and β-globin amino acid sequences of dwarf caiman (Paleosuchus palpebrosus) revealed a unique combination of substitutions at key effector binding sites compared with other vertebrate and crocodilian Hbs: β82Lys→Gln, β143His→Val, and β146His→Tyr. These substitutions delete positive charges and, along with other distinctive changes in residue charge and polarity, may be expected to disrupt allosteric regulation of Hb-O2 affinity. Strikingly, however, P. palpebrosus Hb shows a strong Bohr effect, and marked deoxygenation-linked binding of organic phosphates (ATP and DPG) and CO2 as carbamate (contrasting with HCO3− binding in other crocodilians). Unlike other Hbs, it polymerizes to large complexes in the oxygenated state. The highly unusual properties of P. palpebrosus Hb align with a high content of His residues (potential sites for oxygenation-linked proton binding) and distinctive surface Cys residues that may form intermolecular disulfide bridges upon polymerization. On the basis of its singular properties, P. palpebrosus Hb provides a unique opportunity for studies on structure-function coupling and the evolution of compensatory mechanisms for maintaining tissue O2 delivery in Hbs that lack conventional effector-binding residues. PMID:23720132

Effect of molybdate on phosphating of Nd-Fe-B magnets for corrosion protection

Directory of Open Access Journals (Sweden)

Adonis Marcelo Saliba-Silva

2005-06-01

Full Text Available Nd-Fe-B magnets are highly susceptible to corrosion and need protection against environment attack. The use of organic coatings is one of the main methods of corrosion protection of these materials. Data related to the effect of conversion coatings, such as phosphating, on corrosion performance of these magnets is still scarce. Studies about the effect of phosphating on the corrosion resistance of a commercial Nd-Fe-B sintered magnet indicated that it increases the corrosion resistance of these magnets, compared to non-phosphated magnets. In this study, the solution chemistry of a phosphating bath was altered with the addition of molybdate and its effect on the corrosion resistance of magnets investigated. Sintered magnet specimens were phosphated in solutions of 10 g/L NaH2PO4 (pH 3.8, either with or without molybdate [10-3 M MoO4(2-], to improve their corrosion resistance. The effect of phosphating time was also evaluated, and specimens were phosphated for 4 and 18 hours. To evaluate the corrosion performance of phosphated and unphosphated specimens, a corrosion test based on monitoring hydrogen evolution on the surface of the magnets was used. This technique revealed that the addition of molybdate to the phosphating solution improved the corrosion resistance of the magnets phosphated by immersion for short periods but had no beneficial effect if phosphated by immersion for longer periods.

Synthesis and crystal structure of 4-fluorobenzylammonium dihydrogen phosphate, [FC6H4CH2NH3]H2PO4

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Ali Rayes

2016-12-01

Full Text Available The asymmetric unit of the title salt, [p-FC6H4CH2NH3]+·H2PO4−, contains one 4-fluorobenzylammonium cation and one dihydrogen phosphate anion. In the crystal, the H2PO4− anions are linked by O—H...O hydrogen bonds to build corrugated layers extending parallel to the ab plane. The FC6H4CH2NH3+ cations lie between these anionic layers to maximize the electrostatic interactions and are linked to the H2PO4− anions through N—H...O hydrogen bonds, forming a three-dimensional supramolecular network. Two hydrogen atoms belonging to the dihydrogen phosphate anion are statistically occupied due to disorder along the OH...HO direction.

Computer modelling reveals new conformers of the ATP binding loop of Na+/K+-ATPase involved in the transphosphorylation process of the sodium pump.

Science.gov (United States)

Tejral, Gracian; Sopko, Bruno; Necas, Alois; Schoner, Wilhelm; Amler, Evzen

2017-01-01

Hydrolysis of ATP by Na + /K + -ATPase, a P-Type ATPase, catalyzing active Na + and K + transport through cellular membranes leads transiently to a phosphorylation of its catalytical α -subunit. Surprisingly, three-dimensional molecular structure analysis of P-type ATPases reveals that binding of ATP to the N-domain connected by a hinge to the P-domain is much too far away from the Asp 369 to allow the transfer of ATP's terminal phosphate to its aspartyl-phosphorylation site. In order to get information for how the transfer of the γ -phosphate group of ATP to the Asp 369 is achieved, analogous molecular modeling of the M 4 -M 5 loop of ATPase was performed using the crystal data of Na + /K + -ATPase of different species. Analogous molecular modeling of the cytoplasmic loop between Thr 338 and Ile 760 of the α 2 -subunit of Na + /K + -ATPase and the analysis of distances between the ATP binding site and phosphorylation site revealed the existence of two ATP binding sites in the open conformation; the first one close to Phe 475 in the N-domain, the other one close to Asp 369 in the P-domain. However, binding of Mg 2+ •ATP to any of these sites in the "open conformation" may not lead to phosphorylation of Asp 369 . Additional conformations of the cytoplasmic loop were found wobbling between "open conformation"  "semi-open conformation  "closed conformation" in the absence of 2Mg 2+ •ATP. The cytoplasmic loop's conformational change to the "semi-open conformation"-characterized by a hydrogen bond between Arg 543 and Asp 611 -triggers by binding of 2Mg 2+ •ATP to a single ATP site and conversion to the "closed conformation" the phosphorylation of Asp 369 in the P-domain, and hence the start of Na + /K + -activated ATP hydrolysis.

Mechanism for hydrogen diffusion in amorphous silicon

International Nuclear Information System (INIS)

Biswas, R.; Li, Q.; Pan, B.C.; Yoon, Y.

1998-01-01

Tight-binding molecular-dynamics calculations reveal a mechanism for hydrogen diffusion in hydrogenated amorphous silicon. Hydrogen diffuses through the network by successively bonding with nearby silicons and breaking their Si endash Si bonds. The diffusing hydrogen carries with it a newly created dangling bond. These intermediate transporting states are densely populated in the network, have lower energies than H at the center of stretched Si endash Si bonds, and can play a crucial role in hydrogen diffusion. copyright 1998 The American Physical Society

Interaction of Hydrogen with MOF-5.

Science.gov (United States)

Bordiga, Silvia; Vitillo, Jenny G; Ricchiardi, Gabriele; Regli, Laura; Cocina, Donato; Zecchina, Adriano; Arstad, Bjørnar; Bjørgen, Morten; Hafizovic, Jasmina; Lillerud, Karl Petter

2005-10-06

Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.

Hydrogen storage capacity of titanium met-cars

International Nuclear Information System (INIS)

Akman, N; Durgun, E; Yildirim, T; Ciraci, S

2006-01-01

The adsorption of hydrogen molecules on the titanium metallocarbohedryne (met-car) cluster has been investigated by using the first-principles plane wave method. We have found that, while a single Ti atom at the corner can bind up to three hydrogen molecules, a single Ti atom on the surface of the cluster can bind only one hydrogen molecule. Accordingly, a Ti 8 C 12 met-car can bind up to 16 H 2 molecules and hence can be considered as a high-capacity hydrogen storage medium. Strong interaction between two met-car clusters leading to the dimer formation can affect H 2 storage capacity slightly. Increasing the storage capacity by directly inserting H 2 into the met-car or by functionalizing it with an Na atom have been explored. It is found that the insertion of neither an H 2 molecule nor an Na atom could further promote the H 2 storage capacity of a Ti 8 C 12 cluster. We have also tested the stability of the H 2 -adsorbed Ti 8 C 12 met-car with ab initio molecular dynamics calculations which have been carried out at room temperature

The overexpressed human 46-kDa mannose 6-phosphate receptor mediates endocytosis and sorting of β-glucuronidase

International Nuclear Information System (INIS)

Watanabe, H.; Grubb, J.H.; Sly, W.S.

1990-01-01

The authors studied the function of the human small (46-kDa) mannose 6-phosphate receptor (SMPR) in transfected mouse L cells that do not express the larger insulin-like growth factor II/mannose 6-phosphate receptor. Cells overexpressing human SMPR were studied for enzyme binding to cell surface receptors, for binding to intracellular receptors in permeabilized cells, and for receptor-mediated endocytosis of recombinant human β-glucuronidase. Specific binding to human SMPR in permeabilized cells showed a pH optimum between pH 6.0 and pH 6.5. Binding was significant in the present of EDTA but was enhanced by added divalent cations. Up to 2.3% of the total functional receptor could be detected on the cell surface by enzyme binding. They present experiments showing that at very high levels of overexpression, and at pH 6.5, human SMPR mediated the endocytosis of β-glucuronidase. At pH 7.5, the rate of endocytosis was only 14% the rate seen at pH 6.5. Cells overexpressing human SMPR also showed reduced secretion of newly synthesized β-glucuronidase when compared to cells transfected with vector only, suggesting that overexpressed human SMPR can participate in sorting of newly synthesized β-glucuronidase and partially correct the sorting defect in mouse L cells that do not express the insulin-like growth factor II/mannose 6-phosphate receptor

Supramolecular Properties of Triazole-containing Two Armed Peptidomimetics: From Organogelators to Nucleotide-binding Tweezers

Science.gov (United States)

Chui, Tin Ki

obtain a clearer picture on the mode of association of these two series of branched peptidomimetics, the length of the tripeptidomimetic arms was truncated to a dipeptide, and the amino acid, valine, was used for further studies. Both the two new candidates, 88-K-V2 and 89-B-V2, were shown to dimerize in chloroform as shown from vapor pressure osmometry (VPO) studies. 1H NMR titration experiments indicated a better dimerization strength for the latter candidate due to the intermolecular pi-pi interactions offered by its benzene ring in addition to the intermolecular hydrogen bonding by the amides and triazole units. H/D exchange and 2D NMR experiments, and molecular modeling revealed that 88-K-V2 dimerized through the formation of antiparallel beta-strands whereas formation of parallel beta-strands took place in 89-B-V2. Compound 88-K-V2 was found to form 1:1 complexes with chloride (Ka 640 M-1) and monobasic diethyl phosphate (DEP) ion (Ka 810 M-1) in chloroform. Interestingly, 89-B-V 2 was shown to form the usual 1:1 complex with the former ion (Ka 970 M-1) while forming an unexpected 2:1 complex with the latter with positive cooperativity. It was observed that both the amides and triazole protons were involved in anion-binding. In the 88-K-V2-DEP complex, the host formed a helix-like structure that wrapped around the anion located at the center of the complex as determined by 2D NMR and molecular modeling studies. Finally, further structural modification of 88-K-V2 gave a water-soluble nucleotide-binding tweezer 93-K-R2·4TFA . This tweezer consisted of four arginines (R), two triazole units, two pyrene probes and a small hydrophilic ethanolamine tail. Fluorescence study showed that this tweezer was able to form 1:1 complexes with different nucleotides in water with similar binding strength regardless of the number of phosphate groups present in the nucleotides. Moleular modeling suggested that such a charge-independent binding behavior was due to the similar number

Decontamination of liquid radioactive waste by thorium phosphate

International Nuclear Information System (INIS)

Rousselle, J.; Grandjean, S.; Dacheux, N.; Genet, M.

2004-01-01

In the field of the complete reexamination of the chemistry of thorium phosphate and of the improvement of the homogeneity of Thorium Phosphate Diphosphate (TPD, Th 4 (PO 4 ) 4 P 2 O 7 ) prepared at high temperature, several crystallized compounds were prepared as initial powdered precursors. Due to the very low solubility products associated to these phases, their use in the field of the efficient decontamination of high-level radioactive liquid waste containing actinides (An) was carefully considered. Two main processes (called 'oxalate' and 'hydrothermal' chemical routes) were developed through a new concept combining the decontamination of liquid waste and the immobilization of the actinides in a ceramic matrix (TPD). In phosphoric media ('hydrothermal route'), the key-precursor was the Thorium Phosphate Hydrogen Phosphate hydrate (Th 2 (PO 4 ) 2 (HPO 4 ). H 2 O, TPHP, solubility product log(K S,0 0 ) ∼ - 67). The replacement of thorium by other tetravalent actinides (U, Np, Pu) in the structure, leading to the preparation of Th 2-x/2 An x/2 (PO 4 ) 2 (HPO 4 ). H 2 O solid solutions, was examined. A second method was also considered in parallel to illustrate this concept using the more well-known precipitation of oxalate as the initial decontamination step. For this method, the final transformation to single phase TPD containing actinides was purchased by heating a mixture of phosphate ions with the oxalate precipitate at high temperature. (authors)

Theoretical study of molecular hydrogen and spiltover hydrogen storage on two-dimensional covalent-organic frameworks

International Nuclear Information System (INIS)

Liu Xiu-Ying; He Jie; Yu Jing-Xin; Fan Zhi-Qin; Li Zheng-Xin

2014-01-01

Molecular hydrogen and spiltover hydrogen storages on five two-dimensional (2D) covalent-organic frameworks (COFs) (PPy-COF, TP-COF, BTP-COF, COF-18 Å, and HHTP-DPB COF) are investigated using the grand canonical Monte Carlo (GCMC) simulations and the density functional theory (DFT), respectively. The GCMC simulated results show that HHTP-DPB COF has the best performance for hydrogen storage, followed by BTP-COF, TP-COF, COF-18 Å, and PPy-COF. However, their adsorption amounts at room temperature are all too low to meet the uptake target set by US Department of Energy (US-DOE) and enable practical applications. The effects of pore size, surface area, and isosteric heat of hydrogen on adsorption amount are considered, which indicate that these three factors are all the important factors for determining the H 2 adsorption amount. The chemisorptions of spiltover hydrogen atoms on these five COFs represented by the cluster models are investigated using the DFT method. The saturation cluster models are constructed by considering all possible adsorption sites for these cluster models. The average binding energy of a hydrogen atom and the saturation hydrogen storage density are calculated. The large average binding energy indicates that the spillover process may proceed smoothly and reversibly. The saturation hydrogen storage density is much larger than the physisorption uptake of H 2 molecules at 298 K and 100 bar (1 bar = 10 5 Pa), and is close to or exceeds the 2010 US-DOE target of 6 wt% for hydrogen storage. This suggests that the hydrogen storage capacities of these COFs by spillover may be significantly enhanced. Thus 2D COFs studied in this paper are suitable hydrogen storage media by spillover

On calculation of the electrostatic potential of a phosphatidylinositol phosphate-containing phosphatidylcholine lipid membrane accounting for membrane dynamics.

Directory of Open Access Journals (Sweden)

Jonathan C Fuller

Full Text Available Many signaling events require the binding of cytoplasmic proteins to cell membranes by recognition of specific charged lipids, such as phosphoinositol-phosphates. As a model for a protein-membrane binding site, we consider one charged phosphoinositol phosphate (PtdIns(3P embedded in a phosphatidylcholine bilayer. As the protein-membrane binding is driven by electrostatic interactions, continuum solvent models require an accurate representation of the electrostatic potential of the phosphoinositol phosphate-containing membrane. We computed and analyzed the electrostatic potentials of snapshots taken at regular intervals from molecular dynamics simulations of the bilayer. We observe considerable variation in the electrostatic potential of the bilayer both along a single simulation and between simulations performed with the GAFF or CHARMM c36 force fields. However, we find that the choice of GAFF or CHARMM c36 parameters has little effect on the electrostatic potential of a given configuration of the bilayer with a PtdIns(3P embedded in it. From our results, we propose a remedian averaging method for calculating the electrostatic potential of a membrane system that is suitable for simulations of protein-membrane binding with a continuum solvent model.

Effect of altitude on oxygen binding by hemoglobin and on organic phosphate levels

Science.gov (United States)

Lenfant, Claude; Torrance, John; English, Eugenia; Finch, Clement A.; Reynafarje, Cesar; Ramos, Jose; Faura, Jose

1968-01-01

The relationship between oxygen dissociation and 2,3-diphosphoglycerate (2,3-DPG) in the red cell has been studied in subjects moving from low to high altitude and vice versa. Within 24 hr following the change in altitude there was a change in hemoglobin affinity for oxygen; this modification therefore represents an important rapid adaptive mechanism to anoxia. A parallel change occurred in the organic phosphate content of the red cell. While this study does not provide direct evidence of a cause-effect relationship, the data strongly suggest that with anoxia, the observed rise in organic phosphate content of the red cell is responsible for increased availability of oxygen to tissues. Images PMID:5725278

Reactions of dialkyl hydrogen phosphites with 2,3-diphenylindone

International Nuclear Information System (INIS)

Arbuzov, B.A.; Fuzhenkova, A.V.; Banderova, N.A.

1987-01-01

Dialkyl hydrogen phosphites are found to add to 2,3-diphenylindone at the carbonyl group with the formation of dialkyl 1-hydroxy-2,3-diphenylinden-1-yl phosphonates, which, under conditions of basic catalysis, are rearranged into diakyl 2,3-diphenylinden-1-yl phosphates, presumably as a result of phosphonate-phosphate rearrangement. Data derived by IR and NMR spectroscopy are included on the electronic and molecular structure of the resulting isomers. Electron density and spin-spin coupling constants are also determined

Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

International Nuclear Information System (INIS)

Gao Yi; Zeng, X C

2007-01-01

We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems

HIV-1 Nef binds with human GCC185 protein and regulates mannose 6 phosphate receptor recycling

Energy Technology Data Exchange (ETDEWEB)

Kumar, Manjeet; Kaur, Supinder; Nazir, Aamir; Tripathi, Raj Kamal, E-mail: rajkamalcdri@gmail.com

2016-05-20

HIV-1 Nef modulates cellular function that enhances viral replication in vivo which culminate into AIDS pathogenesis. With no enzymatic activity, Nef regulates cellular function through host protein interaction. Interestingly, trans-cellular introduction of recombinant Nef protein in Caenorhabditis elegans results in AIDS like pathogenesis which might share common pathophysiology because the gene sequence of C. elegans and humans share considerable homology. Therefore employing C. elegans based initial screen complemented with sequence based homology search we identified GCC185 as novel host protein interacting with HIV-1 Nef. The detailed molecular characterization revealed N-terminal EEEE{sub 65} acidic domain of Nef as key region for interaction. GCC185 is a tethering protein that binds with Rab9 transport vesicles. Our results show that Nef-GCC185 interaction disrupts Rab9 interaction resulting in delocalization of CI-MPR (cation independent Mannose 6 phosphate receptor) resulting in elevated secretion of hexosaminidase. In agreement with this, our studies identified novel host GCC185 protein that interacts with Nef EEEE65 acidic domain interfering GCC185-Rab9 vesicle membrane fusion responsible for retrograde vesicular transport of CI-MPR from late endosomes to TGN. In light of existing report suggesting critical role of Nef-GCC185 interaction reveals valuable mechanistic insights affecting specific protein transport pathway in docking of late endosome derived Rab9 bearing transport vesicle at TGN elucidating role of Nef during viral pathogenesis. -- Highlights: •Nef, an accessory protein of HIV-1 interacts with host factor and culminates into AIDS pathogenesis. •Using Caenorhabditis elegans based screen system, novel Nef interacting cellular protein GCC185 was identified. •Molecular characterization of Nef and human protein GCC185 revealed Nef EEEE{sub 65} key region interacted with full length GCC185. •Nef impeded the GCC185-Rab 9 interaction and

The 1.1 Å resolution structure of a periplasmic phosphate-binding protein from Stenotrophomonas maltophilia: a crystallization contaminant identified by molecular replacement using the entire Protein Data Bank.

Science.gov (United States)

Keegan, Ronan; Waterman, David G; Hopper, David J; Coates, Leighton; Taylor, Graham; Guo, Jingxu; Coker, Alun R; Erskine, Peter T; Wood, Steve P; Cooper, Jonathan B

2016-08-01

During efforts to crystallize the enzyme 2,4-dihydroxyacetophenone dioxygenase (DAD) from Alcaligenes sp. 4HAP, a small number of strongly diffracting protein crystals were obtained after two years of crystal growth in one condition. The crystals diffracted synchrotron radiation to almost 1.0 Å resolution and were, until recently, assumed to be formed by the DAD protein. However, when another crystal form of this enzyme was eventually solved at lower resolution, molecular replacement using this new structure as the search model did not give a convincing solution with the original atomic resolution data set. Hence, it was considered that these crystals might have arisen from a protein impurity, although molecular replacement using the structures of common crystallization contaminants as search models again failed. A script to perform molecular replacement using MOLREP in which the first chain of every structure in the PDB was used as a search model was run on a multi-core cluster. This identified a number of prokaryotic phosphate-binding proteins as scoring highly in the MOLREP peak lists. Calculation of an electron-density map at 1.1 Å resolution based on the solution obtained with PDB entry 2q9t allowed most of the amino acids to be identified visually and built into the model. A BLAST search then indicated that the molecule was most probably a phosphate-binding protein from Stenotrophomonas maltophilia (UniProt ID B4SL31; gene ID Smal_2208), and fitting of the corresponding sequence to the atomic resolution map fully corroborated this. Proteins in this family have been linked to the virulence of antibiotic-resistant strains of pathogenic bacteria and with biofilm formation. The structure of the S. maltophilia protein has been refined to an R factor of 10.15% and an Rfree of 12.46% at 1.1 Å resolution. The molecule adopts the type II periplasmic binding protein (PBP) fold with a number of extensively elaborated loop regions. A fully dehydrated phosphate

Effect of humic acid preloading on phosphate adsorption onto zirconium-modified zeolite.

Science.gov (United States)

Lin, Jianwei; Zhang, Zhe; Zhan, Yanhui

2017-05-01

A zirconium-modified zeolite (ZrMZ) was prepared, and then, humic acid (HA) was immobilized on the ZrMZ surface to prepare HA-loaded ZrMZ (HA-ZrMZ). The obtained ZrMZ and HA-ZrMZ were characterized by energy dispersive X-ray spectroscopy, elemental analyzer, N 2 adsorption/desorption isotherms, pH at the point of zero charge, and X-ray photoelectron spectroscopy. The adsorption characteristics of phosphate on ZrMZ and HA-ZrMZ were comparatively investigated in batch mode. The adsorption mechanism of phosphate on ZrMZ and HA-ZrMZ was investigated by ionic strength effect and 31 P nuclear magnetic resonance. The mechanism for phosphate adsorption onto ZrMZ was the formation of inner-sphere phosphate complexes at the solid/solution interface. The preloading of HA on ZrMZ reduced the phosphate adsorption capacity, and the more the HA loading amount, the lower the phosphate adsorption capacity. However, the preloading of HA on ZrMZ did not change the phosphate adsorption mechanism; i.e., the formation of inner-sphere phosphate surface complexes was still responsible for the adsorption of phosphate on HA-ZrMZ. The decreased phosphate adsorption capacity for ZrMZ after HA coating could be attributed to the fact that the coating of HA on ZrMZ reduced the amount of binding active sites available for phosphate adsorption, changed the adsorbent surface charges, and reduced the specific surface areas and pore volumes of ZrMZ.

Conductivity variations in composites of. alpha. -zirconium phosphate and alumina

Energy Technology Data Exchange (ETDEWEB)

Slade, R.C.T.; Knowles, J.A. (Dept. of Chemistry, Exeter Univ. (UK))

Composite proton-conducting solid electrolytes have been formed from {alpha}-zirconium hydrogen phosphate ({alpha}-Zr(HPO{sub 4}){sub 2}.H{sub 2}O, {alpha}-ZrP) and aluminas (Al{sub 2}O{sub 3}) in varying mole ratios. Conductivity variations as a function of temperature have been characterised and compared to that for a delaminated {alpha}-ZrP (no alumina). There are no appreciable conductivity enhancements on composite formation, but conductivity for materials ca. 50 mole% in alumina can be comparable to the delaminated materials. Differential scanning calorimetry shows the composites to have different thermal properties to simple admixtures. High resolution {sup 31}P NMR studies show reaction to form aluminium phosphate at the interface between components. (orig.).

NMR experiments for the rapid identification of P=O···H-X type hydrogen bonds in nucleic acids.

Science.gov (United States)

Duchardt-Ferner, Elke; Wöhnert, Jens

2017-10-01

Hydrogen bonds involving the backbone phosphate groups occur with high frequency in functional RNA molecules. They are often found in well-characterized tertiary structural motifs presenting powerful probes for the rapid identification of these motifs for structure elucidation purposes. We have shown recently that stable hydrogen bonds to the phosphate backbone can in principle be detected by relatively simple NMR-experiments, providing the identity of both the donor hydrogen and the acceptor phosphorous within the same experiment (Duchardt-Ferner et al., Angew Chem Int Ed Engl 50:7927-7930, 2011). However, for imino and hydroxyl hydrogen bond donor groups rapidly exchanging with the solvent as well as amino groups broadened by conformational exchange experimental sensitivity is severely hampered by extensive line broadening. Here, we present improved methods for the rapid identification of hydrogen bonds to phosphate groups in nucleic acids by NMR. The introduction of the SOFAST technique into 1 H, 31 P-correlation experiments as well as a BEST-HNP experiment exploiting 3h J N,P rather than 2h J H,P coupling constants enables the rapid and sensitive identification of these hydrogen bonds in RNA. The experiments are applicable for larger RNAs (up to ~ 100-nt), for donor groups influenced by conformational exchange processes such as amino groups and for hydrogen bonds with rather labile hydrogens such as 2'-OH groups as well as for moderate sample concentrations. Interestingly, the size of the through-hydrogen bond scalar coupling constants depends not only on the type of the donor group but also on the structural context. The largest coupling constants were measured for hydrogen bonds involving the imino groups of protonated cytosine nucleotides as donors.

Preparation and bioactivity of micro-arc oxidized calcium phosphate coatings

Energy Technology Data Exchange (ETDEWEB)

Pan, Y.K. [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Ji' nan, Shandong 250061 (China); School of Materials Science and Engineering, Shandong University, Ji' nan, Shandong 250061 (China); Chen, C.Z., E-mail: czchen@sdu.edu.cn [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Ji' nan, Shandong 250061 (China); School of Materials Science and Engineering, Shandong University, Ji' nan, Shandong 250061 (China); Wang, D.G.; Lin, Z.Q. [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Ji' nan, Shandong 250061 (China); School of Materials Science and Engineering, Shandong University, Ji' nan, Shandong 250061 (China)

2013-09-16

Calcium phosphate (CaP) coatings were prepared on ZK60 magnesium alloy by micro-arc oxidation (MAO) in electrolyte containing calcium acetate monohydrate (CH{sub 3}COO){sub 2}Ca·H{sub 2}O) and disodium hydrogen phosphate dodecahydrate (Na{sub 2}HPO{sub 4}·12H{sub 2}O). Scanning electron microscope (SEM), energy-dispersive X-ray spectrometry (EDX) and X-ray diffractometer (XRD) were employed to characterize the microstructure, elemental distribution and phase composition of the CaP coatings respectively. Simulated body fluid (SBF) immersion test was used to evaluate the coating degradability and bioactivity. After 30 days of SBF immersion, the CaP coatings effectively reduce the degradation rate. The surfaces of CaP coatings are covered by a new layer formed of numerous needle-like, spherical and columned calcium phosphates. SEM, EDX and XRD results suggest that these calcium phosphates are bioactive calcium phosphate phases such as hydroxyapatite (Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}, HA) and calcium pyrophosphates (Ca{sub 2}P{sub 2}O{sub 7}, CPP). The formation of these calcium phosphates indicates that the CaP coatings have bioactivity. - Highlights: • Bioactive CaP coatings are successfully formed on ZK60 magnesium alloy. • CaP coatings consist of MgO, MgF{sub 2}, CaO, CaF{sub 2} and Ca{sub 3}(PO{sub 4}){sub 2}. • Needle-like, spherical and columned calcium phosphates formed in SBF. • CaP coatings exhibit bioactivity and low corrosion rate.

Effect of dipotassium hydrogen phosphate on thermodynamic properties of glycine and L-alanine in aqueous solutions at different temperatures

International Nuclear Information System (INIS)

Kumar, Harsh; Kaur, Kirtanjot

2012-01-01

Highlights: ► Densities and speeds of sound of amino acids in DKHP. ► Apparent molar volume and apparent molar compressibilities were calculated. ► The partial molar expansibilities at infinite dilution φ E 0 were obtained. ► Hydration number n H was calculated. ► The results are discussed in terms of solute–solvent interactions. - Abstract: Densities, ρ, speed of sound, u for glycine, L-alanine have been measured in aqueous solutions of dipotassium hydrogen phosphate (DKHP) ranging from 0.2, 0.4, 0.6 and 0.8 mol·kg −1 at temperatures T = (288.15, 298.15, 308.15 and 318.15) K. The different parameters such as apparent molar volume, limiting apparent molar volume, transfer volume, partial molar expansibility have been derived from density data. Experimental speeds of sound data were used to estimate apparent molar adiabatic compressibility, limiting apparent molar adiabatic compressibility, transfer parameter and hydration number. These parameters have been discussed in the light of ion-ion and ion-solvent interactions.

The RNA-Binding Site of Poliovirus 3C Protein Doubles as a Phosphoinositide-Binding Domain.

Science.gov (United States)

Shengjuler, Djoshkun; Chan, Yan Mei; Sun, Simou; Moustafa, Ibrahim M; Li, Zhen-Lu; Gohara, David W; Buck, Matthias; Cremer, Paul S; Boehr, David D; Cameron, Craig E

2017-12-05

Some viruses use phosphatidylinositol phosphate (PIP) to mark membranes used for genome replication or virion assembly. PIP-binding motifs of cellular proteins do not exist in viral proteins. Molecular-docking simulations revealed a putative site of PIP binding to poliovirus (PV) 3C protein that was validated using nuclear magnetic resonance spectroscopy. The PIP-binding site was located on a highly dynamic α helix, which also functions in RNA binding. Broad PIP-binding activity was observed in solution using a fluorescence polarization assay or in the context of a lipid bilayer using an on-chip, fluorescence assay. All-atom molecular dynamics simulations of the 3C protein-membrane interface revealed PIP clustering and perhaps PIP-dependent conformations. PIP clustering was mediated by interaction with residues that interact with the RNA phosphodiester backbone. We conclude that 3C binding to membranes will be determined by PIP abundance. We suggest that the duality of function observed for 3C may extend to RNA-binding proteins of other viruses. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metal-functionalized silicene for efficient hydrogen storage.

Science.gov (United States)

Hussain, Tanveer; Chakraborty, Sudip; Ahuja, Rajeev

2013-10-21

First-principles calculations based on density functional theory are used to investigate the electronic structure along with the stability, bonding mechanism, band gap, and charge transfer of metal-functionalized silicene to envisage its hydrogen-storage capacity. Various metal atoms including Li, Na, K, Be, Mg, and Ca are doped into the most stable configuration of silicene. The corresponding binding energies and charge-transfer mechanisms are discussed from the perspective of hydrogen-storage compatibility. The Li and Na metal dopants are found to be ideally suitable, not only for strong metal-to-substrate binding and uniform distribution over the substrate, but also for the high-capacity storage of hydrogen. The stabilities of both Li- and Na-functionalized silicene are also confirmed through molecular dynamics simulations. It is found that both of the alkali metals, Li(+) and Na(+), can adsorb five hydrogen molecules, attaining reasonably high storage capacities of 7.75 and 6.9 wt %, respectively, with average adsorption energies within the range suitable for practical hydrogen-storage applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Innovative Approach to Treat Incisors Hypomineralization (MIH): A Combined Use of Casein Phosphopeptide-Amorphous Calcium Phosphate and Hydrogen Peroxide-A Case Report.

Science.gov (United States)

Mastroberardino, Stefano; Campus, Guglielmo; Strohmenger, Laura; Villa, Alessandro; Cagetti, Maria Grazia

2012-01-01

Molar Incisor Hypomineralization (MIH) is characterized by a developmentally derived deficiency in mineral enamel. Affected teeth present demarcated enamel opacities, ranging from white to brown; also hypoplasia can be associated. Patient frequently claims aesthetic discomfort if anterior teeth are involved. This problem leads patients to request a bleaching treatment to improve aestheticconditions.Nevertheless, hydrogen peroxide can produce serious side-effects, resulting from further mineral loss. Microabrasion and/or a composite restoration are the treatments of choice in teeth with mild/moderate MIH, but they also need enamel loss. Recently, a new remineralizing agent based on Casein Phosphopeptide-Amorphous Calcium Phosphate (CPP-ACP) has been proposed to be effective in hypomineralized enamel, improving also aesthetic conditions. The present paper presents a case report of a young man with white opacities on incisors treated with a combined use of CPP-ACP mousse and hydrogen peroxide gel to correct the aesthetic defect. The patient was instructed to use CPP-ACP for two hours per day for three months in order to obtain enamel remineralization followed by a combined use of CPP-ACP and bleaching agent for further two months. At the end of this five-month treatment, a noticeable aesthetic improvement of the opacities was observed.

An Innovative Approach to Treat Incisors Hypomineralization (MIH: A Combined Use of Casein Phosphopeptide-Amorphous Calcium Phosphate and Hydrogen Peroxide—A Case Report

Directory of Open Access Journals (Sweden)

Stefano Mastroberardino

2012-01-01

Full Text Available Molar Incisor Hypomineralization (MIH is characterized by a developmentally derived deficiency in mineral enamel. Affected teeth present demarcated enamel opacities, ranging from white to brown; also hypoplasia can be associated. Patient frequently claims aesthetic discomfort if anterior teeth are involved. This problem leads patients to request a bleaching treatment to improve aestheticconditions.Nevertheless, hydrogen peroxide can produce serious side-effects, resulting from further mineral loss. Microabrasion and/or a composite restoration are the treatments of choice in teeth with mild/moderate MIH, but they also need enamel loss. Recently, a new remineralizing agent based on Casein Phosphopeptide-Amorphous Calcium Phosphate (CPP-ACP has been proposed to be effective in hypomineralized enamel, improving also aesthetic conditions. The present paper presents a case report of a young man with white opacities on incisors treated with a combined use of CPP-ACP mousse and hydrogen peroxide gel to correct the aesthetic defect. The patient was instructed to use CPP-ACP for two hours per day for three months in order to obtain enamel remineralization followed by a combined use of CPP-ACP and bleaching agent for further two months. At the end of this five-month treatment, a noticeable aesthetic improvement of the opacities was observed.

Cation binding at the node of Ranvier: I. Localization of binding sites during development.

Science.gov (United States)

Zagoren, J C; Raine, C S; Suzuki, K

1982-06-17

Cations are known to bind to the node of Ranvier and the paranodal regions of myelinated fibers. The integrity of these specialized structures is essential for normal conduction. Sites of cation binding can be microscopically identified by the electrondense histochemical reaction product formed by the precipitate of copper sulfate/potassium ferrocyanide. This technique was used to study the distribution of cation binding during normal development of myelinating fibers. Sciatic nerves of C57B1 mice, at 1, 3, 5, 6, 7, 8, 9, 13, 16, 18, 24 and 30 days of age, were prepared for electron microscopy following fixation in phosphate-buffered 2.5% glutaraldehyde and 1% osmic acid, microdissection and incubation in phosphate-buffered 0.1 M cupric sulfate followed by 0.1 M potassium ferrocyanide. Localization of reaction product was studied by light and electron microscopy. By light microscopy, no reaction product was observed prior to 9 days of age. At 13 days, a few nodes and paranodes exhibited reaction product. This increased in frequency and intensity up to 30 days when almost all nodes or paranodes exhibited reaction product. Ultrastructurally, diffuse reaction product was first observed at 3 days of age in the axoplasm of the node, in the paranodal extracellular space of the terminal loops, in the Schwann cell proper and in the terminal loops of Schwann cell cytoplasm. When myelinated axons fulfilled the criteria for mature nodes, reaction product was no longer observed in the Schwann cell cytoplasm, while the intensity of reaction product in the nodal axoplasm and paranodal extracellular space of the terminal loops increased. Reaction product in the latter site appeared to be interrupted by the transverse bands. These results suggest that cation binding accompanies nodal maturity and that the Schwann cell may play a role in production or storage of the cation binding substance during myelinogenesis and development.

Oxygen binding to nitric oxide marked hemoglobin

International Nuclear Information System (INIS)

Louro, S.R.W.; Ribeiro, P.C.; Bemski, G.

1979-04-01

Electron spin resonance spectra of organic phosphate free human hemoglobin marked with nitric oxide at the sixth coordination position of one of the four hemes allow to observe the transition from the tense (T) to the relaxed (R) conformation, as a function of parcial oxygen pressure. The spectra are composites of contributions from α sub(T), α sub(R) and β chains spectra, showing the presence of only two conformations: T and R. In the absence of organic phosphates NO binds to α and β chains with the same probability, but in the presence of phosphates NO combines preferentially with α chains. The dissociation of NO proceeds at least an order of magnitude faster in T than in R configuration. (author) [pt

Partitioning of L-methionine in aqueous two-phase systems containing poly(propylene glycol) and sodium phosphate salts

Energy Technology Data Exchange (ETDEWEB)

Salabat, Alireza, E-mail: a-salabat@araku.ac.ir [Chemistry Department, Arak University, P.O. Box 38156-879, Arak (Iran, Islamic Republic of); Sadeghi, Rahmat [Department of Chemistry, University of Kurdistan, Sanandaj, Kurdistan 66135 (Iran, Islamic Republic of); Moghadam, Somayeh Tiani [Chemistry Department, Arak University, P.O. Box 38156-879, Arak (Iran, Islamic Republic of); Jamehbozorg, Bahman [Department of Chemistry, University of Kurdistan, Sanandaj, Kurdistan 66135 (Iran, Islamic Republic of)

2011-10-15

Highlights: > Thermodynamics parameters for partitioning of L-methionine in ATPS. > Investigation of different effects on partition coefficient of the amino acid. > Propose the best condition for L-methionine partitioning. - Abstract: The partitioning behavior of L-methionine has been studied in aqueous two-phase systems of (poly(propylene glycol) + sodium phosphate salts + H{sub 2}O) at different temperatures. The salts used were sodium di-hydrogen phosphate (NaH{sub 2}PO{sub 4}), di-sodium hydrogen phosphate (Na{sub 2}HPO{sub 4}) and tri-sodium phosphate (Na{sub 3}PO{sub 4}). The effects of tie line length, salt type, and temperature on the partition coefficient of this amino acid have been studied. In addition, thermodynamic parameters ({Delta}H{sup o}, {Delta}S{sup o} and {Delta}G{sup o}) as a function of temperature were calculated. The results showed that increasing tie line length led to decreasing of the partition coefficient. We also showed that the partition coefficients of the amino acid in the systems containing Na{sub 3}PO{sub 4} are greater than the other two salts. Moreover, it is verified that increasing temperature led to decreasing the partition coefficient. The experimental partition coefficient data are correlated using a modified virial-type model.

Spectral analysis of naturally occurring methylxanthines (theophylline, theobromine and caffeine) binding with DNA.

Science.gov (United States)

Johnson, Irudayam Maria; Prakash, Halan; Prathiba, Jeyaguru; Raghunathan, Raghavachary; Malathi, Raghunathan

2012-01-01

Nucleic acids exist in a dynamic equilibrium with a number of molecules that constantly interact with them and regulate the cellular activities. The inherent nature of the structure and conformational integrity of these macromolecules can lead to altered biological activity through proper targeting of nucleic acids binding ligands or drug molecules. We studied the interaction of naturally occurring methylxanthines such as theophylline, theobromine and caffeine with DNA, using UV absorption and Fourier transform infrared (FTIR) spectroscopic methods, and especially monitored their binding affinity in the presence of Mg(2+) and during helix-coil transitions of DNA by temperature (T(m)) or pH melting profiles. The study indicates that all these molecules effectively bind to DNA in a dose dependent manner. The overall binding constants of DNA-theophylline = 3.5×10(3) M(-1), DNA-theobromine = 1.1×10(3) M(-1), and DNA-Caffeine = 3.8×10(3) M(-1). On the other hand T(m)/pH melting profiles showed 24-35% of enhanced binding activity of methylxanthines during helix-coil transitions of DNA rather than to its native double helical structure. The FTIR analysis divulged that theophylline, theobromine and caffeine interact with all the base pairs of DNA (A-T; G-C) and phosphate group through hydrogen bond (H-bond) interaction. In the presence of Mg(2+), methylxanthines altered the structure of DNA from B to A-family. However, the B-family structure of DNA remained unaltered in DNA-methylxanthines complexes or in the absence of Mg(2+). The spectral analyses indicated the order of binding affinity as "caffeine≥theophylline>theobromine" to the native double helical DNA, and "theophylline≥theobromine>caffeine to the denatured form of DNA and in the presence of divalent metal ions.

Spectral analysis of naturally occurring methylxanthines (theophylline, theobromine and caffeine binding with DNA.

Directory of Open Access Journals (Sweden)

Irudayam Maria Johnson

Full Text Available Nucleic acids exist in a dynamic equilibrium with a number of molecules that constantly interact with them and regulate the cellular activities. The inherent nature of the structure and conformational integrity of these macromolecules can lead to altered biological activity through proper targeting of nucleic acids binding ligands or drug molecules. We studied the interaction of naturally occurring methylxanthines such as theophylline, theobromine and caffeine with DNA, using UV absorption and Fourier transform infrared (FTIR spectroscopic methods, and especially monitored their binding affinity in the presence of Mg(2+ and during helix-coil transitions of DNA by temperature (T(m or pH melting profiles. The study indicates that all these molecules effectively bind to DNA in a dose dependent manner. The overall binding constants of DNA-theophylline = 3.5×10(3 M(-1, DNA-theobromine = 1.1×10(3 M(-1, and DNA-Caffeine = 3.8×10(3 M(-1. On the other hand T(m/pH melting profiles showed 24-35% of enhanced binding activity of methylxanthines during helix-coil transitions of DNA rather than to its native double helical structure. The FTIR analysis divulged that theophylline, theobromine and caffeine interact with all the base pairs of DNA (A-T; G-C and phosphate group through hydrogen bond (H-bond interaction. In the presence of Mg(2+, methylxanthines altered the structure of DNA from B to A-family. However, the B-family structure of DNA remained unaltered in DNA-methylxanthines complexes or in the absence of Mg(2+. The spectral analyses indicated the order of binding affinity as "caffeine≥theophylline>theobromine" to the native double helical DNA, and "theophylline≥theobromine>caffeine to the denatured form of DNA and in the presence of divalent metal ions.

Stimulation of Suicidal Erythrocyte Death by Increased Extracellular Phosphate Concentrations

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Jakob Voelkl

2014-02-01

Full Text Available Background/Aim: Anemia in renal insufficiency results in part from impaired erythrocyte formation due to erythropoietin and iron deficiency. Beyond that, renal insufficiency enhances eryptosis, the suicidal erythrocyte death characterized by phosphatidylserine-exposure at the erythrocyte surface. Eryptosis may be stimulated by increase of cytosolic Ca2+-activity ([Ca2+]i. Several uremic toxins have previously been shown to stimulate eryptosis. Renal insufficiency is further paralleled by increase of plasma phosphate concentration. The present study thus explored the effect of phosphate on erythrocyte death. Methods: Cell volume was estimated from forward scatter, phosphatidylserine-exposure from annexin V binding, and [Ca2+]i from Fluo3-fluorescence. Results: Following a 48 hours incubation, the percentage of phosphatidylserine exposing erythrocytes markedly increased as a function of extracellular phosphate concentration (from 0-5 mM. The exposure to 2 mM or 5 mM phosphate was followed by slight but significant hemolysis. [Ca2+]i did not change significantly up to 2 mM phosphate but significantly decreased at 5 mM phosphate. The effect of 2 mM phosphate on phosphatidylserine exposure was significantly augmented by increase of extracellular Ca2+ to 1.7 mM, and significantly blunted by nominal absence of extracellular Ca2+, by additional presence of pyrophosphate as well as by presence of p38 inhibitor SB203580. Conclusion: Increasing phosphate concentration stimulates erythrocyte membrane scrambling, an effect depending on extracellular but not intracellular Ca2+ concentration. It is hypothesized that suicidal erythrocyte death is triggered by complexed CaHPO4.

The transport of phosphate between the plasma and dialysate compartments in peritoneal dialysis is influenced by an electric potential difference

DEFF Research Database (Denmark)

Graff, J; Fugleberg, S; Brahm, J

1996-01-01

was not identifiable. Furthermore, it was demonstrated that the electrochemical gradient between plasma water and dialysate favours the diffusive phosphate transport, and both electric and chemical potentials must be taken into account in calculations of the transperitoneal phosphate transport.......Six kinetic models of transperitoneal phosphate transport were formulated and validated on the basis of experimental results obtained from 22 non-diabetic patients undergoing peritoneal dialysis. The models were designed to elucidate the presence or absence of diffusive, non-lymphatic convective......, and lymphatic convective phosphate transport. Calculations allowed for a 20% protein binding of phosphate. The validation procedure demonstrated that only diffusive and non-lymphatic convective phosphate transport mechanisms were identifiable. A lymphatic convective phosphate transport mechanism...

Binding energy and optical properties of an off-center hydrogenic donor impurity in a spherical quantum dot placed at the center of a cylindrical nano-wire

International Nuclear Information System (INIS)

Safarpour, Gh.; Barati, M.; Zamani, A.; Niknam, E.

2014-01-01

The binding energy as well as the linear, third-order nonlinear and total optical absorption coefficient and refractive index changes of an off-center hydrogenic donor impurity in an InAs spherical quantum dot placed at the center of a GaAs cylindrical nano-wire have been investigated. In this regard, the effective-mass approximation approach is considered and eigenvalues and corresponding eigenfunctions are calculated via the finite element method. The binding energy is plotted as a function of the dot size and impurity position along with optical properties as a function of photon energy. In this study two different directions have been considered for impurity position, along the nano-wire axis and perpendicular to it. It has been found that the binding energy, absorption coefficient and refractive index changes are impressively affected not only by the dot radius but also by the position of the impurity and its direction. Additionally, the optical saturation can be tuned by the direction of the impurity and incident optical intensity. -- Highlights: • We consider spherical quantum dot located at the center of a cylindrical nano-wire. • An off-center hydrogenic donor impurity is considered in the system. • Binding energy is affected by orientation of impurity and its distance from center. • Saturation depends on the orientation of impurity position. • By shifting impurity position, orientation and dot radius blue- and red-shifts appear

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

Science.gov (United States)

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.

Communication: Towards the binding energy and vibrational red shift of the simplest organic hydrogen bond: Harmonic constraints for methanol dimer

International Nuclear Information System (INIS)

Heger, Matthias; Suhm, Martin A.; Mata, Ricardo A.

2014-01-01

The discrepancy between experimental and harmonically predicted shifts of the OH stretching fundamental of methanol upon hydrogen bonding to a second methanol unit is too large to be blamed mostly on diagonal and off-diagonal anharmonicity corrections. It is shown that a decisive contribution comes from post-MP2 electron correlation effects, which appear not to be captured by any of the popular density functionals. We also identify that the major deficiency is in the description of the donor OH bond. Together with estimates for the electronic and harmonically zero-point corrected dimer binding energies, this work provides essential constraints for a quantitative description of this simple hydrogen bond. The spectroscopic dissociation energy is predicted to be larger than 18 kJ/mol and the harmonic OH-stretching fundamental shifts by about −121 cm −1 upon dimerization, somewhat more than in the anharmonic experiment (−111 cm −1 )

Two-dimensional metal dichalcogenides and oxides for hydrogen evolution

DEFF Research Database (Denmark)

Pandey, Mohnish; Vojvodic, Aleksandra; Thygesen, Kristian Sommer

2015-01-01

We explore the possibilities of hydrogen evolution by basal planes of 2D metal dichalcogenides and oxides in the 2H and 1T class of structures using the hydrogen binding energy as a computational activity descriptor. For some groups of systems like the Ti, Zr, and Hf dichalcogenides the hydrogen...

Biomimetic fabrication of calcium phosphate/chitosan nanohybrid composite in modified simulated body fluids

Directory of Open Access Journals (Sweden)

K. H. Park

2017-01-01

Full Text Available In this study, nucleation and growth of bone-like hydroxyapatite (HAp mineral in modified simulated body fluids (m-SBF were induced on chitosan (CS substrates, which were prepared by spin coating of chitosan on Ti substrate. The m-SBF showed a two fold increase in the concentrations of calcium and phosphate ions compared to SBF, and the post-NaOH treatment provided stabilization of the coatings. The calcium phosphate/chitosan composite prepared in m-SBF showed homogeneous distribution of approximately 350 nm-sized spherical clusters composed of octacalcium phosphate (OCP; Ca8H2(PO46·5H2O crystalline structure. Chitosan provided a control over the size of calcium phosphate prepared by immersion in m-SBF, and post-NaOH treatment supported the binding of calcium phosphate compound on the Ti surface. Post-NaOH treatment increased hydrophilicity and crystallinity of carbonate apatite, which increased its potential for biomedical application.

Dual and Direction-Selective Mechanisms of Phosphate Transport by the Vesicular Glutamate Transporter

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Julia Preobraschenski

2018-04-01

Full Text Available Summary: Vesicular glutamate transporters (VGLUTs fill synaptic vesicles with glutamate and are thus essential for glutamatergic neurotransmission. However, VGLUTs were originally discovered as members of a transporter subfamily specific for inorganic phosphate (Pi. It is still unclear how VGLUTs accommodate glutamate transport coupled to an electrochemical proton gradient ΔμH+ with inversely directed Pi transport coupled to the Na+ gradient and the membrane potential. Using both functional reconstitution and heterologous expression, we show that VGLUT transports glutamate and Pi using a single substrate binding site but different coupling to cation gradients. When facing the cytoplasm, both ions are transported into synaptic vesicles in a ΔμH+-dependent fashion, with glutamate preferred over Pi. When facing the extracellular space, Pi is transported in a Na+-coupled manner, with glutamate competing for binding but at lower affinity. We conclude that VGLUTs have dual functions in both vesicle transmitter loading and Pi homeostasis within glutamatergic neurons. : Preobraschenski et al. show that the vesicular glutamate transporter functions as a bi-directional phosphate transporter that is coupled with different cations in each direction and hence may play a key role in neuronal phosphate homeostasis. Keywords: VGLUT, SLC17 family, type I Na+-dependent inorganic phosphate transporter, ATPase, proteoliposomes, hybrid vesicles, anti-VGLUT1 nanobody

Phosphorylation and 14-3-3 binding of Arabidopsis trehalose-phosphate synthase 5 in response to 2-deoxyglucose

DEFF Research Database (Denmark)

Harthill, Jean E; Meek, Sarah E M; Morrice, Nick

2006-01-01

Trehalose-6-phosphate is a 'sugar signal' that regulates plant metabolism and development. The Arabidopsis genome encodes trehalose-6-phosphate synthase (TPS) and trehalose-6-phosphatase (TPP) enzymes. It also encodes class II proteins (TPS isoforms 5-11) that contain both TPS-like and TPP...

Stabilization of Cs/Re trapping filters using magnesium phosphate ceramics

International Nuclear Information System (INIS)

Jae Hwan Yang; Jin Myeong Shin; Chang Hwa Lee; Chul Min Heo; Min Ku Jeon; Kweon Ho Kang

2013-01-01

The present study a promising method for stabilizing spent filters trapping cesium and technetium by using magnesium phosphate ceramics. Simulated spent filters were fabricated by vaporizing nonradioactive cesium and rhenium (a surrogate of Tc) through the voloxidizer. In order to reveal the characteristics of spent filters, phase structures and thermal stability were analyzed by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy, and thermogravimetric analysis techniques. Waste forms were fabricated by crushing spent filters and mixing them with magnesium oxide and potassium phosphate. Characterizations of the waste forms were performed by the analyses of compressive strength, apparent porosity, XRD, and scanning electron microscopy. The waste forms showed the excellent mechanical property compared with that of ordinary Portland cement, with the highest compressive strength of 38.1 MPa in the sample with 30 wt% of Cs-filter. Microstructural analysis suggests that waste materials are encapsulated by the binding matrix composed of magnesium potassium phosphate. The results of characterization suggest that fabricating a sound and durable waste form is possible with magnesium phosphate ceramics. (author)

Hydrogen in trapping states innocuous to environmental degradation of high-strength steels

International Nuclear Information System (INIS)

Takai, Kenichi

2003-01-01

Hydrogen in trapping states innocuous to environmental degradation of the mechanical properties of high-strength steels has been separated and extracted using thermal desorption analysis (TDA) and slow strain rate test (SSRT). The high-strength steel occluding only hydrogen desorbed at low temperature (peak 1), as determined by TDA, decreases in maximum stress and plastic elongation with increasing occlusion time of peak 1 hydrogen. Thus the trapping state of peak 1 hydrogen is directly associated with environmental degradation. The trap activation energy for peak 1 hydrogen is 23.4 kJ/mol, so the peak 1 hydrogen corresponds to weaker binding states and diffusible states at room temperature. In contrast, the high-strength steel occluding only hydrogen desorbed at high temperature (peak 2), by TDA, maintains the maximum stress and plastic elongation in spite of an increasing content of peak 2 hydrogen. This result indicates that the peak 2 hydrogen trapping state is innocuous to environmental degradation, even though the steel occludes a large amount of peak 2 hydrogen. The trap activation energy for peak 2 hydrogen is 65.0 kJ/mol, which indicates a stronger binding state and nondiffusibility at room temperature. The trap activation energy for peak 2 hydrogen suggests that the driving force energy required for stress-induced, diffusion during elastic and plastic deformation, and the energy required for hydrogen dragging by dislocation mobility during plastic deformation are lower than the binding energy between hydrogen and trapping sites. The peak 2 hydrogen, therefore, is believed to not accumulate in front of the crack tip and to not cause environmental degradation in spite of being present in amounts as high as 2.9 mass ppm. (author)

Recombinant expression of a functional myo-inositol-1-phosphate synthase (MIPS) in Mycobacterium smegmatis.

Science.gov (United States)

Huang, Xinyi; Hernick, Marcy

2015-10-01

Myo-inositol-1-phosphate synthase (MIPS, E.C. 5.5.1.4) catalyzes the first step in inositol production-the conversion of glucose-6-phosphate (Glc-6P) to myo-inositol-1-phosphate. While the three dimensional structure of MIPS from Mycobacterium tuberculosis has been solved, biochemical studies examining the in vitro activity have not been reported to date. Herein we report the in vitro activity of mycobacterial MIPS expressed in E. coli and Mycobacterium smegmatis. Recombinant expression in E. coli yields a soluble protein capable of binding the NAD(+) cofactor; however, it has no significant activity with the Glc-6P substrate. In contrast, recombinant expression in M. smegmatis mc(2)4517 yields a functionally active protein. Examination of structural data suggests that MtMIPS expressed in E. coli adopts a fold that is missing a key helix containing two critical (conserved) Lys side chains, which likely explains the inability of the E. coli expressed protein to bind and turnover the Glc-6P substrate. Recombinant expression in M. smegmatis may yield a protein that adopts a fold in which this key helix is formed enabling proper positioning of important side chains, thereby allowing for Glc-6P substrate binding and turnover. Detailed mechanistic studies may be feasible following optimization of the recombinant MIPS expression protocol in M. smegmatis.

Methyllithium-Doped Naphthyl-Containing Conjugated Microporous Polymer with Enhanced Hydrogen Storage Performance.

Science.gov (United States)

Xu, Dan; Sun, Lei; Li, Gang; Shang, Jin; Yang, Rui-Xia; Deng, Wei-Qiao

2016-06-01

Hydrogen storage is a primary challenge for using hydrogen as a fuel. With ideal hydrogen storage kinetics, the weak binding strength of hydrogen to sorbents is the key barrier to obtain decent hydrogen storage performance. Here, we reported the rational synthesis of a methyllithium-doped naphthyl-containing conjugated microporous polymer with exceptional binding strength of hydrogen to the polymer guided by theoretical simulations. Meanwhile, the experimental results showed that isosteric heat can reach up to 8.4 kJ mol(-1) and the methyllithium-doped naphthyl-containing conjugated microporous polymer exhibited an enhanced hydrogen storage performance with 150 % enhancement compared with its counterpart naphthyl-containing conjugated microporous polymer. These results indicate that this strategy provides a direction for design and synthesis of new materials that meet the US Department of Energy (DOE) hydrogen storage target. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Binding of ethyl pyruvate to bovine serum albumin: Calorimetric, spectroscopic and molecular docking studies

Energy Technology Data Exchange (ETDEWEB)

Pathak, Mallika [Department of Chemistry, Miranda House, University of Delhi, Delhi 11007 (India); Mishra, Rashmi; Agarwala, Paban K. [Department of Radiation Genetics and Epigenetics, Division of Radioprotective Drug Development Research, Institute of Nuclear Medicine and Allied Sciences, Delhi 110054 (India); Ojha, Himanshu, E-mail: himanshu.drdo@gmail.com [Department of Radiation Genetics and Epigenetics, Division of Radioprotective Drug Development Research, Institute of Nuclear Medicine and Allied Sciences, Delhi 110054 (India); Singh, Bhawna [Department of Radiation Genetics and Epigenetics, Division of Radioprotective Drug Development Research, Institute of Nuclear Medicine and Allied Sciences, Delhi 110054 (India); Singh, Anju; Kukreti, Shrikant [Nucleic Acid Research Laboratory, Department of Chemistry, University of Delhi, Delhi 11007 (India)

2016-06-10

Highlights: • ITC study showed binding of ethyl pyruvate with BSA with high binding affinity. • Ethyl pyruvate binding caused conformation alteration of BSA. • Fluorescence quenching mechanism is static in nature. • Electrostatic, hydrogen bonding and hydrophobic forces involved in binding. • Docking confirmed role of electrostatic, hydrogen bonding and hydrophobic forces. - Abstract: Various in vitro and in vivo studies have shown the anti-inflammatory and anticancer potential role of ethyl pyruvate. Bio-distribution of drugs is significantly influenced by the drug-serum protein binding. Therefore, the binding mechanism of the ethyl pyruvate with bovine serum albumin was investigated using UV–vis absorption, fluorescence, circular dichroism, isothermal titration calorimetry and molecular docking techniques. Absorption and fluorescence quenching studies indicated the binding of ethyl pyruvate with protein. Circular dichroism spectra of bovine serum albumin confirmed significant change in the conformation of protein upon binding. Thermodynamic data confirmed that ethyl pyruvate binds to bovine serum albumin at the two different sites with high affinity. Binding of ethyl pyruvate to bovine serum albumin involves hydrogen bonding, van der Waal and hydrophobic interactions. Further, docking studies indicated that ethyl pyruvate could bind significantly at the three binding sites. The results will definitely contribute to the development of ethyl pyruvate as drug.

In silico docking of forchlorfenuron (FCF to septins suggests that FCF interferes with GTP binding.

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Dimitrios Angelis

Full Text Available Septins are GTP-binding proteins that form cytoskeleton-like filaments, which are essential for many functions in eukaryotic organisms. Small molecule compounds that disrupt septin filament assembly are valuable tools for dissecting septin functions with high temporal control. To date, forchlorfenuron (FCF is the only compound known to affect septin assembly and functions. FCF dampens the dynamics of septin assembly inducing the formation of enlarged stable polymers, but the underlying mechanism of action is unknown. To investigate how FCF binds and affects septins, we performed in silico simulations of FCF docking to all available crystal structures of septins. Docking of FCF with SEPT2 and SEPT3 indicated that FCF interacts preferentially with the nucleotide-binding pockets of septins. Strikingly, FCF is predicted to form hydrogen bonds with residues involved in GDP-binding, mimicking nucleotide binding. FCF docking with the structure of SEPT2-GppNHp, a nonhydrolyzable GTP analog, and SEPT7 showed that FCF may assume two alternative non-overlapping conformations deeply into and on the outer side of the nucleotide-binding pocket. Surprisingly, FCF was predicted to interact with the P-loop Walker A motif GxxxxGKS/T, which binds the phosphates of GTP, and the GTP specificity motif AKAD, which interacts with the guanine base of GTP, and highly conserved amino acids including a threonine, which is critical for GTP hydrolysis. Thus, in silico FCF exhibits a conserved mechanism of binding, interacting with septin signature motifs and residues involved in GTP binding and hydrolysis. Taken together, our results suggest that FCF stabilizes septins by locking them into a conformation that mimics a nucleotide-bound state, preventing further GTP binding and hydrolysis. Overall, this study provides the first insight into how FCF may bind and stabilize septins, and offers a blueprint for the rational design of FCF derivatives that could target septins with

Probing the role of backbone hydrogen bonds in protein-peptide interactions by amide-to-ester mutations

DEFF Research Database (Denmark)

Eildal, Jonas N N; Hultqvist, Greta; Balle, Thomas

2013-01-01

-protein interactions, those of the PDZ domain family involve formation of intermolecular hydrogen bonds: C-termini or internal linear motifs of proteins bind as β-strands to form an extended antiparallel β-sheet with the PDZ domain. Whereas extensive work has focused on the importance of the amino acid side chains...... of the protein ligand, the role of the backbone hydrogen bonds in the binding reaction is not known. Using amide-to-ester substitutions to perturb the backbone hydrogen-bonding pattern, we have systematically probed putative backbone hydrogen bonds between four different PDZ domains and peptides corresponding...... to natural protein ligands. Amide-to-ester mutations of the three C-terminal amides of the peptide ligand severely affected the affinity with the PDZ domain, demonstrating that hydrogen bonds contribute significantly to ligand binding (apparent changes in binding energy, ΔΔG = 1.3 to >3.8 kcal mol(-1...

Structural models of zebrafish (Danio rerio NOD1 and NOD2 NACHT domains suggest differential ATP binding orientations: insights from computational modeling, docking and molecular dynamics simulations.

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Jitendra Maharana

Full Text Available Nucleotide-binding oligomerization domain-containing protein 1 (NOD1 and NOD2 are cytosolic pattern recognition receptors playing pivotal roles in innate immune signaling. NOD1 and NOD2 recognize bacterial peptidoglycan derivatives iE-DAP and MDP, respectively and undergoes conformational alternation and ATP-dependent self-oligomerization of NACHT domain followed by downstream signaling. Lack of structural adequacy of NACHT domain confines our understanding about the NOD-mediated signaling mechanism. Here, we predicted the structure of NACHT domain of both NOD1 and NOD2 from model organism zebrafish (Danio rerio using computational methods. Our study highlighted the differential ATP binding modes in NOD1 and NOD2. In NOD1, γ-phosphate of ATP faced toward the central nucleotide binding cavity like NLRC4, whereas in NOD2 the cavity was occupied by adenine moiety. The conserved 'Lysine' at Walker A formed hydrogen bonds (H-bonds and Aspartic acid (Walker B formed electrostatic interaction with ATP. At Sensor 1, Arg328 of NOD1 exhibited an H-bond with ATP, whereas corresponding Arg404 of NOD2 did not. 'Proline' of GxP motif (Pro386 of NOD1 and Pro464 of NOD2 interacted with adenine moiety and His511 at Sensor 2 of NOD1 interacted with γ-phosphate group of ATP. In contrast, His579 of NOD2 interacted with the adenine moiety having a relatively inverted orientation. Our findings are well supplemented with the molecular interaction of ATP with NLRC4, and consistent with mutagenesis data reported for human, which indicates evolutionary shared NOD signaling mechanism. Together, this study provides novel insights into ATP binding mechanism, and highlights the differential ATP binding modes in zebrafish NOD1 and NOD2.

Stabilization of microtubules by inorganic phosphate and its structural analogues, the fluoride complexes of aluminum and beryllium

International Nuclear Information System (INIS)

Carlier, M.F.; Didry, D.; Melki, R.; Chabre, M.; Pantaloni, D.

1988-01-01

In order to elucidate how the elementary reactions of GTP cleavage and subsequent inorganic phosphate (P/sub i/) release, which accompany microtubule assembly, regulate microtubule dynamics, the effect of P/sub i/ and of its structural analogues AlF 4 - and BeF 3 - on the stability of GDP-microtubules has been investigated. Inorganic phosphate binds to microtubules with a low affinity (K/sub D/ = 25 mM) and slows down the rate of GDP-subunit dissociation by about 2 orders of magnitude. AlF 4 - and BeF 3 - exhibit phosphate-like effects with 1000-fold higher affinity. Evidence has been obtained for direct binding of BeF 3 - to microtubules with a stoichiometry of 1 mol of BeF 3 - per mole of GDP-subunit and an equilibrium dissociation constant of 12-15 μM. AlF 4 - and P/sub i/ compete for this site. Phosphate analogues abolish oscillatory polymerization kinetics and slow down microtubule turnover at steady state. In view of these results, the authors propose that P/sub i/ and its structural analogues bind to the site of the γ-phosphate of GTP in the E site and reconstitute a GDP-P/sub i/-microtubule, from which tubulin subunits dissociate very slowly. They therefore understand that, following GTP cleavage on microtubules, P/sub i/ release in the medium is accompanied by a structural change resulting in a large destabilization of the polymer. A cap of slowly dissociating GDP-P/sub i/-subunits prevents depolymerization of the microtubule GDP-core at steady state. The similarity with the actin system is studied

Understanding the mechanism of DNA deactivation in ion therapy of cancer cells: hydrogen peroxide action*

Science.gov (United States)

Piatnytskyi, Dmytro V.; Zdorevskyi, Oleksiy O.; Perepelytsya, Sergiy M.; Volkov, Sergey N.

2015-11-01

Changes in the medium of biological cells under ion beam irradiation has been considered as a possible cause of cell function disruption in the living body. The interaction of hydrogen peroxide, a long-lived molecular product of water radiolysis, with active sites of DNA macromolecule was studied, and the formation of stable DNA-peroxide complexes was considered. The phosphate groups of the macromolecule backbone were picked out among the atomic groups of DNA double helix as a probable target for interaction with hydrogen peroxide molecules. Complexes consisting of combinations including: the DNA phosphate group, H2O2 and H2O molecules, and Na+ counterion, were considered. The counterions have been taken into consideration insofar as under the natural conditions they neutralise DNA sugar-phosphate backbone. The energy of the complexes have been determined by considering the electrostatic and the Van der Waals interactions within the framework of atom-atom potential functions. As a result, the stability of various configurations of molecular complexes was estimated. It was shown that DNA phosphate groups and counterions can form stable complexes with hydrogen peroxide molecules, which are as stable as the complexes with water molecules. It has been demonstrated that the formation of stable complexes of H2O2-Na+-PO4- may be detected experimentally by observing specific vibrations in the low-frequency Raman spectra. The interaction of H2O2 molecule with phosphate group of the double helix backbone can disrupt DNA biological function and induce the deactivation of the cell genetic apparatus. Thus, the production of hydrogen peroxide molecules in the nucleus of living cells can be considered as an additional mechanism by which high-energy ion beams destroy tumour cells during ion beam therapy. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene

Hydrogen bonds of DsrD protein revealed by neutron crystallography

International Nuclear Information System (INIS)

Chatake, Toshiyuki; Higuchi, Yoshiki; Mizuno, Nobuhiro; Tanaka, Ichiro; Niimura, Nobuo; Morimoto, Yukio

2008-01-01

Hydrogen bonds of DNA-binding protein DsrD have been determined by neutron diffraction. In terms of proton donors and acceptors, DsrD protein shows striking differences from other proteins. The features of hydrogen bonds in DsrD protein from sulfate-reducing bacteria have been investigated by neutron protein crystallography. The function of DsrD has not yet been elucidated clearly, but its X-ray crystal structure revealed that it comprises a winged-helix motif and shows the highest structural homology to the DNA-binding proteins. Since any neutron structure of a DNA recognition protein has not yet been obtained, here detailed information on the hydrogen bonds in the winged-helix-motif protein is given and the following features found. (i) The number of hydrogen bonds per amino acid of DsrD is relatively fewer than for other proteins for which neutron structures were determined previously. (ii) Hydrogen bonds are localized between main-chain and main-chain atoms; there are few hydrogen bonds between main-chain and side-chain atoms and between side-chain and side-chain atoms. (iii) Hydrogen bonds inducted by protonation of specific amino acid residues (Glu50) seem to play an essential role in the dimerization of DsrD. The former two points are related to the function of the DNA-binding protein; the three-dimensional structure was mainly constructed by hydrogen bonds in main chains, while the side chains appeared to be used for another role. The latter point would be expected to contribute to the crystal growth of DsrD

Manufacturing method of hydrogen storage alloy powder for battery; Denchiyo suiso kyuzo gokin funmatsu no seizo hoho

Energy Technology Data Exchange (ETDEWEB)

Furukawa, J.

1997-04-04

To produce hydrogen storage alloy powder for battery, ingot of a hydrogen storage alloy is crushed to coarse grains of a suitable size with a crusher and then, finely pulverized to a certain particle size with a ball mill or some other tools. In this pulverization process, the surface of the pulverized alloy powder is oxidized and the surface activity is partially lost to cause a problem of a decrease of the characteristics of the produced hydrogen storage alloy electrode. In this invention, ingot of hydrogen storage alloy is crushed to coarse alloy grains in a non-oxidizing atmosphere followed by mechanical pulverization in a state contact with a solution of sulfites, hypophosphites, hydrogen phosphates or dihydrogen phosphates. This treatment method prevents surface oxidation of the alloy powder during the pulverization process. As a result, the initial activity of the battery is improved and an increase of the internal pressure of the battery on overcharge is suppressed. The use of an aqueous alkaline solution containing cobalt instead of the above-mentioned solution gives a similar effect. 2 tabs.

Effect of submarine groundwater discharge containing phosphate on coral calcification

Science.gov (United States)

Yasumoto, J.; Yasumoto, K.; Iijima, M.; Nozaki, M.; Asai, K.; Yasumoto, M. H.

2017-12-01

It is well known that the anthropogenic eutrophication enriched with various substances including phosphate in coastal waters has resulted in coral degradation. However, to the best of our knowledge, the phosphate threshold value to inhibit the coral calcification has been unclear, due to the unknown mechanisms involved in the inhibition of the calcification by phosphate. In island regions, groundwater is one of the most important clues to transport the nutrients contained in livestock or agricultural wastewaters. However, the actual conditions of coastal pollution with such nutrients have not been understood because of unperceived submarine groundwater discharge (SGD). In this study, to quantify of extremely rapid and localized SGD from Ryukyu limestone aquifer, we investigated the rate and concentration of phosphate of SGD using automated seepage mater in Yoron Island, which is located southern part of Japan. And, to elucidate the inhibition mechanisms for phosphate against coral calcification, we examined its effect on the bottom skeleton formation in primary polyps of Acropora digitifera by using the fluorescence derivatizing reagent having phosphate group (FITC-AA). As a result, the SGD was found to contain 1 to 2 µM of phosphate as much as the concentration in the coastal ground water under agricultural land. Moreover, the amount of phosphate contained in the surface layers of bottom calcareous sands close to the region of SGD were about 5 µmol/g. When the primary polyps were treated with 50 µM of FITC-AA, the bottom skeleton of the primary polyps showed the fluorescence from FITC-AA within a few minutes, suggesting the phosphate binding. Furthermore, when the polyps were treated with 10 µM of FITC-AA, irregular patterns of the elongated skeleton were observed. These results led us to conclude that phosphate is transported via a paracellular pathway to the subcalicoblastic extracellular calcifying medium. These results indicate that the phosphate adsorbed

High Capacity Hydrogen Storage on Nanoporous Biocarbon

Science.gov (United States)

Burress, Jacob; Wood, Mikael; Gordon, Michael; Parilla, Phillip; Benham, Michael; Wexler, Carlos; Hawthorne, Fred; Pfeifer, Peter

2008-03-01

The Alliance for Collaborative Research in Alternative Fuel Technology (http://all-craft.missouri.edu) has been optimizing nanoporous biocarbon for high capacity hydrogen storage. The hydrogen storage was measured gravimetrically and volumetrically (Sievert's apparatus). These measurements have been validated by NREL and Hiden Isochema. Sample S-33/k, our current best performer, stores 73-91 g H2/kg carbon at 77 K and 47 bar, and 1.0-1.6 g H2/kg carbon at 293 K and 47 bar. Hydrogen isotherms run by Hiden Isochema have given experimental binding energies of 8.8 kJ/mol compared to the binding energy of graphite of 5 kJ/mol. Results from a novel boron doping technique will also be presented. The benefits and validity of using boron-doping on carbon will also be discussed.

The Effect On the Bones of Condensed Phosphate When Used as Food Additives : Its Importance in Relation to Preventive Medicine

OpenAIRE

Miyako, OMOTO; Tsunehiko, IMAI; Kumiko, SEKI; Ryoji, NOMURA; Yumi, OTAHARA; Department of Environmental and Occupational Health, Toho University, School of Medicine; Department of Environmental and Occupational Health, Toho University, School of Medicine; Department of Environmental and Occupational Health, Toho University, School of Medicine; Department of Environmental and Occupational Health, Toho University, School of Medicine; Department of Environmental and Occupational Health, Toho University, School of Medicine

1997-01-01

Based on the fact that chemical products such as binding agents are produced by mixing three kinds of phosphates with different ratios, we mixed metaphosphate, polyphosphate and pyrophosphate. Each was made to Na-phosphate, K-phosphate, and Ca-phosphate and each was mixed with commercial feeds so that the content of P would be approximately 0.1, 0.15, 0.3, 0.4, 0.6 and 1.0%. The prepared pellets were given to ICR, CF # 1 and AKR strains of mice at 29 days of age for 680 days and observations ...

Biomimetic hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Krassen, Henning

2009-05-15

Hydrogenases catalyze the reduction of protons to molecular hydrogen with outstanding efficiency. An electrode surface which is covered with active hydrogenase molecules becomes a promising alternative to platinum for electrochemical hydrogen production. To immobilize the hydrogenase on the electrode, the gold surface was modified by heterobifunctional molecules. A thiol headgroup on one side allowed the binding to the gold surface and the formation of a self-assembled monolayer. The other side of the molecules provided a surface with a high affinity for the hydrogenase CrHydA1 from Chlamydomonas reinhardtii. With methylviologen as a soluble energy carrier, electrons were transferred from carboxy-terminated electrodes to CrHydA1 and conducted to the active site (H-cluster), where they reduce protons to molecular hydrogen. A combined approach of surface-enhanced infrared absorption spectroscopy, gas chromatography, and surface plasmon resonance allowed quantifying the hydrogen production on a molecular level. Hydrogen was produced with a rate of 85 mol H{sub 2} min{sup -1} mol{sup -1}. On a 1'- benzyl-4,4'-bipyridinum (BBP)-terminated surface, the electrons were mediated by the monolayer and no soluble electron carrier was necessary to achieve a comparable hydrogen production rate (approximately 50% of the former system). The hydrogen evolution potential was determined to be -335 mV for the BBP-bound hydrogenase and -290 mV for the hydrogenase which was immobilized on a carboxy-terminated mercaptopropionic acid SAM. Therefore, both systems significantly reduce the hydrogen production overpotential and allow electrochemical hydrogen production at an energy level which is close to the commercially applied platinum electrodes (hydrogen evolution potential of -270 mV). In order to couple hydrogen production and photosynthesis, photosystem I (PS1) from Synechocystis PCC 6803 and membrane-bound hydrogenase (MBH) from Ralstonia eutropha were bound to each other

Hydrogenic systems for calculable frequency standards. Status and options

International Nuclear Information System (INIS)

Flowers, J.; Klein, H.; Knight, D.

2001-01-01

The study of hydrogen and hydrogenic (one-electron) ions is an area of rapid progress and one of great potential for future frequency standards. In 1997, the two-photon 1S-2S transition in the hydrogen atom was included in the list of approved radiations for the practical realisation of the metre, and since then revolutions in optical frequency metrology have reduced the uncertainty in its frequency by more than an order of magnitude, to 1.8 parts in 10 14 . Hydrogenic systems are simple enough that the frequencies of their transitions can be calculated in terms of the Rydberg constant with an accuracy that can approach or exceed the measurement uncertainty. Transitions in such systems can be thought of as forming a natural frequency scale, and offer the prospect of a set of quantum frequency standards which are directly related to the fundamental constants. The Rydberg constant is currently best determined from optical frequency measurements in hydrogen. However, to take full advantage of the recent high accuracy 1S-2S frequency measurement requires: Improved measurements of other transition frequencies in the hydrogen atom; Reduced uncertainty in the quantum electrodynamic (QED) contributions to the energy levels, in particular the two-loop binding corrections; An improved value for the proton charge radius. In He + and one-electron systems of higher atomic number Z, the two-loop binding corrections are a fractionally larger part of the Lamb shift due to their rapid scaling with Z. Measurements of the Lamb shift in medium-Z hydrogenic ions can therefore provide tests of these corrections, and feed in to the theoretical understanding of hydrogen itself Although both theory and experiment are less accurate at higher Z, there is the potential for a new range of X-ray standards, providing that the QED corrections are well understood and new absolute measurement techniques can be developed. A number of areas are suggested for future investigation: Improving the

Oxoanion Recognition by Benzene-based Tripodal Pyrrolic Receptors

Energy Technology Data Exchange (ETDEWEB)

Bill, Nathan [University of Texas at Austin; Kim, Dae-Sik [University of Texas at Austin; Kim, Sung Kuk [University of Texas at Austin; Park, Jung Su [University of Texas at Austin; Lynch, Vincent M. [University of Texas at Austin; Young, Neil J [ORNL; Hay, Benjamin [ORNL; Yang, Youjun [University of Texas at Austin; Anslyn, Eric [University of Texas at Austin; Sessler, Jonathan L. [University of Texas

2012-01-01

Two new tripodal receptors based on pyrrole- and dipyrromethane-functionalised derivatives of a sterically geared precursor, 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene, are reported; these systems, compounds 1 and 2, display high affinity and selectivity for tetrahedral anionic guests, in particular dihydrogen phosphate, pyrophosphate and hydrogen sulphate, in acetonitrile as inferred from isothermal titration calorimetry measurements. Support for the anion-binding ability of these systems comes from theoretical calculations and a single-crystal X-ray diffraction structure of the 2:2 (host:guest) dihydrogen phosphate complex is obtained in the case of the pyrrole-based receptor system, 1. Keywords anion receptors, dihydrogen phosphate, hydrogen sulphate, X-ray structure, theoretical calculations.

Interactions of casein micelles with calcium phosphate particles.

Science.gov (United States)

Tercinier, Lucile; Ye, Aiqian; Anema, Skelte G; Singh, Anne; Singh, Harjinder

2014-06-25

Insoluble calcium phosphate particles, such as hydroxyapatite (HA), are often used in calcium-fortified milks as they are considered to be chemically unreactive. However, this study showed that there was an interaction between the casein micelles in milk and HA particles. The caseins in milk were shown to bind to the HA particles, with the relative proportions of bound β-casein, αS-casein, and κ-casein different from the proportions of the individual caseins present in milk. Transmission electron microscopy showed no evidence of intact casein micelles on the surface of the HA particles, which suggested that the casein micelles dissociated either before or during binding. The HA particles behaved as ion chelators, with the ability to bind the ions contained in the milk serum phase. Consequently, the depletion of the serum minerals disrupted the milk mineral equilibrium, resulting in dissociation of the casein micelles in milk.

Infrared and Raman Spectra of Magnesium Ammonium Phosphate Hexahydrate (Struvite) and its Isomorphous Analogues. VIII. Spectra of Protiated and Partially Deuterated Magnesium Rubidium Phosphate Hexahydrate and Magnesium Thallium Phosphate Hexahydrate.

Science.gov (United States)

Soptrajanov, Bojan; Cahil, Adnan; Najdoski, Metodija; Koleva, Violeta; Stefov, Viktor

2011-09-01

The infrared and Raman spectra of magnesium rubidium phosphate hexahydrate MgRbPO4 • 6H2O and magnesium thallium phosphate hexahydrate, MgTlPO4 • 6H2O were recorded at room temperature (RT) and the boiling temperature of liquid nitrogen (LNT). To facilitate their analysis, also recorded were the spectra of partially deuterated analogues with varying content of deuterium. The effects of deuteration and those of lowering the temperature were the basis of the conclusions drawn regarding the origin of the observed bands which were assigned to vibrations which are predominantly localized in the water molecules (four crystallographically different types of such molecules exist in the structures) and those with PO43- character. It was concluded that in some cases coupling of phosphate and water vibrations is likely to take place. The appearance of the infrared spectra in the O-H stretching regions of the infrared spectra is explained as being the result of an extensive overlap of bands due to components of the fundamental stretching modes of the H2O units with a possible participation of bands due to second-order transitions. A broad band reminiscent of the B band of the well-known ABC trio characteristic of spectra of substances containing strong hydrogen bonds in their structure was found around 2400 cm-1 in the infrared spectra of the two studied compounds.

Electronic and Structural Parameters of Phosphorus-Oxygen Bonds in Inorganic Phosphate Crystals

Science.gov (United States)

Atuchin, V. V.; Kesler, V. G.; Pervukhina, N. V.

Wide set of experimental results on binding energy of photoelectrons emitted from P 2p, P 2s, and O 1s core levels has been observed for inorganic phosphate crystals and the parameters were compared using energy differences Δ(O 1s - P 2p) and Δ (O 1s - P 2s) as most robust characteristics. Linear dependence of the binding energy difference on mean chemical bond length L(P-O) between phosphorus and oxygen atoms has been found. The functions are of the forms: Δ (O 1s - P 2p) (eV) = 375.54 + 0.146 · L(P-O) (pm) and Δ (O 1s - P 2s) (eV) = 320.77 + 0.129 · L(P-O) (pm). The dependencies are general for inorganic phosphates and may be used in quantitative component analysis of X-ray photoemission spectra of complex oxide compounds including functional groups with different coordination of P and O atoms.

Thermochemical hydrogen production studies at LLNL: a status report

International Nuclear Information System (INIS)

Krikorian, O.H.

1982-01-01

Currently, studies are underway at the Lawrence Livermore National Laboratory (LLNL) on thermochemical hydrogen production based on magnetic fusion energy (MFE) and solar central receivers as heat sources. These areas of study were described earlier at the previous IEA Annex I Hydrogen Workshop (Juelich, West Germany, September 23-25, 1981), and a brief update will be given here. Some basic research has also been underway at LLNL on the electrolysis of water from fused phosphate salts, but there are no current results in that area, and the work is being terminated

Shallow hydrogen-related donors in silicon

International Nuclear Information System (INIS)

Hartung, J.; Weber, J.

1993-01-01

Photothermal ionization spectroscopy on neutron-irradiated and subsequently hydrogen-plasma-treated silicon reveals the existence of new shallow donors. The binding energies of the observed effective-mass-like donors are between 34 and 53 meV. The optical dipole transitions of the different donors are shifted towards higher energies by ΔE=0.1--0.2 cm -1 , when deuterium is used in the plasma instead of hydrogen. This isotope shift of the optical dipole transitions between the electronic levels of the defects is direct proof of the incorporation of hydrogen in these defects

Phosphate binding by natural iron-rich colloids in streams

NARCIS (Netherlands)

Baken, S.; Moens, C.; Griffioen, J.J.; Smolders, E.

2016-01-01

Phosphorus (P) in natural waters may be bound to iron (Fe) bearing colloids. However, the natural variation in composition and P binding strength of these colloids remain unclear. We related the composition of "coarse colloids" (colloids in the 0.1-1.2 μm size range) in 47 Belgian streams to the

Heat, hydrogen peroxide, and UV resistance of Bacillus subtilis spores with increased core water content and with or without major DNA-binding proteins

International Nuclear Information System (INIS)

Popham, D.L.; Sengupta, S.; Setlow, P.

1995-01-01

Spores of a Bacillus subtilis strain with an insertion mutation in the dacB gene, which codes for an enzyme involved in spore cortex biosynthesis, have a higher core water content than wild-type spores. Spores lacking the two major α/β-type small, acid-soluble proteins (SASP) (termed a α - β - spores) have the same core water content as do wild-type spores, but α - β - dacB spores had more core water than did dacB spores. The resistance of α - β - , α - β - dacB, dacB, and wild-type spores to dry and moist heat, hydrogen peroxide, and UV radiation has been determined, as has the role of DNA damage in spore killing by moist heat and hydrogen peroxide. These data (1) suggest that core water content has little if any role in spore UV resistance and are consistent with binding of α/β-type SASP to DNA being the major mechanism providing protection to spores from UV radiation; (2) suggest that binding of αβ-type SASP to DNA is the major mechanism unique to spores providing protection from dry heat; (3) suggest that spore resistance to moist heat and hydrogen peroxide is affected to a large degree by the core water content, as increased core water resulted in large decreases in spore resistance to these agents; and (4) indicate that since this decreased resistance (i.e., in dacB spores) is not associated with increased spore killing by DNA damage, spore DNA must normally be extremely well protected against such damage, presumably by the saturation of spore DNA by α/β-type SASP. 19 refs., 2 figs., 5 tabs

Theoretical investigation on the alkali-metal doped BN fullerene as a material for hydrogen storage

International Nuclear Information System (INIS)

Venkataramanan, Natarajan Sathiyamoorthy; Belosludov, Rodion Vladimirovich; Note, Ryunosuke; Sahara, Ryoji; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

2010-01-01

Graphical abstract: First-principles calculations have been used to investigate hydrogen adsorption on alkali atom doped B 36 N 36 clusters. Adsorption of alkali atoms involves a charge transfer process, creating positively-charged alkali atoms and this polarizes the H 2 molecules and increases their binding energy. The maximum hydrogen storage capacity of Li doped BN fullerene is 8.9 wt.% in which 60 hydrogen atoms were chemisorbed and 12 H 2 were adsorbed in molecular form. - Abstract: First-principles calculations have been used to investigate hydrogen adsorption on alkali atom doped B 36 N 36 clusters. The alkali atom adsorption takes place near the six tetragonal bridge sites available on the cage, thereby avoiding the notorious clustering problem. Adsorption of alkali atoms involves a charge transfer process, creating positively charged alkali atoms and this polarizes the H 2 molecules thereby, increasing their binding energy. Li atom has been found to adsorb up to three hydrogen molecules with an average binding energy of 0.189 eV. The fully doped Li 6 B 36 N 36 cluster has been found to hold up to 18 hydrogen molecules with the average binding energy of 0.146 eV. This corresponds to a gravimetric density of hydrogen storage of 3.7 wt.%. Chemisorption on the Li 6 B 36 N 36 has been found to be an exothermic reaction, in which 60 hydrogen atoms chemisorbed with an average chemisorption energy of -2.13 eV. Thus, the maximum hydrogen storage capacity of Li doped BN fullerene is 8.9 wt.% in which 60 hydrogen atoms were chemisorbed and 12 hydrogen molecules were adsorbed in molecular form.

Hydrogen atom addition to the surface of graphene nanoflakes: A density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Tachikawa, Hiroto, E-mail: hiroto@eng.hokudai.ac.jp

2017-02-28

Highlights: • The reaction pathway of the hydrogen addition to graphene surface was determined by the DFT method. • Binding energies of atomic hydrogen to graphene surface were determined. • Absorption spectrum of hydrogenated graphene was theoretically predicted. • Hyperfine coupling constant of hydrogenated graphene was theoretically predicted. - Abstract: Polycyclic aromatic hydrocarbons (PAHs) provide a 2-dimensional (2D) reaction surface in 3-dimensional (3D) interstellar space and have been utilized as a model of graphene surfaces. In the present study, the reaction of PAHs with atomic hydrogen was investigated by means of density functional theory (DFT) to systematically elucidate the binding nature of atomic hydrogen to graphene nanoflakes. PAHs with n = 4–37 were chosen, where n indicates the number of benzene rings. Activation energies of hydrogen addition to the graphene surface were calculated to be 5.2–7.0 kcal/mol at the CAM-B3LYP/6-311G(d,p) level, which is almost constant for all PAHs. The binding energies of hydrogen atom were slightly dependent on the size (n): 14.8–28.5 kcal/mol. The absorption spectra showed that a long tail is generated at the low-energy region after hydrogen addition to the graphene surface. The electronic states of hydrogenated graphenes were discussed on the basis of theoretical results.

The binding cavity of mouse major urinary protein is optimised for a variety of ligand binding modes

Energy Technology Data Exchange (ETDEWEB)

Pertinhez, Thelma A.; Ferrari, Elena; Casali, Emanuela [Department of Experimental Medicine, University of Parma, Via Volturno, 39, 43100 Parma (Italy); Patel, Jital A. [Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford OX1 3QR (United Kingdom); Spisni, Alberto, E-mail: alberto.spisni@unipr.it [Department of Experimental Medicine, University of Parma, Via Volturno, 39, 43100 Parma (Italy); Smith, Lorna J., E-mail: lorna.smith@chem.ox.ac.uk [Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford OX1 3QR (United Kingdom)

2009-12-25

{sup 15}N and {sup 1}HN chemical shift data and {sup 15}N relaxation studies have been used to characterise the binding of N-phenyl-naphthylamine (NPN) to mouse major urinary protein (MUP). NPN binds in the {beta}-barrel cavity of MUP, hydrogen bonding to Tyr120 and making extensive non-bonded contacts with hydrophobic side chains. In contrast to the natural pheromone 2-sec-butyl-4,5-dihydrothiazole, NPN binding gives no change to the overall mobility of the protein backbone of MUP. Comparison with 11 different ligands that bind to MUP shows a range of binding modes involving 16 different residues in the {beta}-barrel cavity. These finding justify why MUP is able to adapt to allow for many successful binding partners.

Designing calcium phosphate-based bifunctional nanocapsules with bone-targeting properties

Energy Technology Data Exchange (ETDEWEB)

Khung, Yit-Lung; Bastari, Kelsen; Cho, Xing Ling; Yee, Wu Aik; Loo, Say Chye Joachim, E-mail: joachimloo@ntu.edu.sg [Nanyang Technological University, School of Materials Science and Engineering (Singapore)

2012-06-15

Using sodium dodecyl sulphate micelles as template, hollow-cored calcium phosphate nanocapsules were produced. The surfaces of the nanocapsule were subsequently silanised by a polyethylene glycol (PEG)-based silane with an N-hydroxysuccinimide ester end groups which permits for further attachment with bisphosphonates (BP). Characterisations of these nanocapsules were investigated using Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy, Fourier Transform Infra-Red Spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Dynamic Light Scattering. To further validate the bone-targeting potential, dentine discs were incubated with these functionalised nanocapsules. FESEM analysis showed that these surface-modified nanocapsules would bind strongly to dentine surfaces compared to non-functionalised nanocapsules. We envisage that respective components would give this construct a bifunctional attribute, whereby (1) the shell of the calcium phosphate nanocapsule would serve as biocompatible coating aiding in gradual osteoconduction, while (2) surface BP moieties, acting as targeting ligands, would provide the bone-targeting potential of these calcium phosphate nanocapsules.

Designing calcium phosphate-based bifunctional nanocapsules with bone-targeting properties

International Nuclear Information System (INIS)

Khung, Yit-Lung; Bastari, Kelsen; Cho, Xing Ling; Yee, Wu Aik; Loo, Say Chye Joachim

2012-01-01

Using sodium dodecyl sulphate micelles as template, hollow-cored calcium phosphate nanocapsules were produced. The surfaces of the nanocapsule were subsequently silanised by a polyethylene glycol (PEG)-based silane with an N-hydroxysuccinimide ester end groups which permits for further attachment with bisphosphonates (BP). Characterisations of these nanocapsules were investigated using Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy, Fourier Transform Infra-Red Spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Dynamic Light Scattering. To further validate the bone-targeting potential, dentine discs were incubated with these functionalised nanocapsules. FESEM analysis showed that these surface-modified nanocapsules would bind strongly to dentine surfaces compared to non-functionalised nanocapsules. We envisage that respective components would give this construct a bifunctional attribute, whereby (1) the shell of the calcium phosphate nanocapsule would serve as biocompatible coating aiding in gradual osteoconduction, while (2) surface BP moieties, acting as targeting ligands, would provide the bone-targeting potential of these calcium phosphate nanocapsules.

Computer modelling reveals new conformers of the ATP binding loop of Na+/K+-ATPase involved in the transphosphorylation process of the sodium pump

Directory of Open Access Journals (Sweden)

Gracian Tejral

2017-03-01

Full Text Available Hydrolysis of ATP by Na+/K+-ATPase, a P-Type ATPase, catalyzing active Na+ and K+ transport through cellular membranes leads transiently to a phosphorylation of its catalytical α-subunit. Surprisingly, three-dimensional molecular structure analysis of P-type ATPases reveals that binding of ATP to the N-domain connected by a hinge to the P-domain is much too far away from the Asp369 to allow the transfer of ATP’s terminal phosphate to its aspartyl-phosphorylation site. In order to get information for how the transfer of the γ-phosphate group of ATP to the Asp369 is achieved, analogous molecular modeling of the M4–M5 loop of ATPase was performed using the crystal data of Na+/K+-ATPase of different species. Analogous molecular modeling of the cytoplasmic loop between Thr338 and Ile760 of the α2-subunit of Na+/K+-ATPase and the analysis of distances between the ATP binding site and phosphorylation site revealed the existence of two ATP binding sites in the open conformation; the first one close to Phe475 in the N-domain, the other one close to Asp369 in the P-domain. However, binding of Mg2+•ATP to any of these sites in the “open conformation” may not lead to phosphorylation of Asp369. Additional conformations of the cytoplasmic loop were found wobbling between “open conformation”  “semi-open conformation  “closed conformation” in the absence of 2Mg2+•ATP. The cytoplasmic loop’s conformational change to the “semi-open conformation”—characterized by a hydrogen bond between Arg543 and Asp611—triggers by binding of 2Mg2+•ATP to a single ATP site and conversion to the “closed conformation” the phosphorylation of Asp369 in the P-domain, and hence the start of Na+/K+-activated ATP hydrolysis.

[Modification of retinal photoreceptor membranes and Ca ion binding].

Science.gov (United States)

Korchagin, V P; Berman, A L; Shukoliukov, S A; Rychkova, M P; Etingof, R N

1978-10-01

Calcium binding by modified photoreceptor membranes of cattle retina has been studied. Ca2+-binding the membranes significantly changes after C-phospholipase treatment, displaying the initial growth (less than 65% of lipid phosphorus removed) with subsequent decrease (more than 65% of phosphorus removed). Liposomes of the photoreceptor membranes lipids were found to bind more calcium than do the native photoreceptor membranes. Proteolytic enzymes (papaine, pronase) splitting some rhodopsin fragments do not affect the ability of the membrane to bind Ca2+. The increase of light-induced Ca-binding is observed only after the outer segments preincubation under conditions providing for rhodopsin phosphorylation. This effect was observed also after the splitting of the rhodopsin fragment by papaine. It is concluded that calcium binding in the photoreceptor membranes is mainly due to the phosphate groups of phospholipids.

Preparation and thermogravimetric study of some uranyl phosphates

International Nuclear Information System (INIS)

Schaekers, J.M.

1970-10-01

The preparation of uranyl ammonium phosphate trihydrate (UAP = UO 2 NH 4 PO 4 .3H 2 O), acid uranyl phosphate tetrahydrate(AUP = UO 2 HPO 4 .4H 2 O) and neutral uranyl phosphate tetrahydrate (NUPT = (UO 2 ) 3 (PO 4 ) 2 .4H 2 O) was investigated during the data from the literature. The thermal decomposition in different atmospheres, such as air, oxygen, nitrogen and argon, was studied in the temperature range 25-1000 0 C. It was found that the pyrophosphate U 2 O 3 P 2 O 7 is a stable decomposition product of UAP as well as of AUP. A mixture of U 3 O 8 and U 2 O 3 P 2 O 7 is obtained when the NUPT is decomposed in an oxygen-free atmosphere. NUPT however is stable in an oxidising atmosphere. Hydrogen and carbon reductions were also carried out, and UO 2 or (UO) 2 P 2 O 7 as well as mixtures of these two products can be obtained, depending on the starting material and the reduction temperature. The different reduction and decomposition reactions were studied by means of thermogravimetric analysis, and activation energies were calculated where possible. I.R. spectral analysis was also used to identify various products with the same composition [af

Improved Hydrogen Gas Getters for TRU Waste -- Final Report

International Nuclear Information System (INIS)

Mark Stone; Michael Benson; Christopher Orme; Thomas Luther; Eric Peterson

2005-01-01

Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage containers. For that reason, the Nuclear Regulatory Commission limits the flammable gas (hydrogen) concentration in the Transuranic Package Transporter-II (TRUPACT-II) containers to 5 vol% of hydrogen in air, which is the lower explosion limit. Consequently, a method is needed to prevent the build up of hydrogen to 5 vol% during the storage and transport of the TRUPACT-II containers (up to 60 days). One promising option is the use of hydrogen getters. These materials scavenge hydrogen from the gas phase and irreversibly bind it in the solid phase. One proven getter is a material called 1,4-bis (phenylethynyl) benzene, or DEB, characterized by the presence of carbon-carbon triple bonds. Carbon may, in the presence of suitable precious metal catalysts such as palladium, irreversibly react with and bind hydrogen. In the presence of oxygen, the precious metal may also eliminate hydrogen by catalyzing the formation of water. This reaction is called catalytic recombination. DEB has the needed binding rate and capacity for hydrogen that potentially could be generated in the TRUPACT II. Phases 1 and 2 of this project showed that uncoated DEB performed satisfactorily in lab scale tests. Based upon these results, Phase 3, the final project phase, included larger scale testing. Test vessels were scaled to replicate the ratio between void space in the inner containment vessel of a TRUPACT-II container and a payload of seven 55-gallon drums. The tests were run with an atmosphere of air for 63.9 days at ambient temperature (15-27 C) and a scaled hydrogen generation rate of 2.60E-07 moles per second (0.35 cc/min). A second type of getter known as VEI, a proprietary polymer hydrogen getter characterized by carbon-carbon double bonds, was also tested in Phase 3. Hydrogen was successfully ''gettered'' by both getter systems. Hydrogen concentrations remained below 5 vol% (in

Improved Hydrogen Gas Getters for TRU Waste -- Final Report

Energy Technology Data Exchange (ETDEWEB)

Mark Stone; Michael Benson; Christopher Orme; Thomas Luther; Eric Peterson

2005-09-01

Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage containers. For that reason, the Nuclear Regulatory Commission limits the flammable gas (hydrogen) concentration in the Transuranic Package Transporter-II (TRUPACT-II) containers to 5 vol% of hydrogen in air, which is the lower explosion limit. Consequently, a method is needed to prevent the build up of hydrogen to 5 vol% during the storage and transport of the TRUPACT-II containers (up to 60 days). One promising option is the use of hydrogen getters. These materials scavenge hydrogen from the gas phase and irreversibly bind it in the solid phase. One proven getter is a material called 1,4-bis (phenylethynyl) benzene, or DEB, characterized by the presence of carbon-carbon triple bonds. Carbon may, in the presence of suitable precious metal catalysts such as palladium, irreversibly react with and bind hydrogen. In the presence of oxygen, the precious metal may also eliminate hydrogen by catalyzing the formation of water. This reaction is called catalytic recombination. DEB has the needed binding rate and capacity for hydrogen that potentially could be generated in the TRUPACT II. Phases 1 and 2 of this project showed that uncoated DEB performed satisfactorily in lab scale tests. Based upon these results, Phase 3, the final project phase, included larger scale testing. Test vessels were scaled to replicate the ratio between void space in the inner containment vessel of a TRUPACT-II container and a payload of seven 55-gallon drums. The tests were run with an atmosphere of air for 63.9 days at ambient temperature (15-27°C) and a scaled hydrogen generation rate of 2.60E-07 moles per second (0.35 cc/min). A second type of getter known as VEI, a proprietary polymer hydrogen getter characterized by carbon-carbon double bonds, was also tested in Phase 3. Hydrogen was successfully “gettered” by both getter systems. Hydrogen concentrations remained below 5 vol% (in

Potential of AlN nanostructures as hydrogen storage materials.

Science.gov (United States)

Wang, Qian; Sun, Qiang; Jena, Puru; Kawazoe, Yoshiyuki

2009-03-24

The capability of AlN nanostructures (nanocages, nanocones, nanotubes, and nanowires) to store hydrogen has been studied using gradient-corrected density functional theory. In contrast to bulk AlN, which has the wurtzite structure and four-fold coordination, the Al sites in AlN nanostructures are unsaturated and have two- and three-fold coordination. Each Al atom is capable of binding one H(2) molecule in quasi-molecular form, leading to 4.7 wt % hydrogen, irrespective of the topology of the nanostructures. With the exception of AlN nanotubes, energetics does not support the adsorption of additional hydrogen. The binding energies of hydrogen to these unsaturated metal sites lie in the range of 0.1-0.2 eV/H(2) and are ideal for applications under ambient thermodynamic conditions. Furthermore, these materials do not suffer from the clustering problem that often plagues metal-coated carbon nanostructures.

The Strength of Hydrogen Bonds between Fluoro-Organics and Alcohols, a Theoretical Study.

Science.gov (United States)

Rosenberg, Robert E

2018-05-10

Fluorinated organic compounds are ubiquitous in the pharmaceutical and agricultural industries. To better discern the mode of action of these compounds, it is critical to understand the strengths of hydrogen bonds involving fluorine. There are only a few published examples of the strengths of these bonds. This study provides a high level ab initio study of inter- and intramolecular hydrogen bonds between RF and R'OH, where R and R' are aryl, vinyl, alkyl, and cycloalkyl. Intermolecular binding energies average near 5 kcal/mol, while intramolecular binding energies average about 3 kcal/mol. Inclusion of zero-point energies and applying a counterpoise correction lessen the difference. In both series, modest increases in binding energies are seen with increased acidity of R'OH and increased electron donation of R in RF. In the intramolecular compounds, binding energy increases with the rigidity of the F-(C) n -OH ring. Inclusion of free energy corrections at 298 K results in exoergic binding energies for the intramolecular compounds and endoergic binding energies for the intermolecular compounds. Parameters such as bond lengths, vibrational frequencies, and atomic populations are consistent with formation of a hydrogen bond and with slightly stronger binding in the intermolecular cases over the intramolecular cases. However, these parameters correlated poorly with binding energies.

Developing porous carbon with dihydrogen phosphate groups as sulfur host for high performance lithium sulfur batteries

Science.gov (United States)

Cui, Yanhui; Zhang, Qi; Wu, Junwei; Liang, Xiao; Baker, Andrew P.; Qu, Deyang; Zhang, Hui; Zhang, Huayu; Zhang, Xinhe

2018-02-01

Carbon matrix (CM) derived from biomass is low cost and easily mass produced, showing great potential as sulfur host for lithium sulfur batteries. In this paper we report on a dihydrogen phosphate modified CM (PCM-650) prepared from luffa sponge (luffa acutangula) by phosphoric acid treatment. The phosphoric acid not only increases the surface area of the PCM-650, but also introduces dihydrogen phosphate onto PCM-650 (2.28 at% P). Sulfur impregnated (63.6 wt%) PCM-650/S, in comparison with samples with less dihydrogen phosphate LPCM-650/S, shows a significant performance improvement. XPS analysis is conducted for sulfur at different stages, including sulfur (undischarged), polysulfides (discharge to 2.1 V) and short chain sulfides (discharge to 1.7 V). The results consistently show chemical shifts for S2p in PCM-650, suggesting an enhanced adsorption effect. Furthermore, density functional theory (DFT) calculations is used to clarify the molecular binding: carbon/sulfur (0.86 eV), carbon/Li2S (0.3 eV), CH3-O-PO3H2/sulfur (1.24 eV), and CH3-O-PO3H2/Li2S (1.81 eV). It shows that dihydrogen phosphate group can significantly enhance the binding with sulfur and sulfide, consistent with XPS results. Consequently a CM functionalised with dihydrogen phosphate shows great potential as the sulfur host in a Li-S battery.

Evaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cells

International Nuclear Information System (INIS)

Ozden, Adnan; Ercelik, Mustafa; Devrim, Yilser; Colpan, C. Ozgur; Hamdullahpur, Feridun

2017-01-01

Highlights: •Very thin SPSf/ZrP composite membranes were prepared by solution casting method. •The viability of SPSf/ZrP membranes for DMFCs was investigated for the first time. •Superior proton conductivity over Nafion ® 115 was achieved between 45–80 °C. •Desired membrane characteristics, along with low manufacturing cost were achieved. •Single cell DMFC performance was improved up to 13%. -- Abstract: Direct methanol fuel cell (DMFC) technology has advanced perceivably, but technical challenges remain that must be overcome for further performance improvements. Thus, in this study, sulfonated polysulfone/zirconium hydrogen phosphate (SPSf/ZrP) composite membranes with various sulfonation degrees (20%, 35%, and 42%) and a constant concentration of ZrP (2.5%) were prepared to mitigate the technical challenges associated with the use of conventional Nafion ® membranes in DMFCs. The composite membranes were investigated through Scanning Electron Microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), Thermogravimetric Analysis (TGA), oxidative stability and water uptake measurements, and single cell testing. Comparison was also made with Nafion ® 115. Single cell tests were performed under various methanol concentrations and cell temperatures. Stability characteristics of the DMFCs under charging and discharging conditions were investigated via 1200 min short-term stability tests. The response characteristics of the DMFCs under dynamic conditions were determined at the start-up and shut-down stages. Composite membranes with sulfonation degrees of 35% and 42% were found to be highly promising due to their advanced characteristics with respect to proton conductivity, water uptake, thermal resistance, oxidative stability, and methanol suppression. For the whole range of parameters studied, the maximum power density obtained for SPSf/ZrP-42 (119 mW cm −2 ) was found to be 13% higher than that obtained for Nafion ® 115 (105 mW cm −2 ).

Structural, kinetic and proteomic characterization of acetyl phosphate-dependent bacterial protein acetylation.

Directory of Open Access Journals (Sweden)

Misty L Kuhn

Full Text Available The emerging view of Nε-lysine acetylation in eukaryotes is of a relatively abundant post-translational modification (PTM that has a major impact on the function, structure, stability and/or location of thousands of proteins involved in diverse cellular processes. This PTM is typically considered to arise by the donation of the acetyl group from acetyl-coenzyme A (acCoA to the ε-amino group of a lysine residue that is reversibly catalyzed by lysine acetyltransferases and deacetylases. Here, we provide genetic, mass spectrometric, biochemical and structural evidence that Nε-lysine acetylation is an equally abundant and important PTM in bacteria. Applying a recently developed, label-free and global mass spectrometric approach to an isogenic set of mutants, we detected acetylation of thousands of lysine residues on hundreds of Escherichia coli proteins that participate in diverse and often essential cellular processes, including translation, transcription and central metabolism. Many of these acetylations were regulated in an acetyl phosphate (acP-dependent manner, providing compelling evidence for a recently reported mechanism of bacterial Nε-lysine acetylation. These mass spectrometric data, coupled with observations made by crystallography, biochemistry, and additional mass spectrometry showed that this acP-dependent acetylation is both non-enzymatic and specific, with specificity determined by the accessibility, reactivity and three-dimensional microenvironment of the target lysine. Crystallographic evidence shows acP can bind to proteins in active sites and cofactor binding sites, but also potentially anywhere molecules with a phosphate moiety could bind. Finally, we provide evidence that acP-dependent acetylation can impact the function of critical enzymes, including glyceraldehyde-3-phosphate dehydrogenase, triosephosphate isomerase, and RNA polymerase.

External electric field and hydrostatic pressure effects on the binding energy and self-polarization of an off-center hydrogenic impurity confined in a GaAs/AlGaAs square quantum well wire

International Nuclear Information System (INIS)

Rezaei, G.; Mousavi, S.; Sadeghi, E.

2012-01-01

Based on the effective-mass approximation within a variational scheme, binding energy and self-polarization of hydrogenic impurity confined in a finite confining potential square quantum well wire, under the action of external electric field and hydrostatic pressure, are investigated. The binding energy and self-polarization are computed as functions of the well width, impurity position, electric field, and hydrostatic pressure. Our results show that the external electric field and hydrostatic pressure as well as the well width and impurity position have a great influence on the binding energy and self-polarization.

Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

Science.gov (United States)

Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

2009-01-01

One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

Effectiveness and cost-efficiency of phosphate binders in hemodialysis

Directory of Open Access Journals (Sweden)

Zsifkovits, Johannes

2009-06-01

Full Text Available Health political background: In 2006, the prevalence of chronic renal insufficiency in Germany was 91,718, of which 66,508 patients were on dialysis. The tendency is clearly growing. Scientific background: Chronic renal insufficiency results in a disturbance of the mineral balance. It leads to hyperphosphataemia, which is the strongest independent risk factor for mortality in renal patients. Usually, a reduction in the phosphate intake through nutrition and the amount of phosphate filtered out during dialysis are not sufficient to reduce the serum phosphate values to the recommended value. Therefore, phosphate binders are used to bind ingested phosphate in the digestive tract in order to lower the phosphate concentration in the serum. Four different groups of phosphate binders are available: calcium- and aluminium salts are the traditional therapies. Sevelamer and Lanthanum are recent developments on the market. In varying doses, all phosphate binders are able to effectively lower phosphate concentrations. However, drug therapies have achieved recommended phosphate levels in only 50 percent of patients during the last years. Research questions: How effective and efficient are the different phosphate binders in chronic renal insufficient patients? Methods: The systematic literature search yielded 1,251 abstracts. Following a two-part selection process with predefined criteria 18 publications were included in the assessment. Results: All studies evaluated conclude that serum phosphate, serum calcium and intact parathyroid hormone can be controlled effectively with all phosphate binders. Only the number of episodes of hypercalcaemia is higher when using calcium-containing phosphatebinders compared to Sevelamer and Lanthanum. Regarding the mortality rate, the cardiovascular artery calcification and bone metabolism no definite conclusions can be drawn. In any case, the amount of calcification at study start seems to be crucial for the further

Theory of Hydrogen Storage: A New Strategy within Organometallic Chemistry

Science.gov (United States)

Zhao, Yufeng

2006-03-01

As one of the most vigorous fields in modern chemistry, organometallic chemistry has made vast contributions to a broad variety of technological fields including catalysis, light emitters, molecular devices, liquid crystals, and even superconductivity. Here we show that organometallic chemistry in nanoscale could be the frontier in hydrogen storage. Our study is based on the notion that the 3d transition metal (TM) atoms are superb absorbers for H storage, as their empty d orbital can bind dihydrogen ligands (elongated but non-dissociated H2) with high capacity at nearly ideal binding energy for reversible hydrogen storage. By embedding the TM atoms into a carbon-based nanostructures, high H capacity can be maintained. This presentation contains four parts. First, by comparing the conventional hydrogen storage media, e.g., metal hydrides and carbon-based materials, the general principles for designing hydrogen storage materials are outlined. Second, organometallic buckyballs are studied to demonstrate the novel strategy. The amount of H2 adsorbed on a Sc-coated fullerene, C48B12 [ScH]12, could approach 9 wt%, with binding energies of 30-40 kJ/mol. Third, the method is applied to the transition-metal carbide nanoparticles that have been synthesized experimentally. The similar non-dissociative H2 binding is revealed in our calculation, thereby demonstrating the resilience of the overall mechanism. Moreover, a novel self-catalysis process is identified. In the fourth part, transition-metal functionalization of highly porous carbon-based materials is discussed heuristically to foresee macroscopic media for hydrogen storage. Finally follows the summary and discussion of the remaining challenges to practical hydrogen storage. Work in collaboration with A. C. Dillon, Y.-H. Kim, M. Heben & S. B. Zhang and supported by the U.S. DOE/EERE under contract No. DE-AC36-99GO10337.

Mechanism of conformational coupling in SecA: Key role of hydrogen-bonding networks and water interactions.

Science.gov (United States)

Milenkovic, Stefan; Bondar, Ana-Nicoleta

2016-02-01

SecA uses the energy yielded by the binding and hydrolysis of adenosine triphosphate (ATP) to push secretory pre-proteins across the plasma membrane in bacteria. Hydrolysis of ATP occurs at the nucleotide-binding site, which contains the conserved carboxylate groups of the DEAD-box helicases. Although crystal structures provide valuable snapshots of SecA along its reaction cycle, the mechanism that ensures conformational coupling between the nucleotide-binding site and the other domains of SecA remains unclear. The observation that SecA contains numerous hydrogen-bonding groups raises important questions about the role of hydrogen-bonding networks and hydrogen-bond dynamics in long-distance conformational couplings. To address these questions, we explored the molecular dynamics of SecA from three different organisms, with and without bound nucleotide, in water. By computing two-dimensional hydrogen-bonding maps we identify networks of hydrogen bonds that connect the nucleotide-binding site to remote regions of the protein, and sites in the protein that respond to specific perturbations. We find that the nucleotide-binding site of ADP-bound SecA has a preferred geometry whereby the first two carboxylates of the DEAD motif bridge via hydrogen-bonding water. Simulations of a mutant with perturbed ATP hydrolysis highlight the water-bridged geometry as a key structural element of the reaction path. Copyright © 2015. Published by Elsevier B.V.

Phosphate recovery as struvite within a single chamber microbial electrolysis cell.

Science.gov (United States)

Cusick, Roland D; Logan, Bruce E

2012-03-01

An energy efficient method of concurrent hydrogen gas and struvite (MgNH(4)PO(4)·6H(2)O) production was investigated based on bioelectrochemically driven struvite crystallization at the cathode of a single chamber microbial electrolysis struvite-precipitation cell (MESC). The MESC cathodes were either stainless steel 304 mesh or flat plates. Phosphate removal ranged from 20% to 40%, with higher removals obtained using mesh cathodes than with flat plates. Cathode accumulated crystals were verified as struvite using a scanning electron microscope capable of energy dispersive spectroscopy (SEM-EDS). Crystal accumulation did not affect the rate of hydrogen production in struvite reactors. The rate of struvite crystallization (g/m(2)-h) and hydrogen production (m(3)/m(3)-d) were shown to be dependent on applied voltage and cathode material. Overall energy efficiencies (substrate and electricity) were high (73 ± 4%) and not dependent on applied voltage. These results show that MESCs may be useful both as a method for hydrogen gas and struvite production. Copyright © 2011 Elsevier Ltd. All rights reserved.

Phosphate recovery as struvite within a single chamber microbial electrolysis cell

KAUST Repository

Cusick, Roland D.

2012-03-01

An energy efficient method of concurrent hydrogen gas and struvite (MgNH 4PO 4·6H 2O) production was investigated based on bioelectrochemically driven struvite crystallization at the cathode of a single chamber microbial electrolysis struvite-precipitation cell (MESC). The MESC cathodes were either stainless steel 304 mesh or flat plates. Phosphate removal ranged from 20% to 40%, with higher removals obtained using mesh cathodes than with flat plates. Cathode accumulated crystals were verified as struvite using a scanning electron microscope capable of energy dispersive spectroscopy (SEM-EDS). Crystal accumulation did not affect the rate of hydrogen production in struvite reactors. The rate of struvite crystallization (g/m 2-h) and hydrogen production (m 3/m 3-d) were shown to be dependent on applied voltage and cathode material. Overall energy efficiencies (substrate and electricity) were high (73±4%) and not dependent on applied voltage. These results show that MESCs may be useful both as a method for hydrogen gas and struvite production. © 2011 Elsevier Ltd.

Amide linkages mimic phosphates in RNA interactions with proteins and are well tolerated in the guide strand of short interfering RNAs

Energy Technology Data Exchange (ETDEWEB)

Mutisya, Daniel; Hardcastle, Travis; Cheruiyot, Samwel K.; Pallan, Pradeep S.; Kennedy, Scott D.; Egli, Martin; Kelley, Melissa L.; Smith, Anja van Brabant; Rozners, Eriks

2017-06-27

While the use of RNA interference (RNAi) in molecular biology and functional genomics is a well-established technology, in vivo applications of synthetic short interfering RNAs (siRNAs) require chemical modifications. We recently found that amides as non-ionic replacements for phosphodiesters may be useful modifications for optimization of siRNAs. Herein, we report a comprehensive study of systematic replacement of a single phosphate with an amide linkage throughout the guide strand of siRNAs. The results show that amides are surprisingly well tolerated in the seed and central regions of the guide strand and increase the silencing activity when placed between nucleosides 10 and 12, at the catalytic site of Argonaute. A potential explanation is provided by the first crystal structure of an amide-modified RNA–DNA with Bacillus halodurans RNase H1. The structure reveals how small changes in both RNA and protein conformation allow the amide to establish hydrogen bonding interactions with the protein. Molecular dynamics simulations suggest that these alternative binding modes may compensate for interactions lost due to the absence of a phosphodiester moiety. Our results suggest that an amide can mimic important hydrogen bonding interactions with proteins required for RNAi activity and may be a promising modification for optimization of biological properties of siRNAs.

Nature-Inspired Design of Artificial Solar-to-Fuel Conversion Systems based on Copper Phosphate Microflowers.

Science.gov (United States)

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.

Mevalonate 5-diphosphate mediates ATP binding to the mevalonate diphosphate decarboxylase from the bacterial pathogen Enterococcus faecalis

Energy Technology Data Exchange (ETDEWEB)

Chen, Chun-Liang; Mermoud, James C.; Paul, Lake N.; Steussy, Calvin Nicklaus; Stauffacher, Cynthia V. (Purdue)

2017-10-12

The mevalonate pathway produces isopentenyl diphosphate (IPP), a building block for polyisoprenoid synthesis, and is a crucial pathway for growth of the human bacterial pathogen Enterococcus faecalis. The final enzyme in this pathway, mevalonate diphosphate decarboxylase (MDD), acts on mevalonate diphosphate (MVAPP) to produce IPP while consuming ATP. This essential enzyme has been suggested as a therapeutic target for the treatment of drug-resistant bacterial infections. Here, we report functional and structural studies on the mevalonate diphosphate decarboxylase from E. faecalis (MDDEF). The MDDEF crystal structure in complex with ATP (MDDEF–ATP) revealed that the phosphate-binding loop (amino acids 97–105) is not involved in ATP binding and that the phosphate tail of ATP in this structure is in an outward-facing position pointing away from the active site. This suggested that binding of MDDEF to MVAPP is necessary to guide ATP into a catalytically favorable position. Enzymology experiments show that the MDDEF performs a sequential ordered bi-substrate reaction with MVAPP as the first substrate, consistent with the isothermal titration calorimetry (ITC) experiments. On the basis of ITC results, we propose that this initial prerequisite binding of MVAPP enhances ATP binding. In summary, our findings reveal a substrate-induced substrate-binding event that occurs during the MDDEF-catalyzed reaction. The disengagement of the phosphate-binding loop concomitant with the alternative ATP-binding configuration may provide the structural basis for antimicrobial design against these pathogenic enterococci.

Tuning hydrogen storage in lithium-functionalized BC2N sheets by doping with boron and carbon.

Science.gov (United States)

Qiu, Nian-xiang; Zhang, Cheng-hua; Xue, Ying

2014-10-06

First-principles calculations are used to explore the strong binding of lithium to boron- and carbon-doped BC2N monolayers (BC2NBC and BC2NCN, respectively) without the formation of lithium clusters. In comparison to BC2N and BC2NCB, lithium-decorated BC2NBC and BC2NCN systems possess stronger s-p and p-p hybridization and, hence, the binding energy is higher. Lithium becomes partially positively charged by donating electron density to the more electronegative atoms of the sheet. Attractive van der Waals interactions are responsible for binding hydrogen molecules around the lithium atoms. Each lithium atom can adsorb three hydrogen molecules on both sides of the sheet, with an average hydrogen binding energy of approximately 0.2 eV, which is in the range required for practical applications. The BC2NBC-Li and BC2NCN-Li complexes can serve as high-capacity hydrogen-storage media with gravimetric hydrogen capacities of 9.88 and 9.94 wt %, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure of glycerol-3-phosphate dehydrogenase, an essential monotopic membrane enzyme involved in respiration and metabolism

International Nuclear Information System (INIS)

Yeh, Joanne I.; Chinte, Unmesh; Du, Shoucheng

2008-01-01

Sn-glycerol-3-phosphate dehydrogenase (GlpD) is an essential membrane enzyme, functioning at the central junction of respiration, glycolysis, and phospholipid biosynthesis. Its critical role is indicated by the multitiered regulatory mechanisms that stringently controls its expression and function. Once expressed, GlpD activity is regulated through lipid-enzyme interactions in Escherichia coli. Here, we report seven previously undescribed structures of the fully active E. coli GlpD, up to 1.75 (angstrom) resolution. In addition to elucidating the structure of the native enzyme, we have determined the structures of GlpD complexed with substrate analogues phosphoenolpyruvate, glyceric acid 2-phosphate, glyceraldehyde-3-phosphate, and product, dihydroxyacetone phosphate. These structural results reveal conformational states of the enzyme, delineating the residues involved in substrate binding and catalysis at the glycerol-3-phosphate site. Two probable mechanisms for catalyzing the dehydrogenation of glycerol-3-phosphate are envisioned, based on the conformational states of the complexes. To further correlate catalytic dehydrogenation to respiration, we have additionally determined the structures of GlpD bound with ubiquinone analogues menadione and 2-n-heptyl-4-hydroxyquinoline N-oxide, identifying a hydrophobic plateau that is likely the ubiquinone-binding site. These structures illuminate probable mechanisms of catalysis and suggest how GlpD shuttles electrons into the respiratory pathway. Glycerol metabolism has been implicated in insulin signaling and perturbations in glycerol uptake and catabolism are linked to obesity in humans. Homologs of GlpD are found in practically all organisms, from prokaryotes to humans, with >45% consensus protein sequences, signifying that these structural results on the prokaryotic enzyme may be readily applied to the eukaryotic GlpD enzymes.

Hydrogen Storage in Metal-Organic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Long, Jeffrey R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2016-04-28

The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H₂ storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H₂ at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H₂ adsorption measurements, to provide a comprehensive picture of H₂ adsorption at all relevant pressures. A

Binding Characteristics of Sphingosine-1-Phosphate to ApoM hints to Assisted Release Mechanism via the ApoM Calyx-Opening

Science.gov (United States)

Zhang, Hansi; Pluhackova, Kristyna; Jiang, Zhenyan; Böckmann, Rainer A.

2016-08-01

Sphingosine-1-phosphate (S1P) is a lysophospholipid mediator carried by the HDL-associated apoM protein in blood, regulating many physiological processes by activating the G protein-coupled S1P receptor in mammals. Despite the solved crystal structure of the apoM-S1P complex, the mechanism of S1P release from apoM as a part of the S1P pathway is unknown. Here, the dynamics of the wild type apoM-S1P complex as well as of mutants were investigated by means of atomistic molecular dynamics simulations. The potential of mean force for S1P unbinding from apoM reflected a large binding strength of more than 60 kJ/mol. This high unbinding free energy for S1P underlines the observed specificity of the physiological effects of S1P as it suggests that the spontaneous release of S1P from apoM is unlikely. Instead, S1P release and thus the control of this bioactive lipid probably requires the tight interaction with other molecules, e.g. with the S1P receptor. Mutations of specific S1P anchoring residues of apoM decreased the energetic barrier by up to 20 kJ/mol. Moreover, the ligand-free apoM protein is shown to adopt a more open upper hydrophilic binding pocket and to result in complete closure of the lower hydrophobic cavity, suggesting a mechanism for adjusting the gate for ligand access.

Identification of Glyceraldehyde-3-phosphate dehydrogenase (GAPDH as a binding protein for a 68-kDa Bacillus thuringiensis parasporal protein cytotoxic against leukaemic cells

Directory of Open Access Journals (Sweden)

Nadarajah Vishna

2010-11-01

Full Text Available Abstract Background Bacillus thuringiensis (Bt, an ubiquitous gram-positive spore-forming bacterium forms parasporal proteins during the stationary phase of its growth. Recent findings of selective human cancer cell-killing activity in non-insecticidal Bt isolates resulted in a new category of Bt parasporal protein called parasporin. However, little is known about the receptor molecules that bind parasporins and the mechanism of anti-cancer activity. A Malaysian Bt isolate, designated Bt18 produces parasporal protein that exhibit preferential cytotoxic activity for human leukaemic T cells (CEM-SS but is non-cytotoxic to normal T cells or other cancer cell lines such as human cervical cancer (HeLa, human breast cancer (MCF-7 and colon cancer (HT-29 suggesting properties similar to parasporin. In this study we aim to identify the binding protein for Bt18 in human leukaemic T cells. Methods Bt18 parasporal protein was separated using Mono Q anion exchange column attached to a HPLC system and antibody was raised against the purified 68-kDa parasporal protein. Receptor binding assay was used to detect the binding protein for Bt18 parasporal protein in CEM-SS cells and the identified protein was sent for N-terminal sequencing. NCBI protein BLAST was used to analyse the protein sequence. Double immunofluorescence staining techniques was applied to localise Bt18 and binding protein on CEM-SS cell. Results Anion exchange separation of Bt18 parasporal protein yielded a 68-kDa parasporal protein with specific cytotoxic activity. Polyclonal IgG (anti-Bt18 for the 68-kDa parasporal protein was successfully raised and purified. Receptor binding assay showed that Bt18 parasporal protein bound to a 36-kDa protein from the CEM-SS cells lysate. N-terminal amino acid sequence of the 36-kDa protein was GKVKVGVNGFGRIGG. NCBI protein BLAST revealed that the binding protein was Glyceraldehyde-3-phosphate dehydrogenase (GAPDH. Double immunofluorescence staining showed

Analysis of RNA binding by the dengue virus NS5 RNA capping enzyme.

Directory of Open Access Journals (Sweden)

Brittney R Henderson

Full Text Available Flaviviruses are small, capped positive sense RNA viruses that replicate in the cytoplasm of infected cells. Dengue virus and other related flaviviruses have evolved RNA capping enzymes to form the viral RNA cap structure that protects the viral genome and directs efficient viral polyprotein translation. The N-terminal domain of NS5 possesses the methyltransferase and guanylyltransferase activities necessary for forming mature RNA cap structures. The mechanism for flavivirus guanylyltransferase activity is currently unknown, and how the capping enzyme binds its diphosphorylated RNA substrate is important for deciphering how the flavivirus guanylyltransferase functions. In this report we examine how flavivirus NS5 N-terminal capping enzymes bind to the 5' end of the viral RNA using a fluorescence polarization-based RNA binding assay. We observed that the K(D for RNA binding is approximately 200 nM Dengue, Yellow Fever, and West Nile virus capping enzymes. Removal of one or both of the 5' phosphates reduces binding affinity, indicating that the terminal phosphates contribute significantly to binding. RNA binding affinity is negatively affected by the presence of GTP or ATP and positively affected by S-adensyl methoninine (SAM. Structural superpositioning of the dengue virus capping enzyme with the Vaccinia virus VP39 protein bound to RNA suggests how the flavivirus capping enzyme may bind RNA, and mutagenesis analysis of residues in the putative RNA binding site demonstrate that several basic residues are critical for RNA binding. Several mutants show differential binding to 5' di-, mono-, and un-phosphorylated RNAs. The mode of RNA binding appears similar to that found with other methyltransferase enzymes, and a discussion of diphosphorylated RNA binding is presented.

Computational Design of Biomimetic Phosphate Scavengers

DEFF Research Database (Denmark)

Gruber, Mathias Felix; Wood, Elizabeth Baker; Truelsen, Sigurd Friis

2015-01-01

Phosphorus has long been the target of much research, but in recent years the focus has shifted from being limited only to reducing its detrimental environmental impact, to also looking at how it is linked to the global food security. Therefore, the interest in finding novel techniques for phosph......Phosphorus has long been the target of much research, but in recent years the focus has shifted from being limited only to reducing its detrimental environmental impact, to also looking at how it is linked to the global food security. Therefore, the interest in finding novel techniques...... for phosphorus recovery, as well as improving existing techniques, has increased. In this study we apply a hybrid simulation approach of molecular dynamics and quantum mechanics to investigate the binding modes of phosphate anions by a small intrinsically disordered peptide. Our results confirm...... phosphate could be the starting point of new novel technological approaches toward phosphorus recovery, and they represent an excellent model system for investigating the nature and dynamics of functional de novo designed intrinsically disordered proteins....

Phosphate and arsenate removal efficiency by thermostable ferritin enzyme from Pyrococcus furiosus using radioisotopes

KAUST Repository

Sevcenco, Ana-Maria

2015-03-13

Oxo-anion binding properties of the thermostable enzyme ferritin from Pyrococcus furiosus were characterized with radiography. Radioisotopes 32P and 76As present as oxoanions were used to measure the extent and the rate of their absorption by the ferritin. Thermostable ferritin proved to be an excellent system for rapid phosphate and arsenate removal from aqueous solutions down to residual concentrations at the picomolar level. These very low concentrations make thermostable ferritin a potential tool to considerably mitigate industrial biofouling by phosphate limitation or to remove arsenate from drinking water.

Reversible and Irreversible Binding of Nanoparticles to Polymeric Surfaces

Directory of Open Access Journals (Sweden)

Wolfgang H. Binder

2009-01-01

Full Text Available Reversible and irreversible binding of CdSe-nanoparticles and nanorods to polymeric surfaces via a strong, multiple hydrogen bond (= Hamilton-receptor/barbituric acid is described. Based on ROMP-copolymers, the supramolecular interaction on a thin polymer film is controlled by living polymerization methods, attaching the Hamilton-receptor in various architectures, and concentrations. Strong binding is observed with CdSe-nanoparticles and CdSe-nanorods, whose surfaces are equipped with matching barbituric acid-moieties. Addition of polar solvents, able to break the hydrogen bonds leads to the detachment of the nanoparticles from the polymeric film. Irreversible binding is observed if an azide/alkine-“click”-reaction is conducted after supramolecular recognition of the nanoparticles on the polymeric surface. Thus reversible or irreversible attachment of the nanosized objects can be achieved.

Reaction of dimethyl hydrogen phosphite with acecyclone

International Nuclear Information System (INIS)

Arbuzov, B.A.; Fuzhenkova, A.V.; Tyryshkin, N.I.

1987-01-01

In the presence of bases acecyclone reacts with dimethyl hydrogen phosphite with the formation of gamma-keto phosphonates with conjugated and unconjugated structures, and also an enol phosphate, a product containing a bond between oxygen of the cyclone and phosphorus. In the absence of bases, as well as the beta-keto phosphonate, gamma-keto phosphonates of cis and trans structure are formed; they are products of the 1,4 addition of dimethyl hydrogen phosphite to the conjugated fragment C=C-C=O of the cyclone. The compositions of the reaction mixture were determined by IR and NMR spectroscopy and TLC. Full-scale analysis of chemical shifts and spin-spin coupling constants was performed

Interstellar hydrogen bonding

Science.gov (United States)

Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

2018-06-01

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

Effects of an electric field on the confined hydrogen atom in a parabolic potential well

International Nuclear Information System (INIS)

Xie Wenfang

2009-01-01

Using the perturbation method, the confined hydrogen atom by a parabolic potential well is investigated. The binding energy of the confined hydrogen atom in a parabolic potential well is calculated as a function of the confined potential radius and as a function of the intensity of an applied electric field. It is shown that the binding energy of the confined hydrogen atom is highly dependent on the confined potential radius and the intensity of an applied electric field.

X-ray structures of uridine phosphorylase from Vibrio cholerae in complexes with uridine, thymidine, uracil, thymine, and phosphate anion: Substrate specificity of bacterial uridine phosphorylases

Energy Technology Data Exchange (ETDEWEB)

Prokofev, I. I.; Lashkov, A. A., E-mail: alashkov83@gmail.com; Gabdulkhakov, A. G.; Balaev, V. V.; Seregina, T. A. [Russian Academy of Sciences, Shubnikov Institute of Crystallography of Federal Scientific Research Centre “Crystallography and Photonics” (Russian Federation); Mironov, A. S. [State Research Institute of Genetics and Selection of Industrial Microorganisms (Russian Federation); Betzel, C. [University of Hamburg (Germany); Mikhailov, A. M. [Russian Academy of Sciences, Shubnikov Institute of Crystallography of Federal Scientific Research Centre “Crystallography and Photonics” (Russian Federation)

2016-11-15

In many types of human tumor cells and infectious agents, the demand for pyrimidine nitrogen bases increases during the development of the disease, thus increasing the role of the enzyme uridine phosphorylase in metabolic processes. The rational use of uridine phosphorylase and its ligands in pharmaceutical and biotechnology industries requires knowledge of the structural basis for the substrate specificity of the target enzyme. This paper summarizes the results of the systematic study of the three-dimensional structure of uridine phosphorylase from the pathogenic bacterium Vibrio cholerae in complexes with substrates of enzymatic reactions—uridine, phosphate anion, thymidine, uracil, and thymine. These data, supplemented with the results of molecular modeling, were used to consider in detail the structural basis for the substrate specificity of uridine phosphorylases. It was shown for the first time that the formation of a hydrogen-bond network between the 2′-hydroxy group of uridine and atoms of the active-site residues of uridine phosphorylase leads to conformational changes of the ribose moiety of uridine, resulting in an increase in the reactivity of uridine compared to thymidine. Since the binding of thymidine to residues of uridine phosphorylase causes a smaller local strain of the β-N1-glycosidic bond in this the substrate compared to the uridine molecule, the β-N1-glycosidic bond in thymidine is more stable and less reactive than that in uridine. It was shown for the first time that the phosphate anion, which is the second substrate bound at the active site, interacts simultaneously with the residues of the β5-strand and the β1-strand through hydrogen bonding, thus securing the gate loop in a conformation.

X-ray structures of uridine phosphorylase from Vibrio cholerae in complexes with uridine, thymidine, uracil, thymine, and phosphate anion: Substrate specificity of bacterial uridine phosphorylases

Science.gov (United States)

Prokofev, I. I.; Lashkov, A. A.; Gabdulkhakov, A. G.; Balaev, V. V.; Seregina, T. A.; Mironov, A. S.; Betzel, C.; Mikhailov, A. M.

2016-11-01

In many types of human tumor cells and infectious agents, the demand for pyrimidine nitrogen bases increases during the development of the disease, thus increasing the role of the enzyme uridine phosphorylase in metabolic processes. The rational use of uridine phosphorylase and its ligands in pharmaceutical and biotechnology industries requires knowledge of the structural basis for the substrate specificity of the target enzyme. This paper summarizes the results of the systematic study of the three-dimensional structure of uridine phosphorylase from the pathogenic bacterium Vibrio cholerae in complexes with substrates of enzymatic reactions—uridine, phosphate anion, thymidine, uracil, and thymine. These data, supplemented with the results of molecular modeling, were used to consider in detail the structural basis for the substrate specificity of uridine phosphorylases. It was shown for the first time that the formation of a hydrogen-bond network between the 2'-hydroxy group of uridine and atoms of the active-site residues of uridine phosphorylase leads to conformational changes of the ribose moiety of uridine, resulting in an increase in the reactivity of uridine compared to thymidine. Since the binding of thymidine to residues of uridine phosphorylase causes a smaller local strain of the β-N1-glycosidic bond in this the substrate compared to the uridine molecule, the β-N1-glycosidic bond in thymidine is more stable and less reactive than that in uridine. It was shown for the first time that the phosphate anion, which is the second substrate bound at the active site, interacts simultaneously with the residues of the β5-strand and the β1-strand through hydrogen bonding, thus securing the gate loop in a conformation

Turn-on fluorescent sensor for Zinc and Cadmium ions based on quinolone and its sequential response to phosphate

International Nuclear Information System (INIS)

Liu, Xiaoyan; Wang, Peng; Fu, Jiaxin; Yao, Kun; Xue, Kun; Xu, Kuoxi

2017-01-01

Sequential fluorescence sensing of Zn 2+ /Cd 2+ ions and phosphate anion by new quinoline based sensors(L1 and L2) have been presented. Sensors exhibit highly selective fluorescence “turn-on” sensing properties to Zn 2+ /Cd 2+ ions in CH 3 OH/H 2 O(1/1, v/v, Tris, 10 mol·L −1 , pH 7.4) solution with a 1:1 binding stoichiometry. The complexes display high selectivity to H 2 PO 4 - and HPO 4 2- anions through fluorescence “turn-off” respond. The results of Zn 2+ /Cd 2+ ions and phosphate anion sequential recognition via fluorescence changes make sensors L1 and L2 have potential utility for Zn 2+ / Cd 2+ ions and phosphate anion detection in aqueous media. - Graphical abstract: Sequential fluorescence sensing of Zn 2+ /Cd 2+ ions and phosphate anion by new quinoline based sensors (L1 and L2) have been presented. Sensors exhibit highly selective and sensitive fluorescence “turn-on” sensing properties to Zn 2+ /Cd 2+ ions in CH 3 OH/H 2 O(1/1, v/v, Tris, 10 mM, pH 7.4) solution with a 1:1 binding stoichiometry. The complexes display high selectivity to H 2 PO 4 - and HPO 4 2- anions through fluorescence “turn-off” respond. Zn 2+ /Cd 2+ ions and phosphate anion sequential recognition via fluorescence changes make sensors L1 and L2 have potential utility for Zn 2+ / Cd 2+ ions and phosphate anion detection in aqueous media.

Hydrogen storage inside graphene-oxide frameworks

International Nuclear Information System (INIS)

Chan Yue; Hill, James M

2011-01-01

In this paper, we use applied mathematical modelling to investigate the storage of hydrogen molecules inside graphene-oxide frameworks, which comprise two parallel graphenes rigidly separated by perpendicular ligands. Hydrogen uptake is calculated for graphene-oxide frameworks using the continuous approximation and an equation of state for both the bulk and adsorption gas phases. We first validate our approach by obtaining results for two parallel graphene sheets. This result agrees well with an existing theoretical result, namely 1.85 wt% from our calculations, and 2 wt% arising from an ab initio and grand canonical Monte Carlo calculation. This provides confidence to the determination of the hydrogen uptake for the four graphene-oxide frameworks, GOF-120, GOF-66, GOF-28 and GOF-6, and we obtain 1.68, 2, 6.33 and 0 wt%, respectively. The high value obtained for GOF-28 may be partly explained by the fact that the benzenediboronic acid pillars between graphene sheets not only provide mechanical support and porous spaces for the molecular structure but also provide the higher binding energy to enhance the hydrogen storage inside graphene-oxide frameworks. For the other three structures, this binding energy is not as large in comparison to that of GOF-28 and this effect diminishes as the ligand density decreases. In the absence of conflicting data, the present work indicates GOF-28 as a likely contender for practical hydrogen storage.

A macrocyclic ligand as receptor and Zn(II)-complex receptor for anions in water: binding properties and crystal structures.

Science.gov (United States)

Ambrosi, Gianluca; Formica, Mauro; Fusi, Vieri; Giorgi, Luca; Macedi, Eleonora; Micheloni, Mauro; Paoli, Paola; Pontellini, Roberto; Rossi, Patrizia

2011-02-01

Binding properties of 24,29-dimethyl-6,7,15,16-tetraoxotetracyclo[19.5.5.0(5,8).0(14,17)]-1,4,9,13,18,21,24,29-octaazaenatriaconta-Δ(5,8),Δ(14,17)-diene ligand L towards Zn(II) and anions, such as the halide series and inorganic oxoanions (phosphate (Pi), sulfate, pyrophosphate (PPi), and others), were investigated in aqueous solution; in addition, the Zn(II)/L system was tested as a metal-ion-based receptor for the halide series. Ligand L is a cryptand receptor incorporating two squaramide functions in an over-structured chain that connects two opposite nitrogen atoms of the Me(2)[12]aneN(4) polyaza macrocyclic base. It binds Zn(II) to form mononuclear species in which the metal ion, coordinated by the Me(2)[12]aneN(4) moiety, lodges inside the three-dimensional cavity. Zn(II)-containing species are able to bind chloride and fluoride at the physiologically important pH value of 7.4; the anion is coordinated to the metal center but the squaramide units play the key role in stabilizing the anion through a hydrogen-bonding network; two crystal structures reported here clearly show this aspect. Free L is able to bind fluoride, chloride, bromide, sulfate, Pi, and PPi in aqueous solution. The halides are bound at acidic pH, whereas the oxoanions are bound in a wide range of pH values ranging from acidic to basic. The cryptand cavity, abundant in hydrogen-bonding sites at all pH values, allows excellent selectivity towards Pi to be achieved mainly at physiological pH 7.4. By joining amine and squaramide moieties and using this preorganized topology, it was possible, with preservation of the solubility of the receptor, to achieve a very wide pH range in which oxoanions can be bound. The good selectivity towards Pi allows its discrimination in a manner not easily obtainable with nonmetallic systems in aqueous environment. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density Functional Theory Study of the Interaction of Hydrogen with Li6C60.

Science.gov (United States)

Wang, Qian; Jena, Puru

2012-05-03

Hydrogen storage properties of Li-coated C60 fullerene have been studied using density functional theory within the local density as well as generalized gradient approximation. Hydrogen atoms are found to bind to Li6C60 in two distinct forms, with the first set attaching to C atoms, not linked to Li, in atomic form. Once all such C atoms are saturated with hydrogen, the second set of hydrogen atoms bind quasi-molecularly to the Li atoms, five of which remain in the exohedral and the sixth in the endohedral position. The corresponding hydrogen gravimetric density in Li6C60H40 is 5 wt %. Desorption of hydrogen takes place in succession, the ones bound quasi-molecularly desorbing at a temperature lower than the ones bound atomically. The results are compared with the recent experiment on hydrogen adsorption in Li6C60.

It takes two to tango: defining an essential second active site in pyridoxal 5'-phosphate synthase.

Directory of Open Access Journals (Sweden)

Cyril Moccand

Full Text Available The prevalent de novo biosynthetic pathway of vitamin B6 involves only two enzymes (Pdx1 and Pdx2 that form an ornate multisubunit complex functioning as a glutamine amidotransferase. The synthase subunit, Pdx1, utilizes ribose 5-phosphate and glyceraldehyde 3-phosphate, as well as ammonia derived from the glutaminase activity of Pdx2 to directly form the cofactor vitamer, pyridoxal 5'-phosphate. Given the fact that a single enzyme performs the majority of the chemistry behind this reaction, a complicated mechanism is anticipated. Recently, the individual steps along the reaction co-ordinate are beginning to be unraveled. In particular, the binding of the pentose substrate and the first steps of the reaction have been elucidated but it is not known if the latter part of the chemistry, involving the triose sugar, takes place in the same or a disparate site. Here, we demonstrate through the use of enzyme assays, enzyme kinetics, and mutagenesis studies that indeed a second site is involved in binding the triose sugar and moreover, is the location of the final vitamin product, pyridoxal 5'-phosphate. Furthermore, we show that product release is triggered by the presence of a PLP-dependent enzyme. Finally, we provide evidence that a single arginine residue of the C terminus of Pdx1 is responsible for coordinating co-operativity in this elaborate protein machinery.

First principles study of inert-gas (helium, neon, and argon) interactions with hydrogen in tungsten

Energy Technology Data Exchange (ETDEWEB)

Kong, Xiang-Shan [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P. O. Box 1129, Hefei 230031 (China); Hou, Jie [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P. O. Box 1129, Hefei 230031 (China); University of Science and Technology of China, Hefei 230026 (China); Li, Xiang-Yan [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P. O. Box 1129, Hefei 230031 (China); Wu, Xuebang, E-mail: xbwu@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P. O. Box 1129, Hefei 230031 (China); Liu, C.S., E-mail: csliu@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P. O. Box 1129, Hefei 230031 (China); Chen, Jun-Ling; Luo, G.-N. [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China)

2017-04-15

We have systematically evaluated binding energies of hydrogen with inert-gas (helium, neon, and argon) defects, including interstitial clusters and vacancy-inert-gas complexes, and their stable configurations using first-principles calculations. Our calculations show that these inert-gas defects have large positive binding energies with hydrogen, 0.4–1.1 eV, 0.7–1.0 eV, and 0.6–0.8 eV for helium, neon, and argon, respectively. This indicates that these inert-gas defects can act as traps for hydrogen in tungsten, and impede or interrupt the diffusion of hydrogen in tungsten, which supports the discussion on the influence of inert-gas on hydrogen retention in recent experimental literature. The interaction between these inert-gas defects and hydrogen can be understood by the attractive interaction due to the distortion of the lattice structure induced by inert-gas defects, the intrinsic repulsive interaction between inert-gas atoms and hydrogen, and the hydrogen-hydrogen repelling in tungsten lattice.

Bioactivity tests of calcium phosphates with variant molar ratios of main components.

Science.gov (United States)

Pluta, Klaudia; Sobczak-Kupiec, Agnieszka; Półtorak, Olga; Malina, Dagmara; Tyliszczak, Bożena

2018-03-09

Calcium phosphates constitute attractive materials of biomedical applications. Among them particular attention is devoted to bioactive hydroxyapatite (HAp) and bioresorbable tricalcium phosphate (TCP) that possess ability to bind to living bones and can be used clinically as important bone substitutes. Notably, in vivo bone bioactivity can be predicted from apatite formation of bone immersed in SBF fluids. Thus, analyses of behavior of calcium phosphates immersed in various bio fluids are of great importance. Recently, stoichiometric HAp and TCP structures have been widely studied, whereas only limited number of publications have been devoted to analyses of nonstoichiometric calcium phosphates. Here, we report physicochemical analysis of natural and synthetic phosphates with variable Ca/P molar ratios. Subsequently attained structures were subjected to incubation in either artificial saliva or Ringer's fluids. Both pH and conductivity of such fluids were determined before and after incubation. Furthermore, the influence of the Ca/P values on such parameters was exemplified. Physicochemical analysis of received materials was performed by XRD and FT-IR characterization techniques. Their potential antibacterial activity and behavior in the presence of infectious microorganisms as Escherichia coli and Staphylococcus aureus was also evaluated. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2018. © 2018 Wiley Periodicals, Inc.

Deep levels due to hydrogen in ZnO single crystals

Science.gov (United States)

Parmar, Narendra; Weber, Marc; Lynn, Kelvin

2009-05-01

Hydrogen impurities and oxygen vacancies are involved in the ˜0.7 eV shift of the optical absorption edge of ZnO. Deuterium causes a smaller shift. Titanium metal is used to bind hydrogen as it diffuses out of ZnO. Positron annihilation spectroscopy coupled with other techniques point to the presence of oxygen vacancies. Removing hydrogen followed by annealing in oxygen reduces the carrier concentration.

Interactions of benzoic acid and phosphates with iron oxide colloids using chemical force titration.

Science.gov (United States)

Liang, Jana; Horton, J Hugh

2005-11-08

Colloidal iron oxides are an important component in soil systems and in water treatment processes. Humic-based organic compounds, containing both phenol and benzoate functional groups, are often present in these systems and compete strongly with phosphate species for binding sites on the iron oxide surfaces. Here, we examine the interaction of benzoate and phenolic groups with various iron oxide colloids using atomic force microscopy (AFM) chemical force titration measurements. Self-assembled monolayers (SAMs) of 4-(12-mercaptododecyloxy)benzoic acid and 4-(12-mercaptododecyloxy)phenol were used to prepare chemically modified Au-coated AFM tips, and these were used to probe the surface chemistry of a series of iron oxide colloids. The SAMs formed were also characterized using scanning tunneling microscopy, reflection-absorption infrared spectroscopy, and X-ray photoelectron spectroscopy. The surface pK(a) of 4-(12- mercaptododecyloxy)benzoic acid has been determined to be 4.0 +/- 0.5, and the interaction between the tip and the sample coated with a SAM of this species is dominated by hydrogen bonding. The chemical force titraton profile for an AFM probe coated with 4-(12- mercaptododecyloxy)benzoic acid and a bare iron oxide colloid demonstrates that the benzoic acid function group interacts with all three types of iron oxide sites present on the colloid surface over a wide pH range. Similar experiments were carried out on colloids precipitated in the presence of phosphoric, gallic, and tannic acids. The results are discussed in the context of the competitive binding interactions of solution species present in soils or in water treatment processes.

Structural basis of non-steroidal anti-inflammatory drug diclofenac binding to human serum albumin.

Science.gov (United States)

Zhang, Yao; Lee, Philbert; Liang, Shichu; Zhou, Zuping; Wu, Xiaoyang; Yang, Feng; Liang, Hong

2015-11-01

Human serum albumin (HSA) is the most abundant protein in plasma, which plays a central role in drug pharmacokinetics because most compounds bound to HSA in blood circulation. To understand binding characterization of non-steroidal anti-inflammatory drugs to HSA, we resolved the structure of diclofenac and HSA complex by X-ray crystallography. HSA-palmitic acid-diclofenac structure reveals two distinct binding sites for three diclofenac in HSA. One diclofenac is located at the IB subdomain, and its carboxylate group projects toward polar environment, forming hydrogen bond with one water molecule. The other two diclofenac molecules cobind in big hydrophobic cavity of the IIA subdomain without interactive association. Among them, one binds in main chamber of big hydrophobic cavity, and its carboxylate group forms hydrogen bonds with Lys199 and Arg218, as well as one water molecule, whereas another diclofenac binds in side chamber, its carboxylate group projects out cavity, forming hydrogen bond with Ser480. © 2015 John Wiley & Sons A/S.

Hydrogenic impurity in double quantum dots

International Nuclear Information System (INIS)

Wang, X.F.

2007-01-01

The ground state binding energy and the average interparticle distances for a hydrogenic impurity in double quantum dots with Gaussian confinement potential are studied by the variational method. The probability density of the electron is calculated, too. The dependence of the binding energy on the impurity position is investigated for GaAs quantum dots. The result shows that the binding energy has a minimum as a function of the distance between the two quantum dots when the impurity is located at the center of one quantum dot or at the center of the edge of one quantum dot. When the impurity is located at the center of the two dots, the binding energy decreases monotonically

Structural and Functional Insight of Sphingosine 1-Phosphate-Mediated Pathogenic Metabolic Reprogramming in Sickle Cell Disease.

Science.gov (United States)

Sun, Kaiqi; D'Alessandro, Angelo; Ahmed, Mostafa H; Zhang, Yujin; Song, Anren; Ko, Tzu-Ping; Nemkov, Travis; Reisz, Julie A; Wu, Hongyu; Adebiyi, Morayo; Peng, Zhangzhe; Gong, Jing; Liu, Hong; Huang, Aji; Wen, Yuan Edward; Wen, Alexander Q; Berka, Vladimir; Bogdanov, Mikhail V; Abdulmalik, Osheiza; Han, Leng; Tsai, Ah-Lim; Idowu, Modupe; Juneja, Harinder S; Kellems, Rodney E; Dowhan, William; Hansen, Kirk C; Safo, Martin K; Xia, Yang

2017-11-10

Elevated sphingosine 1-phosphate (S1P) is detrimental in Sickle Cell Disease (SCD), but the mechanistic basis remains obscure. Here, we report that increased erythrocyte S1P binds to deoxygenated sickle Hb (deoxyHbS), facilitates deoxyHbS anchoring to the membrane, induces release of membrane-bound glycolytic enzymes and in turn switches glucose flux towards glycolysis relative to the pentose phosphate pathway (PPP). Suppressed PPP causes compromised glutathione homeostasis and increased oxidative stress, while enhanced glycolysis induces production of 2,3-bisphosphoglycerate (2,3-BPG) and thus increases deoxyHbS polymerization, sickling, hemolysis and disease progression. Functional studies revealed that S1P and 2,3-BPG work synergistically to decrease both HbA and HbS oxygen binding affinity. The crystal structure at 1.9 Å resolution deciphered that S1P binds to the surface of 2,3-BPG-deoxyHbA and causes additional conformation changes to the T-state Hb. Phosphate moiety of the surface bound S1P engages in a highly positive region close to α1-heme while its aliphatic chain snakes along a shallow cavity making hydrophobic interactions in the "switch region", as well as with α2-heme like a molecular "sticky tape" with the last 3-4 carbon atoms sticking out into bulk solvent. Altogether, our findings provide functional and structural bases underlying S1P-mediated pathogenic metabolic reprogramming in SCD and novel therapeutic avenues.

A comparative study for Hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers

International Nuclear Information System (INIS)

Lu, Jinlian; Guo, Yanhua; Zhang, Yun; Tang, Yingru; Cao, Juexian

2015-01-01

A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%, 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. - Graphical abstract: Metal atoms (Li, Ca, Sc and Ti) can strongly bind to graphyne nanotubes to avoid the formation of metal clusters, and a capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube. - Highlights: • The binding strength for metal on graphyne nanotubes is much stronger than that on γ-graphyne monolayer. • Metal atoms can strongly bind to the curving triangle acetylenes rings to avoid the formation of metal clusters. • A capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015.

Hydrogen energy technology development conference. From production of hydrogen to application of utilization technologies and metal hydrides, and examples; Suiso energy gijutsu kaihatsu kaigi. Suiso no seizo kara riyo gijutsu kinzoku suisokabutsu no oyo to jirei

Energy Technology Data Exchange (ETDEWEB)

NONE

1984-02-14

The hydrogen energy technology development conference was held on February 14 to 17, 1984 in Tokyo. For hydrogen energy systems and production of hydrogen from water, 6 papers were presented for, e.g., the future of hydrogen energy, current state and future of hydrogen production processes, and current state of thermochemical hydrogen technology development. For hydrogen production, 6 papers were presented for, e.g., production of hydrogen from steel mill gas, coal and methanol. For metal hydrides and their applications, 6 papers were presented for, e.g., current state of development of hydrogen-occluding alloy materials, analysis of heat transfer in metal hydride layers modified with an organic compound and its simulation, and development of a large-size hydrogen storage system for industrial purposes. For hydrogen utilization technologies, 8 papers were presented for, e.g., combustion technologies, engines incorporating metal hydrides, safety of metal hydrides, hydrogen embrittlement of system materials, development trends of phosphate type fuel cells, and alkali and other low-temperature type fuel cells. (NEDO)

Reaction of hydrogen with Ag(111): binding states, minimum energy paths, and kinetics.

Science.gov (United States)

Montoya, Alejandro; Schlunke, Anna; Haynes, Brian S

2006-08-31

The interaction of atomic and molecular hydrogen with the Ag(111) surface is studied using periodic density functional total-energy calculations. This paper focuses on the site preference for adsorption, ordered structures, and energy barriers for H diffusion and H recombination. Chemisorbed H atoms are unstable with respect to the H(2) molecule in all adsorption sites below monolayer coverage. The three-hollow sites are energetically the most favorable for H chemisorption. The binding energy of H to the surface decreases slightly up to one monolayer, suggesting a small repulsive H-H interaction on nonadjacent sites. Subsurface and vacancy sites are energetically less favorable for H adsorption than on-top sites. Recombination of chemisorbed H atoms leads to the formation of gas-phase H(2) with no molecular chemisorbed state. Recombination is an exothermic process and occurs on the bridge site with a pronounced energy barrier. This energy barrier is significantly higher than that inferred from experimental temperature-programmed desorption (TPD) studies. However, there is significant permeability of H atoms through the recombination energy barrier at low temperatures, thus increasing the rate constant for H(2) desorption due to quantum tunneling effects, and improving the agreement between experiment and theory.

Adsorption and diffusion characteristics of lithium on hydrogenated α- and β-silicene.

Science.gov (United States)

Iyikanat, Fadil; Kandemir, Ali; Bacaksiz, Cihan; Sahin, Hasan

2017-01-01

Using first-principles density functional theory calculations, we investigate adsorption properties and the diffusion mechanism of a Li atom on hydrogenated single-layer α- and β-silicene on a Ag(111) surface. It is found that a Li atom binds strongly on the surfaces of both α- and β-silicene, and it forms an ionic bond through the transfer of charge from the adsorbed atom to the surface. The binding energies of a Li atom on these surfaces are very similar. However, the diffusion barrier of a Li atom on H-α-Si is much higher than that on H-β-Si. The energy surface calculations show that a Li atom does not prefer to bind in the vicinity of the hydrogenated upper-Si atoms. Strong interaction between Li atoms and hydrogenated silicene phases and low diffusion barriers show that α- and β-silicene are promising platforms for Li-storage applications.

The Stringent Response Induced by Phosphate Limitation Promotes Purine Salvage in Agrobacterium fabrum.

Science.gov (United States)

Sivapragasam, Smitha; Deochand, Dinesh K; Meariman, Jacob K; Grove, Anne

2017-10-31

Agrobacterium fabrum induces tumor growth in susceptible plant species. The upregulation of virulence genes that occurs when the bacterium senses plant-derived compounds is enhanced by acidic pH and limiting inorganic phosphate. Nutrient starvation may also trigger the stringent response, and purine salvage is among the pathways expected to be favored under such conditions. We show here that phosphate limitation induces the stringent response, as evidenced by production of (p)ppGpp, and that the xdhCSML operon encoding the purine salvage enzyme xanthine dehydrogenase is upregulated ∼15-fold. The xdhCSML operon is under control of the TetR family transcription factor XdhR; direct binding of ppGpp to XdhR attenuates DNA binding, and the enhanced xdhCSML expression correlates with increased cellular levels of (p)ppGpp. Xanthine dehydrogenase may also divert purines away from salvage pathways to form urate, the ligand for the transcription factor PecS, which in the plant pathogen Dickeya dadantii is a key regulator of virulence gene expression. However, urate levels remain low under conditions that produce increased levels of xdhCSML expression, and neither acidic pH nor limiting phosphate results in induction of genes under control of PecS. Instead, expression of such genes is induced only by externally supplemented urate. Taken together, our data indicate that purine salvage is favored during the stringent response induced by phosphate starvation, suggesting that control of this pathway may constitute a novel approach to modulating virulence. Because bacterial purine catabolism appears to be unaffected, as evidenced by the absence of urate accumulation, we further propose that the PecS regulon is induced by only host-derived urate.

Agonist-dependent effects of mutations in the sphingosine-1-phosphate type 1 receptor

NARCIS (Netherlands)

van Loenen, Pieter B.; de Graaf, Chris; Verzijl, Dennis; Leurs, Rob; Rognan, Didier; Peters, Stephan L. M.; Alewijnse, Astrid E.

2011-01-01

The sphingosine-1-phosphate type 1 (S1P(1)) receptor is a new target in the treatment of auto-immune diseases as evidenced by the recent approval of FTY720 (Fingolimod). The ligand-binding pocket of the S1P(1) receptor has been generally characterised but detailed insight into ligand-specific

Hydrogen storage in carbon nanotubes.

Science.gov (United States)

Hirscher, M; Becher, M

2003-01-01

The article gives a comprehensive overview of hydrogen storage in carbon nanostructures, including experimental results and theoretical calculations. Soon after the discovery of carbon nanotubes in 1991, different research groups succeeded in filling carbon nanotubes with some elements, and, therefore, the question arose of filling carbon nanotubes with hydrogen by possibly using new effects such as nano-capillarity. Subsequently, very promising experiments claiming high hydrogen storage capacities in different carbon nanostructures initiated enormous research activity. Hydrogen storage capacities have been reported that exceed the benchmark for automotive application of 6.5 wt% set by the U.S. Department of Energy. However, the experimental data obtained with different methods for various carbon nanostructures show an extreme scatter. Classical calculations based on physisorption of hydrogen molecules could not explain the high storage capacities measured at ambient temperature, and, assuming chemisorption of hydrogen atoms, hydrogen release requires temperatures too high for technical applications. Up to now, only a few calculations and experiments indicate the possibility of an intermediate binding energy. Recently, serious doubt has arisen in relation to several key experiments, causing considerable controversy. Furthermore, high hydrogen storage capacities measured for carbon nanofibers did not survive cross-checking in different laboratories. Therefore, in light of today's knowledge, it is becoming less likely that at moderate pressures around room temperature carbon nanostructures can store the amount of hydrogen required for automotive applications.

Method for the enzymatic production of hydrogen

Science.gov (United States)

Woodward, J.; Mattingly, S.M.

1999-08-24

The present invention is an enzymatic method for producing hydrogen comprising the steps of: (a) forming a reaction mixture within a reaction vessel comprising a substrate capable of undergoing oxidation within a catabolic reaction, such as glucose, galactose, xylose, mannose, sucrose, lactose, cellulose, xylan and starch; the reaction mixture also comprising an amount of glucose dehydrogenase in an amount sufficient to catalyze the oxidation of the substrate, an amount of hydrogenase sufficient to catalyze an electron-requiring reaction wherein a stoichiometric yield of hydrogen is produced, an amount of pH buffer in an amount sufficient to provide an environment that allows the hydrogenase and the glucose dehydrogenase to retain sufficient activity for the production of hydrogen to occur and also comprising an amount of nicotinamide adenine dinucleotide phosphate sufficient to transfer electrons from the catabolic reaction to the electron-requiring reaction; (b) heating the reaction mixture at a temperature sufficient for glucose dehydrogenase and the hydrogenase to retain sufficient activity and sufficient for the production of hydrogen to occur, and heating for a period of time that continues until the hydrogen is no longer produced by the reaction mixture, wherein the catabolic reaction and the electron-requiring reactions have rates of reaction dependent upon the temperature; and (c) detecting the hydrogen produced from the reaction mixture. 8 figs.

Zinc-phosphate nanoparticles with reversibly attached TNF-α analogs: an interesting concept for potential use in active immunotherapy

International Nuclear Information System (INIS)

Hribar, Gorazd; Žnidaršič, Andrej; Bele, Marjan; Maver, Uroš; Caserman, Simon; Gaberšček, Miran; Gaberc-Porekar, Vladka

2011-01-01

The authors’ intention was to prepare nanometer-sized zinc-phosphate nanoparticles that would be capable of binding histidine-rich TNF-α analogs onto their surface via a coordinative bond. Zinc-phosphate nanoparticles with a size of around 60 nm were prepared by a wet precipitation method and characterized using SEM, EDX, XRD, and DLS. First, BSA was bound as a testing protein, afterward two TNF-α analogs with decreased activity were bound to the described nanoparticles. The efficiency of binding and the existence of coordinative bond were confirmed with SDS-PAGE analysis. During binding, particle storage, and release experiments, the prepared TNF-α analogs retained their biological activity—hence the epitopes necessary for formation of antibodies stayed intact. The particle size did not change within a period of 2 weeks. No significant agglomeration was observed, the particles could be quickly dispersed in ultrasound. The present nanoparticles and the general approach of coordinative binding are widely applicable for natural and engineered histidine-rich proteins. The nanoparticles bearing appropriate TNF-α analogs could also be potentially used for active immunotherapy to tackle the chronic inflammatory diseases associated with pathogenically elevated levels of TNF-α.

Triiodothyronine (T3)-associated upregulation and downregulation of nuclear T3 binding in the human fibroblast cell (MRC-5)--stimulation of malic enzyme, glucose-6-phosphate-dehydrogenase, and 6-phosphogluconate-dehydrogenase by insulin, but not by T3

DEFF Research Database (Denmark)

Matzen, L E; Kristensen, S R; Kvetny, J

1991-01-01

The specific nuclear binding of triiodothyronine (T3) (NBT3) and the activity of malic enzyme (ME), glucose-6-phosphate-dehydrogenase (G6PD), and 6-phosphogluconate-dehydrogenase (6PGD) were studied in the human fibroblast cell (MRC-5). The overall apparent binding affinity (Ka) was 2.7 x 10(9) L.......mol-1 estimated from kinetic studies of nuclear T3 binding, and 2.5 x 10(9) L.mol-1 estimated from equilibrium studies. The scatchard plots were curvilinear and composed of a high-affinity binding site with Ka1 3.4 +/- 0.7 x 10(9) L.mol-1 and maximal binding capacity (MBC) MBC1 57.0 +/- 11.9 fmol/mg DNA...... and a low-affinity binding site with Ka2 2.9 +/- 1.1 x 10(8) L.mol-1 and MBC2 124.7 +/- 22.1 fmol/mg DNA (n = 6). Incubation of cells with 6 nmol/L T3 for 20 hours reduced NBT3 to 62.2% +/- 15.7% (P less than .01, n = 11). The Ka estimated from kinetic studies was reduced to 6.7 x 10(7) L.mol-1...

Band structure of hydrogenated Si nanosheets and nanotubes

International Nuclear Information System (INIS)

Guzman-Verri, G G; Lew Yan Voon, L C

2011-01-01

The band structures of fully hydrogenated Si nanosheets and nanotubes are elucidated by the use of an empirical tight-binding model. The hydrogenated Si sheet is a semiconductor with an indirect band gap of about 2.2 eV. The symmetries of the wavefunctions allow us to explain the origin of the gap. We predict that, for certain chiralities, hydrogenated Si nanotubes represent a new type of semiconductor, one with coexisting direct and indirect gaps of exactly the same magnitude. This behavior is different from that governed by the Hamada rule established for non-hydrogenated carbon and silicon nanotubes. A comparison to the results of an ab initio calculation is made.

Perturbation method for calculating impurity binding energy in an ...

Indian Academy of Sciences (India)

Nilanjan Sil

2017-12-18

Dec 18, 2017 ... Abstract. In the present paper, we have studied the binding energy of the shallow donor hydrogenic impurity, which is confined in an inhomogeneous cylindrical quantum dot (CQD) of GaAs-AlxGa1−xAs. Perturbation method is used to calculate the binding energy within the framework of effective mass ...

Electric field improved hydrogen storage of Ca-decorated monolayer MoS{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Song, Nahong [College of Computer and Information Engineering, Henan University of Economics and Law, Zhengzhou 450002 (China); International Joint Research Laboratory for Quantum Functional Materials of Henan, and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Wang, Yusheng [College of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou 450011 (China); International Joint Research Laboratory for Quantum Functional Materials of Henan, and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Gao, Haiyan; Jiang, Weifen; Zhang, Jing; Xu, Bin [College of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou 450011 (China); Sun, Qiang [International Joint Research Laboratory for Quantum Functional Materials of Henan, and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Jia, Yu, E-mail: jiayu@zzu.edu.cn [International Joint Research Laboratory for Quantum Functional Materials of Henan, and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China)

2015-04-17

Hydrogen storage property of Ca-decorated MoS{sub 2} is carried out using first-principles calculations. Our calculations demonstrate that the preferential binding of Ca atoms on MoS{sub 2} effectively prevent the Ca clustering. Six H{sub 2} molecules per Ca atom can be adsorbed with a desirable adsorption energy of 0.14 eV/H{sub 2}. Both hybridization of the Ca-3d and S-2s with the H-1s orbital and the polarization of the H{sub 2} molecules contribute to the hydrogen adsorption. Our results show that the external electric field can effectively tune the hydrogen adsorption energy, therefore making hydrogen storage and release reversible. - Highlights: • Ca binds with MoS{sub 2} stalely without clustering. • It can operate under ambient thermodynamic conditions. • External electric field can effectively tune the hydrogen adsorption energy.

Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage

Energy Technology Data Exchange (ETDEWEB)

Pfeifer, Peter [Univ. of Missouri, Columbia, MO (United States). Dept. of Physics; Gillespie, Andrew [Univ. of Missouri, Columbia, MO (United States). Dept. of Physics; Stalla, David [Univ. of Missouri, Columbia, MO (United States). Dept. of Physics; Dohnke, Elmar [Univ. of Missouri, Columbia, MO (United States). Dept. of Physics

2017-02-20

The purpose of the project “Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage” is the development of materials that store hydrogen (H₂) by adsorption in quantities and at conditions that outperform current compressed-gas H₂ storage systems for electric power generation from hydrogen fuel cells (HFCs). Prominent areas of interest for HFCs are light-duty vehicles (“hydrogen cars”) and replacement of batteries with HFC systems in a wide spectrum of applications, ranging from forklifts to unmanned areal vehicles to portable power sources. State-of-the-art compressed H₂ tanks operate at pressures between 350 and 700 bar at ambient temperature and store 3-4 percent of H₂ by weight (wt%) and less than 25 grams of H₂ per liter (g/L) of tank volume. Thus, the purpose of the project is to engineer adsorbents that achieve storage capacities better than compressed H₂ at pressures less than 350 bar. Adsorption holds H₂ molecules as a high-density film on the surface of a solid at low pressure, by virtue of attractive surface-gas interactions. At a given pressure, the density of the adsorbed film is the higher the stronger the binding of the molecules to the surface is (high binding energies). Thus, critical for high storage capacities are high surface areas, high binding energies, and low void fractions (high void fractions, such as in interstitial space between adsorbent particles, “waste” storage volume by holding hydrogen as non-adsorbed gas). Coexistence of high surface area and low void fraction makes the ideal adsorbent a nanoporous monolith, with pores wide enough to hold high-density hydrogen films, narrow enough to minimize storage as non-adsorbed gas, and thin walls between pores to minimize the volume occupied by solid instead of hydrogen. A monolith can be machined to fit into a rectangular tank (low pressure, conformable tank), cylindrical tank

Theoretical examination of the trapping of ion-implanted hydrogen in metals

International Nuclear Information System (INIS)

Myers, S.M.; Nordlander, P.; Besenbacher, F.; Norskov, J.K.

1986-01-01

Theoretical analysis of the defect trapping of ion-implanted hydrogen in metals has been extended in two respects. A new transport formalism has been developed which takes account not only of the diffusion, trapping, and surface release of the hydrogen, which were included in earlier treatments, but also the diffusion, recombination, agglomeration, and surface annihilation of the vacancy and interstitial traps. In addition, effective-medium theory has been used to examine multiple hydrogen occupancy of the vacancy, and, for the fcc structure, appreciable binding enthalpies relative to the solution site have been found for occupancies of up to six. These extensions have been employed to model the depth distribution of ion-implanted hydrogen in Ni and Al during linear ramping of temperature, and the results have been used to interpret previously published data from these metals. The agreement between theory and experiment is good for both systems. In the case of Ni, the two experimentally observed hydrogen-release stages are both accounted for in terms of trapping at vacancies with a binding enthalpy that depends upon occupancy in accord with effective-medium theory

The Production and Utilization of GDP-glucose in the Biosynthesis of Trehalose 6-Phosphate by Streptomyces venezuelae.

Science.gov (United States)

Asención Diez, Matías D; Miah, Farzana; Stevenson, Clare E M; Lawson, David M; Iglesias, Alberto A; Bornemann, Stephen

2017-01-20

Trehalose-6-phosphate synthase OtsA from streptomycetes is unusual in that it uses GDP-glucose as the donor substrate rather than the more commonly used UDP-glucose. We now confirm that OtsA from Streptomyces venezuelae has such a preference for GDP-glucose and can utilize ADP-glucose to some extent too. A crystal structure of the enzyme shows that it shares twin Rossmann-like domains with the UDP-glucose-specific OtsA from Escherichia coli However, it is structurally more similar to Streptomyces hygroscopicus VldE, a GDP-valienol-dependent pseudoglycosyltransferase enzyme. Comparison of the donor binding sites reveals that the amino acids associated with the binding of diphosphoribose are almost all identical in these three enzymes. By contrast, the amino acids associated with binding guanine in VldE (Asn, Thr, and Val) are similar in S. venezuelae OtsA (Asp, Ser, and Phe, respectively) but not conserved in E. coli OtsA (His, Leu, and Asp, respectively), providing a rationale for the purine base specificity of S. venezuelae OtsA. To establish which donor is used in vivo, we generated an otsA null mutant in S. venezuelae The mutant had a cell density-dependent growth phenotype and accumulated galactose 1-phosphate, glucose 1-phosphate, and GDP-glucose when grown on galactose. To determine how the GDP-glucose is generated, we characterized three candidate GDP-glucose pyrophosphorylases. SVEN_3027 is a UDP-glucose pyrophosphorylase, SVEN_3972 is an unusual ITP-mannose pyrophosphorylase, and SVEN_2781 is a pyrophosphorylase that is capable of generating GDP-glucose as well as GDP-mannose. We have therefore established how S. venezuelae can make and utilize GDP-glucose in the biosynthesis of trehalose 6-phosphate. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

The Production and Utilization of GDP-glucose in the Biosynthesis of Trehalose 6-Phosphate by Streptomyces venezuelae*

Science.gov (United States)

Asención Diez, Matías D.; Miah, Farzana; Stevenson, Clare E. M.; Lawson, David M.; Iglesias, Alberto A.; Bornemann, Stephen

2017-01-01

Trehalose-6-phosphate synthase OtsA from streptomycetes is unusual in that it uses GDP-glucose as the donor substrate rather than the more commonly used UDP-glucose. We now confirm that OtsA from Streptomyces venezuelae has such a preference for GDP-glucose and can utilize ADP-glucose to some extent too. A crystal structure of the enzyme shows that it shares twin Rossmann-like domains with the UDP-glucose-specific OtsA from Escherichia coli. However, it is structurally more similar to Streptomyces hygroscopicus VldE, a GDP-valienol-dependent pseudoglycosyltransferase enzyme. Comparison of the donor binding sites reveals that the amino acids associated with the binding of diphosphoribose are almost all identical in these three enzymes. By contrast, the amino acids associated with binding guanine in VldE (Asn, Thr, and Val) are similar in S. venezuelae OtsA (Asp, Ser, and Phe, respectively) but not conserved in E. coli OtsA (His, Leu, and Asp, respectively), providing a rationale for the purine base specificity of S. venezuelae OtsA. To establish which donor is used in vivo, we generated an otsA null mutant in S. venezuelae. The mutant had a cell density-dependent growth phenotype and accumulated galactose 1-phosphate, glucose 1-phosphate, and GDP-glucose when grown on galactose. To determine how the GDP-glucose is generated, we characterized three candidate GDP-glucose pyrophosphorylases. SVEN_3027 is a UDP-glucose pyrophosphorylase, SVEN_3972 is an unusual ITP-mannose pyrophosphorylase, and SVEN_2781 is a pyrophosphorylase that is capable of generating GDP-glucose as well as GDP-mannose. We have therefore established how S. venezuelae can make and utilize GDP-glucose in the biosynthesis of trehalose 6-phosphate. PMID:27903647

Positively-charged semi-tunnel is a structural and surface characteristic of polyphosphate-binding proteins: an in-silico study.

Directory of Open Access Journals (Sweden)

Zheng Zachory Wei

Full Text Available Phosphate is essential for all major life processes, especially energy metabolism and signal transduction. A linear phosphate polymer, polyphosphate (polyP, linked by high-energy phosphoanhydride bonds, can interact with various proteins, playing important roles as an energy source and regulatory factor. However, polyP-binding structures are largely unknown. Here we proposed a putative polyP binding site, a positively-charged semi-tunnel (PCST, identified by surface electrostatics analyses in polyP kinases (PPKs and many other polyP-related proteins. We found that the PCSTs in varied proteins were folded in different secondary structure compositions. Molecular docking calculations revealed a significant value for binding affinity to polyP in PCST-containing proteins. Utilizing the PCST identified in the β subunit of PPK3, we predicted the potential polyP-binding domain of PPK3. The discovery of this feature facilitates future searches for polyP-binding proteins and discovery of the mechanisms for polyP-binding activities. This should greatly enhance the understanding of the many physiological functions of protein-bound polyP and the involvement of polyP and polyP-binding proteins in various human diseases.

Titanium-decorated graphene for high-capacity hydrogen storage studied by density functional simulations

International Nuclear Information System (INIS)

Liu Yali; Ren Ling; He Yao; Cheng Haiping

2010-01-01

We present results of density functional theory (DFT) calculations of the adsorption of hydrogen molecules on Ti-decorated graphene. Our results indicate that the binding energies of molecular hydrogen on Ti-decorated graphene can be dramatically enhanced to 0.23-0.60 eV. The hybridization of the Ti 3d orbitals with the H 2 σ and σ* orbitals plays a central role in the enhanced binding. There is also a contribution from the attractive interaction between the surface dipole and the dipole of polarized H 2 . It can be expected that Ti-decorated graphene could be considered as a potential high-capacity hydrogen storage medium.

Inhibitory heterotrimeric GTP-binding proteins inhibit hydrogen peroxide-induced apoptosis by up-regulation of Bcl-2 via NF-κB in H1299 human lung cancer cells

International Nuclear Information System (INIS)

Seo, Mi Ran; Nam, Hyo-Jung; Kim, So-Young; Juhnn, Yong-Sung

2009-01-01

Inhibitory heterotrimeric GTP-binding proteins (Gi proteins) mediate a variety of signaling pathways by coupling receptors and effectors to regulate cellular proliferation, differentiation, and apoptosis. However, the role of Gi proteins in the modulation of hydrogen peroxide-induced apoptosis is not clearly understood. Thus, we investigated the effect of Gi proteins on hydrogen peroxide-induced apoptosis and the underlying mechanisms in H1299 human lung cancer cells. The stable expression of constitutively active alpha subunits of Gi1 (Gαi1QL), Gi2, or Gi3 inhibited hydrogen peroxide-induced apoptosis. The expression of Gαi1QL up-regulated Bcl-2 expression, and the knockdown of Bcl-2 with siRNA abolished the anti-apoptotic effect of Gαi1QL. Gαi1 induced the transcription of Bcl-2 by activation of NF-κB, which resulted from an increase in NF-κB p50 protein. We conclude that Gαi1 inhibits hydrogen peroxide-induced apoptosis of H1299 lung cancer cells by up-regulating the transcription of Bcl-2 through a p50-mediated NF-κB activation.

Amide linkages mimic phosphates in RNA interactions with proteins and are well tolerated in the guide strand of short interfering RNAs.

Science.gov (United States)

Mutisya, Daniel; Hardcastle, Travis; Cheruiyot, Samwel K; Pallan, Pradeep S; Kennedy, Scott D; Egli, Martin; Kelley, Melissa L; Smith, Anja van Brabant; Rozners, Eriks

2017-08-21

While the use of RNA interference (RNAi) in molecular biology and functional genomics is a well-established technology, in vivo applications of synthetic short interfering RNAs (siRNAs) require chemical modifications. We recently found that amides as non-ionic replacements for phosphodiesters may be useful modifications for optimization of siRNAs. Herein, we report a comprehensive study of systematic replacement of a single phosphate with an amide linkage throughout the guide strand of siRNAs. The results show that amides are surprisingly well tolerated in the seed and central regions of the guide strand and increase the silencing activity when placed between nucleosides 10 and 12, at the catalytic site of Argonaute. A potential explanation is provided by the first crystal structure of an amide-modified RNA-DNA with Bacillus halodurans RNase H1. The structure reveals how small changes in both RNA and protein conformation allow the amide to establish hydrogen bonding interactions with the protein. Molecular dynamics simulations suggest that these alternative binding modes may compensate for interactions lost due to the absence of a phosphodiester moiety. Our results suggest that an amide can mimic important hydrogen bonding interactions with proteins required for RNAi activity and may be a promising modification for optimization of biological properties of siRNAs. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

A phosphate starvation-driven bidirectional promoter as a potential tool for crop improvement and in vitro plant biotechnology.

Science.gov (United States)

Araceli, Oropeza-Aburto; Alfredo, Cruz-Ramírez; Javier, Mora-Macías; Luis, Herrera-Estrella

2017-05-01

Phosphate (Pi)-deficient soils are a major limitant factor for crop production in many regions of the world. Despite that plants have innovated several developmental and biochemical strategies to deal with this stress, there are still massive extensions of land which combine several abiotic stresses, including phosphate starvation, that limit their use for plant growth and food production. In several plant species, a genetic programme underlies the biochemical and developmental responses of the organism to cope with low phosphate (Pi) availability. Both protein- and miRNA-coding genes involved in the adaptative response are transcriptionally activated upon Pi starvation. Several of the responsive genes have been identified as transcriptional targets of PHR1, a transcription factor that binds a conserved cis-element called PHR1-binding site (P1BS). Our group has previously described and characterized a minimal genetic arrangement that includes two P1BS elements, as a phosphate-responsive enhancer (EZ2). Here, we report the engineering and successful use of a phosphate-dependent bidirectional promoter, which has been designed and constructed based on the palindromic sequences of the two P1BS elements present in EZ2. This bidirectional promoter has a potential use in both plant in vitro approaches and in the generation of improved crops adapted to Pi starvation and other abiotic stresses. © 2016 The Authors. Plant Biotechnology Journal published by Society for Experimental Biology and The Association of Applied Biologists and John Wiley & Sons Ltd.

Adsorption and diffusion characteristics of lithium on hydrogenated α- and β-silicene

Directory of Open Access Journals (Sweden)

Fadil Iyikanat

2017-08-01

Full Text Available Using first-principles density functional theory calculations, we investigate adsorption properties and the diffusion mechanism of a Li atom on hydrogenated single-layer α- and β-silicene on a Ag(111 surface. It is found that a Li atom binds strongly on the surfaces of both α- and β-silicene, and it forms an ionic bond through the transfer of charge from the adsorbed atom to the surface. The binding energies of a Li atom on these surfaces are very similar. However, the diffusion barrier of a Li atom on H-α-Si is much higher than that on H-β-Si. The energy surface calculations show that a Li atom does not prefer to bind in the vicinity of the hydrogenated upper-Si atoms. Strong interaction between Li atoms and hydrogenated silicene phases and low diffusion barriers show that α- and β-silicene are promising platforms for Li-storage applications.

Oxygen binding properties of hemoglobin from the white rhinoceros (beta 2-GLU) and the tapir.

Science.gov (United States)

Baumann, R; Mazur, G; Braunitzer, G

1984-04-01

The beta-chain of rhinoceros hemoglobin contains glutamic acid at position beta 2, and important site for the binding of organic phosphates. We have investigated the oxygen binding properties of this hemoglobin and its interaction with ATP, 2,3-diphosphoglycerate, CO2 and chloride. The results show that the presence of GLU at position beta 2 nearly abolishes the effect of organic phosphates and CO2, whereas the oxygen-linked binding of chloride is not affected. Thus rhinoceros hemoglobin has only protons and chloride anions as major allosteric effectors for the control of its oxygen affinity. From the results obtained with hemoglobin solutions it can be calculated that the blood oxygen affinity of the rhinoceros must be rather high with a P50 of about 20 torr at pH 7.4 and 37 degrees C, which conforms with observations obtained for other large mammals.

Molecular recognition of nucleotides in micelles and the development and expansion of a chemistry outreach program

Science.gov (United States)

Schechinger, Linda Sue

I. To investigate the delivery of nucleotide-based drugs, we are studying molecular recognition of nucleotide derivatives in environments that are similar to cell membranes. The Nowick group previously discovered that membrane-like surfactant micelles tetradecyltrimethylammonium bromide (TTAB) micelle facilitate molecular of adenosine monophosphate (AMP) recognition. The micelles bind nucleotides by means of electrostatic interactions and hydrogen bonding. We observed binding by following 1H NMR chemical shift changes of unique hexylthymine protons upon addition of AMP. Cationic micelles are required for binding. In surfactant-free or sodium dodecylsulfate solutions, no hydrogen bonding is observed. These observations suggest that the cationic surfactant headgroups bind the nucleotide phosphate group, while the intramicellar base binds the nucleotide base. The micellar system was optimized to enhance binding and selectivity for adenosine nucleotides. The selectivity for adenosine and the number of phosphate groups attached to the adenosine were both investigated. Addition of cytidine, guanidine, or uridine monophosphates, results in no significant downfield shifting of the NH resonance. Selectivity for the phosphate is limited, since adenosine mono-, di-, and triphosphates all have similar binding constants. We successfully achieved molecular recognition of adenosine nucleotides in micellar environments. There is significant difference in the binding interactions between the adenosine nucleotides and three other natural nucleotides. II. The UCI Chemistry Outreach Program (UCICOP) addresses the declining interest of the nations youth for science. UCICOP brings fun and exciting chemistry experiments to local high schools, to remind students that science is fun and has many practical uses. Volunteer students and alumni of UCI perform the demonstrations using scripts and material provided by UCICOP. The preparation of scripts and materials is done by two coordinators

Structural and electronic properties of free standing one-sided and two-sided hydrogenated silicene: A first principle study

International Nuclear Information System (INIS)

Mohan, Brij; Kumar, Ashok; Ahluwalia, P. K.

2014-01-01

We performed first-principle study of the structural and electronic properties of two-dimensional hydrogenated silicene for two configurations; one is hydrogenation along one side of silicene sheet and second is hydrogenation in both sides of silicene sheet. The one-side hydrogenated silicene is found stable at planar geometry while increased buckling of 0.725 Å is found for both-side hydrogenated silicene. The result shows that the hydrogenation occupy the extended π-bonding network of silicene, and thus it exhibits semi-conducting behaviour with a band gap of 1.77 eV and 2.19 eV for one-side hydrogenated silicene and both-side hydrogenated silicene respectively. However, both-side hydrogenated silicene of binding energy 4.56 eV is more stable than one-side hydrogenated silicene of binding energy 4.30 eV, but experimentally silicene is synthesized on substrates which interacts one side of silicene layer and only other side is available for H-atoms. Therefore, practically one-side hydrogenation is also important

Thermodynamic study of dihydrogen phosphate dimerisation and complexation with novel urea- and thiourea-based receptors.

Science.gov (United States)

Bregović, Nikola; Cindro, Nikola; Frkanec, Leo; Užarević, Krunoslav; Tomišić, Vladislav

2014-11-24

Complexation of dihydrogen phosphate by novel thiourea and urea receptors in acetonitrile and dimethyl sulfoxide was studied in detail by an integrated approach by using several methods (isothermal titration calorimetry, ESI-MS, and (1)H NMR and UV spectroscopy). Thermodynamic investigations into H2PO4(-) dimerisation, which is a process that has been frequently recognised, but rarely quantitatively described, were carried out as well. The corresponding equilibrium was taken into account in the anion-binding studies, which enabled reliable determination of the complexation thermodynamic quantities. In both solvents the thiourea derivatives exhibited considerably higher binding affinities with respect to those containing the urea moiety. In acetonitrile, 1:1 and 2:1 (anion/receptor) complexes formed, whereas in dimethyl sulfoxide only the significantly less stable complexes of 1:1 stoichiometry were detected. The solvent effects on the thermodynamic parameters of dihydrogen phosphate dimerisation and complexation reactions are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Indirect coupling of phosphate release to de novo tension generation during muscle contraction.

Science.gov (United States)

Davis, J S; Rodgers, M E

1995-01-01

A key question in muscle contraction is how tension generation is coupled to the chemistry of the actomyosin ATPase. Biochemical and mechanochemical experiments link tension generation to a change in structure associated with phosphate release. Length-jump and temperature-jump experiments, on the other hand, implicate phase 2slow, a significantly faster, markedly strain-sensitive kinetic process in tension generation. We use a laser temperature jump to probe the kinetics and mechanism of tension generation in skinned rabbit psoas fibers--an appropriate method since both phosphate release and phase 2slow are readily perturbed by temperature. Kinetics characteristic of the structural change associated with phosphate release are observed only when phosphate is added to fibers. When present, it causes a reduction in fiber tension; otherwise, no force is generated when it is perturbed. We therefore exclude this step from tension generation. The kinetics of de novo tension generation by the temperature-jump equivalent of phase 2slow appear unaffected by phosphate binding. We therefore propose that phosphate release is indirectly coupled to de novo tension generation via a steady-state flux through an irreversible step. We conclude that tension generation occurs in the absence of chemical change as the result of an entropy-driven transition between strongly bound crossbridges in the actomyosin-ADP state. The mechanism resembles the operation of a clock, with phosphate release providing the energy to tension the spring, and the irreversible step functions as the escapement mechanism, which is followed in turn by tension generation as the movement of the hands. Images Fig. 6 PMID:7479824

Exposure to tri-o-cresyl phosphate detected in jet airplane passengers

International Nuclear Information System (INIS)

Liyasova, Mariya; Li, Bin; Schopfer, Lawrence M.; Nachon, Florian; Masson, Patrick; Furlong, Clement E.; Lockridge, Oksana

2011-01-01

The aircraft cabin and flight deck ventilation are supplied from partially compressed unfiltered bleed air directly from the engine. Worn or defective engine seals can result in the release of engine oil into the cabin air supply. Aircrew and passengers have complained of illness following such “fume events”. Adverse health effects are hypothesized to result from exposure to tricresyl phosphate mixed esters, a chemical added to jet engine oil and hydraulic fluid for its anti-wear properties. Our goal was to develop a laboratory test for exposure to tricresyl phosphate. The assay was based on the fact that the active-site serine of butyrylcholinesterase reacts with the active metabolite of tri-o-cresyl phosphate, cresyl saligenin phosphate, to make a stable phosphorylated adduct with an added mass of 80 Da. No other organophosphorus agent makes this adduct in vivo on butyrylcholinesterase. Blood samples from jet airplane passengers were obtained 24–48 h after completing a flight. Butyrylcholinesterase was partially purified from 25 ml serum or plasma, digested with pepsin, enriched for phosphorylated peptides by binding to titanium oxide, and analyzed by mass spectrometry. Of 12 jet airplane passengers tested, 6 were positive for exposure to tri-o-cresyl phosphate that is, they had detectable amounts of the phosphorylated peptide FGEpSAGAAS. The level of exposure was very low. No more than 0.05 to 3% of plasma butyrylcholinesterase was modified. None of the subjects had toxic symptoms. Four of the positive subjects were retested 3 to 7 months following their last airplane trip and were found to be negative for phosphorylated butyrylcholinesterase. In conclusion, this is the first report of an assay that detects exposure to tri-o-cresyl phosphate in jet airplane travelers. -- Highlights: ► Travel on jet airplanes is associated with an illness, aerotoxic syndrome. ► A possible cause is exposure to tricresyl phosphate in engine lubricating oil. ► A blood

Exposure to tri-o-cresyl phosphate detected in jet airplane passengers

Energy Technology Data Exchange (ETDEWEB)

Liyasova, Mariya, E-mail: mliyasov@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Department of Environmental, Agricultural, and Occupational Health, University of Nebraska Medical Center, Omaha, NE (United States); Li, Bin, E-mail: binli@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Schopfer, Lawrence M., E-mail: lmschopf@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Nachon, Florian, E-mail: fnachon@nachon.net [Departement de Toxicologie, Institut de Recherche Biomedicale des Armees, 24 avenue des Marquis du Gresivaudan, 38702 La Tronche (France); Masson, Patrick, E-mail: pmasson@unmc.edu [Departement de Toxicologie, Institut de Recherche Biomedicale des Armees, 24 avenue des Marquis du Gresivaudan, 38702 La Tronche (France); Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Furlong, Clement E., E-mail: clem@uw.edu [Department of Medicine (Div. Medical Genetics) and Genome Sciences, University of Washington, Seattle, WA 98195 (United States); Lockridge, Oksana, E-mail: olockrid@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Department of Environmental, Agricultural, and Occupational Health, University of Nebraska Medical Center, Omaha, NE (United States)

2011-11-15

The aircraft cabin and flight deck ventilation are supplied from partially compressed unfiltered bleed air directly from the engine. Worn or defective engine seals can result in the release of engine oil into the cabin air supply. Aircrew and passengers have complained of illness following such 'fume events'. Adverse health effects are hypothesized to result from exposure to tricresyl phosphate mixed esters, a chemical added to jet engine oil and hydraulic fluid for its anti-wear properties. Our goal was to develop a laboratory test for exposure to tricresyl phosphate. The assay was based on the fact that the active-site serine of butyrylcholinesterase reacts with the active metabolite of tri-o-cresyl phosphate, cresyl saligenin phosphate, to make a stable phosphorylated adduct with an added mass of 80 Da. No other organophosphorus agent makes this adduct in vivo on butyrylcholinesterase. Blood samples from jet airplane passengers were obtained 24-48 h after completing a flight. Butyrylcholinesterase was partially purified from 25 ml serum or plasma, digested with pepsin, enriched for phosphorylated peptides by binding to titanium oxide, and analyzed by mass spectrometry. Of 12 jet airplane passengers tested, 6 were positive for exposure to tri-o-cresyl phosphate that is, they had detectable amounts of the phosphorylated peptide FGEpSAGAAS. The level of exposure was very low. No more than 0.05 to 3% of plasma butyrylcholinesterase was modified. None of the subjects had toxic symptoms. Four of the positive subjects were retested 3 to 7 months following their last airplane trip and were found to be negative for phosphorylated butyrylcholinesterase. In conclusion, this is the first report of an assay that detects exposure to tri-o-cresyl phosphate in jet airplane travelers. -- Highlights: Black-Right-Pointing-Pointer Travel on jet airplanes is associated with an illness, aerotoxic syndrome. Black-Right-Pointing-Pointer A possible cause is exposure to

Alpha 1A and alpha 1B-adrenoceptors enhance inositol phosphate generation in rat renal cortex

NARCIS (Netherlands)

Michel, M. C.; Büscher, R.; Philipp, T.; Brodde, O. E.

1993-01-01

We have studied the role of alpha 1A- and alpha 1B-adrenoceptors in noradrenaline- and methoxamine-stimulated inositol phosphate accumulation in rat renal cortical slices. [3H]Prazosin binding studies with and without inactivation of alpha 1B-adrenoceptors by chloroethylclonidine treatment suggested

Turn-on fluorescent sensor for Zinc and Cadmium ions based on quinolone and its sequential response to phosphate

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiaoyan; Wang, Peng; Fu, Jiaxin; Yao, Kun; Xue, Kun [Engineering Laboratory for Flame Retardant and Functional Materials of Hennan Province, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Xu, Kuoxi, E-mail: xukx@henu.edu.cn [Engineering Laboratory for Flame Retardant and Functional Materials of Hennan Province, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China)

2017-06-15

Sequential fluorescence sensing of Zn{sup 2+}/Cd{sup 2+} ions and phosphate anion by new quinoline based sensors(L1 and L2) have been presented. Sensors exhibit highly selective fluorescence “turn-on” sensing properties to Zn{sup 2+}/Cd{sup 2+} ions in CH{sub 3}OH/H{sub 2}O(1/1, v/v, Tris, 10 mol·L{sup −1}, pH 7.4) solution with a 1:1 binding stoichiometry. The complexes display high selectivity to H{sub 2}PO{sub 4}{sup -} and HPO{sub 4}{sup 2-} anions through fluorescence “turn-off” respond. The results of Zn{sup 2+}/Cd{sup 2+} ions and phosphate anion sequential recognition via fluorescence changes make sensors L1 and L2 have potential utility for Zn{sup 2+}/ Cd{sup 2+} ions and phosphate anion detection in aqueous media. - Graphical abstract: Sequential fluorescence sensing of Zn{sup 2+}/Cd{sup 2+} ions and phosphate anion by new quinoline based sensors (L1 and L2) have been presented. Sensors exhibit highly selective and sensitive fluorescence “turn-on” sensing properties to Zn{sup 2+}/Cd{sup 2+} ions in CH{sub 3}OH/H{sub 2}O(1/1, v/v, Tris, 10 mM, pH 7.4) solution with a 1:1 binding stoichiometry. The complexes display high selectivity to H{sub 2}PO{sub 4}{sup -} and HPO{sub 4}{sup 2-} anions through fluorescence “turn-off” respond. Zn{sup 2+}/Cd{sup 2+} ions and phosphate anion sequential recognition via fluorescence changes make sensors L1 and L2 have potential utility for Zn{sup 2+}/ Cd{sup 2+} ions and phosphate anion detection in aqueous media.

Cleanup of 7.5% tributyl phosphate/n-paraffin solvent-extraction solvent

International Nuclear Information System (INIS)

Reif, D.J.

1987-02-01

The HM process at the Savannah River Plant uses 7.5% tributyl phosphate in n-paraffin as an extraction solvent. During use, the solvent is altered due to hydrolysis and radiolysis, forming materials which influence product losses, product decontamination, and separation efficiencies. Laboratory studies to improve online solvent cleaning have shown that carbonate washing, although removing residual solvent activity, does not remove binding ligands which hold fission products in the solvent. Treatment of solvent by an alumina adsorption process removes binding ligands and significantly improves recycle solvent performance. Both laboratory work defining a full-scale alumina adsorption process and the use of the process to clean HM process first cycle solvent is discussed

Analysis of phosphate esters in plant material. Extraction and purification.

Science.gov (United States)

Isherwood, F A; Barrett, F C

1967-09-01

1. A critical study was made of the quantitative extraction of nucleotide and sugar phosphates from plant tissue by either boiling aqueous ethanol or cold trichloroacetic acid. The effect of the extraction technique on the inactivation of the enzymes in the plant tissue and the possibility of adsorption of the phosphate esters on the cell wall were especially considered. 2. In the recommended method the plant tissue was frozen in liquid nitrogen, ground to a powder and then blended with cold aqueous trichloroacetic acid containing 8-hydroxyquinoline to prevent adsorption. 3. The extract contained large amounts of trichloroacetic acid, cations, chloride, sugars, amino acids, hydroxy organic acids, phytic acid, orthophosphoric acid and high-molecular-weight material including some phosphorus-containing compounds. All of these were removed as they were liable to interfere with the chromatographic or enzymic assay of the individual nucleotide or sugar phosphates. 4. The procedure was as follows: the last traces of trichloroacetic acid were extracted with ether after the solution had been passed through a column of Dowex AG 50 in the hydrogen form to remove all cations. High-molecular-weight compounds were removed by ultrafiltration and low-molecular-weight solutes by a two-stage chromatography on cellulose columns with organic solvents. In the first stage, sugars, amino acids, chloride and phytic acid were separated by using a basic solvent (propan-1-ol-water-aqueous ammonia) and, in the second stage, the organic acids and orthophosphoric acid were separated by using an acidic solvent (di-isopropyl ether-formic acid-2-methylpropan-2-ol-water). The final solution of nucleotide and sugar phosphates was substantially free from other solutes and was suitable for the detection of individual phosphate esters by either chromatography or enzymic assay. 5. The recovery of d-glucose 6-phosphate or adenosine 5'-triphosphate added to a trichloroacetic acid extract simulating that

Structural Analysis of Substrate, Reaction Intermediate, and Product Binding in Haemophilus influenzae Biotin Carboxylase

Science.gov (United States)

Broussard, Tyler C.; Pakhomova, Svetlana; Neau, David B.; Bonnot, Ross; Waldrop, Grover L.

2015-01-01

Acetyl-CoA carboxylase catalyzes the first and regulated step in fatty acid synthesis. In most Gram-negative and Gram-positive bacteria, the enzyme is composed of three proteins: biotin carboxylase, a biotin carboxyl carrier protein (BCCP), and carboxyltransferase. The reaction mechanism involves two half-reactions with biotin carboxylase catalyzing the ATP-dependent carboxylation of biotin-BCCP in the first reaction. In the second reaction, carboxyltransferase catalyzes the transfer of the carboxyl group from biotin-BCCP to acetyl-CoA to form malonyl-CoA. In this report, high-resolution crystal structures of biotin carboxylase from Haemophilus influenzae were determined with bicarbonate, the ATP analogue AMPPCP; the carboxyphosphate intermediate analogues, phosphonoacetamide and phosphonoformate; the products ADP and phosphate; and the carboxybiotin analogue N1′-methoxycarbonyl biotin methyl ester. The structures have a common theme in that bicarbonate, phosphate, and the methyl ester of the carboxyl group of N1′-methoxycarbonyl biotin methyl ester all bound in the same pocket in the active site of biotin carboxylase and as such utilize the same set of amino acids for binding. This finding suggests a catalytic mechanism for biotin carboxylase in which the binding pocket that binds tetrahedral phosphate also accommodates and stabilizes a tetrahedral dianionic transition state resulting from direct transfer of CO2 from the carboxyphosphate intermediate to biotin. PMID:26020841

Phosphorus release from phosphate rock and iron phosphate by low-molecular-weight organic acids.

Science.gov (United States)

Xu, Ren-kou; Zhu, Yong-guan; Chittleborough, David

2004-01-01

Low-molecular-weight(LMW) organic acids widely exist in soils, particularly in the rhizosphere. A series of batch experiments were carried out to investigate the phosphorus release from rock phosphate and iron phosphate by low-molecular-weight organic acids. Results showed that citric acid had the highest capacity to solubilize P from both rock and iron phosphate. P solubilization from rock phosphate and iron phosphate resulted in net proton consumption. P release from rock phosphate was positively correlated with the pKa values. P release from iron phosphate was positively correlated with Fe-organic acid stability constants except for aromatic acids, but was notcorrelated with pKa. Increase in the concentrations of organic acids enhanced P solubilization from both rock and iron phosphate almost linearly. Addition of phenolic compounds further increased the P release from iron phosphate. Initial solution pH had much more substantial effect on P release from rock phosphate than from iron phosphate.

Electrocatalytic hydrogen evolution under densely buffered neutral pH conditions

KAUST Repository

Shinagawa, Tatsuya

2015-08-18

Under buffered neutral pH conditions, solute concentrations drastically influence the hydrogen evolution reaction (HER). The iR-free HER performance as a function of solute concentration was found to exhibit a volcano-shaped trend in sodium phosphate solution at pH 5, with the maximum occurring at 2 M. A detailed microkinetic model that includes calculated activity coefficients, solution resistance, and mass-transport parameters accurately describes the measured values, clarifying that the overall HER performance is predominantly governed by mass-transport of slow phosphate ions (weak acid). In the HER at the optimum concentration of approximately 2 M sodium phosphate at pH 5, our theoretical model predicts that the concentration overpotential accounts for more than half of the required overpotential. The substantial concentration overpotential would originate from the electrolyte property, suggesting that the proper electrolyte engineering will result in an improved apparent HER performances. The significance of concentration overpotential shown in the study is critical in the advancement of electrocatalysis, biocatalysis, and photocatalysis.

Electrocatalytic hydrogen evolution under densely buffered neutral pH conditions

KAUST Repository

Shinagawa, Tatsuya; Takanabe, Kazuhiro

2015-01-01

Under buffered neutral pH conditions, solute concentrations drastically influence the hydrogen evolution reaction (HER). The iR-free HER performance as a function of solute concentration was found to exhibit a volcano-shaped trend in sodium phosphate solution at pH 5, with the maximum occurring at 2 M. A detailed microkinetic model that includes calculated activity coefficients, solution resistance, and mass-transport parameters accurately describes the measured values, clarifying that the overall HER performance is predominantly governed by mass-transport of slow phosphate ions (weak acid). In the HER at the optimum concentration of approximately 2 M sodium phosphate at pH 5, our theoretical model predicts that the concentration overpotential accounts for more than half of the required overpotential. The substantial concentration overpotential would originate from the electrolyte property, suggesting that the proper electrolyte engineering will result in an improved apparent HER performances. The significance of concentration overpotential shown in the study is critical in the advancement of electrocatalysis, biocatalysis, and photocatalysis.

Davisson-Germer Prize Talk: Hydrogen storage in nanoporous materials

Science.gov (United States)

Chabal, Yves

2009-03-01

To develop a hydrogen-based energy technology, several classes of materials are being considered to achieve the DOE targets for gravimetric and volumetric hydrogen densities for hydrogen storage, including liquids (e.g. ammonium borohydrides), clathrate structures, complex metal hydrides, nanostructured (e.g. carbon) an nanoporous materials. Fundamental studies are necessary to determine the ultimate hydrogen capacity of each system. Nanoporous Metal-organic Framework (MOF) materials are promising candidates for hydrogen storage because the chemical nature and size of their unit cell can be tailored to weakly attract and incorporate H2 molecules, with good volumetric and mass density. In this talk, we consider the structure M2(BDC)2(TED), where M is a metal atom (Zn, Ni, Cu), BDC is benzenedicarboxylate and TED triethylenediamine, to determine the location and interaction of H2 molecules within the MOF. These compounds are isostructural and crystallize in the tetragonal phase (space group P4/ncc), they construct 3D porous structures with relatively large pore size (˜7-8 A ), pore volume (˜0.63-0.84 cc/g) and BET surface area (˜1500-1900 m^2/g). At high pressures (300-800 psi), the perturbation of the H-H stretching mode can be measured with IR absorption spectroscopy, showing a 35 cm-1 redshift from the unperturbed ortho (4155 cm-1 ) and para (4161 cm-1 ) frequencies. Using a newly developed non empirical van der Waals DFT method vdW-DFT),ootnotetextJ.Y. Lee, D.H. Olson, L. Pan, T.J. Emge, J. Li, Adv. Func. Mater. 17, 1255 (2007) it can be shown that the locus of the deepest H2 binding positions lies within to types of narrow channels. The energies of the most stable binding sites, as well as the number of such binding sites, are consistent with the values obtained from experimental adsorption isotherms, and heat of adsorption) data.ootnotetextM. Dion, H. Ryberg, E. Schroder, D. C. Langreth, B.I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004). Importantly, the

Modelling phosphate adsorption to the soil: Application of the non-ideal competitive adsorption model

International Nuclear Information System (INIS)

Abou Nohra, Joumana S.; Madramootoo, Chandra A.; Hendershot, William H.

2007-01-01

Phosphorus (P) transport in subsurface runoff has increased despite the limited mobility of P in soils. This study investigated the ability of the non-ideal competitive adsorption (NICA) model to describe phosphate (PO 4 ) adsorption for soils in southern Quebec (Canada). We measured the surface charge and PO 4 adsorption capacity for 11 agricultural soils. Using the experimental data and a nonlinear fitting function, we derived the NICA model parameters. We found that the NICA model described accurately the surface charge of these soils with a mean R 2 > 0.99, and described the adsorption data with a mean R 2 = 0.96. We also found that the variable surface charge was distributed over the two binding sites with the low pH sites demonstrating a stronger binding energy for hydroxyl and PO 4 ions. We established that the NICA model is able to describe P adsorption for the soils considered in this study. - The NICA model accurately described the adsorption of phosphate to some southern Quebec soils

Ternary complex formation of lanthanides and radiolanthanides with phosphate and serum proteins

International Nuclear Information System (INIS)

Neumaier, B.; Roesch, F.

1999-01-01

Radioyttrium was recently reported to form ternary complexes with phosphate and serum proteins in blood. In the present work it was investigated whether the trivalent radiolanthanides react in a chemically similar way. In systematic binding studies using gel filtration a ternary complex formation between different lanthanides, phosphate and serum proteins could be identified. The tendency to build a ternary compound of the type Ln III - phosphate - serum protein, however, is dependent on the ionic radii of the lanthanides. Whereas the light and transition lanthanides have a strong inclination to build a ternary complex, this tendency is weaker for the heavier ones. Taking into account the high content of phosphate in human blood, the corresponding ternary complexes of radiolanthanides represent an important transport form of these elements in blood. This finding may contribute to an understanding of the nuclear medical observation on the biodistribution of radiolanthanides. The heavy radiolanthanides can be classified as bone seeking metals, whereas the light and transition lanthanide elements accumulate mainly in the liver and the spleen. For the lighter radiolanthanides the corresponding ternary complexes thus represent an important transport form in blood. This physicochemical form of lanthanides mainly results in reticulo endothelial accumulation; on the other hand, the lower tendency of heavier lanthanides leads to preferential skeletal deposition. (orig.)

Effects of phosphate addition on methane fermentation in the batch and upflow anaerobic sludge blanket (UASB) reactors.

Science.gov (United States)

Suzuki, Sho; Shintani, Masaki; Sanchez, Zoe Kuizon; Kimura, Kohei; Numata, Mitsuru; Yamazoe, Atsushi; Kimbara, Kazuhide

2015-12-01

Ammonia inhibition of methane fermentation is one of the leading causes of failure of anaerobic digestion reactors. In a batch anaerobic digestion reactor with 429 mM NH3-N/L of ammonia, the addition of 25 mM phosphate resulted in an increase in methane production rate. Similar results were obtained with the addition of disodium phosphate in continuous anaerobic digestion using an upflow anaerobic sludge blanket (UASB) reactor. While methane content and production rate decreased in the presence of more than 143 mM NH3-N/L of ammonium chloride in UASB, the addition of 5 mM disodium phosphate suppressed ammonia inhibition at 214 mM NH3-N/L of ammonium chloride. The addition prevented acetate/propionate accumulation, which might be one of the effects of the phosphate on the ammonia inhibition. The effects on the microbial community in the UASB reactor was also assessed, which was composed of Bacteria involved in hydrolysis, acidogenesis, acetogenesis, and dehydrogenation, as well as Archaea carrying out methanogenesis. The change in the microbial community was observed by ammonia inhibition and the addition of phosphate. The change indicates that the suppression of ammonia inhibition by disodium phosphate addition could stimulate the activity of methanogens, reduce shift in bacterial community, and enhance hydrogen-producing bacteria. The addition of phosphate will be an important treatment for future studies of methane fermentation.

Brittle and ductile adjustable cement derived from calcium phosphate cement/polyacrylic acid composites.

Science.gov (United States)

Chen, Wen-Cheng; Ju, Chien-Ping; Wang, Jen-Chyan; Hung, Chun-Cheng; Chern Lin, Jiin-Huey

2008-12-01

Bone filler has been used over the years in dental and biomedical applications. The present work is to characterize a non-dispersive, fast setting, modulus adjustable, high bioresorbable composite bone cement derived from calcium phosphate-based cement combined with polymer and binding agents. This cement, we hope, will not swell in simulated body fluid and keep the osteogenetic properties of the dry bone and avoid its disadvantages of being brittle. We developed a calcium phosphate cement (CPC) of tetracalcium phosphate/dicalcium phosphate anhydrous (TTCP/DCPA)-polyacrylic acid with tartaric acid, calcium fluoride additives and phosphate hardening solution. The results show that while composite, the hard-brittle properties of 25wt% polyacrylic acid are proportional to CPC and mixing with additives is the same as those of the CPC without polyacrylic acid added. With an increase of polyacrylic acid/CPC ratio, the 67wt% samples revealed ductile-tough properties and 100wt% samples kept ductile or elastic properties after 24h of immersion. The modulus range of this development was from 200 to 2600MPa after getting immersed in simulated body fluid for 24h. The TTCP/DCPA-polyacrylic acid based CPC demonstrates adjustable brittle/ductile strength during setting and after immersion, and the final reaction products consist of high bioresorbable monetite/brushite/calcium fluoride composite with polyacrylic acid.

Interaction of bovine gallbladder mucin and calcium-binding protein: effects on calcium phosphate precipitation

NARCIS (Netherlands)

Afdhal, N. H.; Ostrow, J. D.; Koehler, R.; Niu, N.; Groen, A. K.; Veis, A.; Nunes, D. P.; Offner, G. D.

1995-01-01

Gallstones consist of calcium salts and cholesterol crystals, arrayed on a matrix of gallbladder mucin (GBM), and regulatory proteins like calcium-binding protein (CBP). To determine if interactions between CBP and GBM follow a biomineralization scheme, their mutual binding and effects on CaHPO4

Lithium-Ion Mobility in Quaternary Boro-Germano-Phosphate Glasses.

Science.gov (United States)

Moguš-Milanković, Andrea; Sklepić, Kristina; Mošner, Petr; Koudelka, Ladislav; Kalenda, Petr

2016-04-28

Effect of the structural changes, electrical conductivity, and dielectric properties on the addition of a third glass-former, GeO2, to the borophosphate glasses, 40Li2O-10B2O3-(50 - x)P2O5-xGeO2, x = 0-25 mol %, has been studied. Introduction of GeO2 causes the structural modifications in the glass network, which results in a continuous increase in electrical conductivity. Glasses with low GeO2 content, up to 10 mol %, show a rapid increase in dc conductivity as a result of the interlinkage of slightly depolymerized phosphate chains and negatively charged [GeO4](-) units, which enhances the migration of Li(+) ions. The Li(+) ions compensate these delocalized charges connecting both phosphate and germanium units, which results in reduction of both bond effectiveness and binding energy of Li(+) ions and therefore enables their hop to the next charge-compensating site. For higher GeO2 content, the dc conductivity increases slightly, tending to approach a maximum in Li(+) ion mobility caused by the incorporation of GeO2 units into phosphate network combined with conversion of GeO4 to GeO6 units. The strong cross-linkage of germanium and phosphate units creates heteroatomic P-O-Ge bonds responsible for more effectively trapped Li(+) ions. A close correspondence between dielectric and conductivity parameters at high frequencies indicates that the increase in conductivity indeed is controlled by the modification of structure as a function of GeO2 addition.

Formation of vacancy clusters in tungsten crystals under hydrogen-rich condition

Energy Technology Data Exchange (ETDEWEB)

Kato, Daiji, E-mail: kato.daiji@nifs.ac.jp [National Institute for Fusion Science, 322-6 Oroshi-cho, Toki, Gifu 509-5292 (Japan); Iwakiri, Hirotomo, E-mail: iwakiri@edu.u-ryukyu.ac.jp [University of the Ryukyus, Okinawa 903-0213 (Japan); Morishita, Kazunori, E-mail: morishita@iae.kyoto-u.ac.jp [Institute of Advanced Energy, Kyoto University, Kyoto 611-0011 (Japan)

2011-10-01

Di-vacancy formation assisted by hydrogen trapping is studied in terms of nucleation free-energies evaluated with density functional theory. Calculations give binding energies for single hydrogen atom as first- and second-nearest-neighbor of di-vacancies of 1.80 and 2.15 eV, respectively, which are significantly larger than that for mono-vacancies. At elevated atomic concentrations of interstitial hydrogen atoms, evaluated nucleation free-energies indicate that the hydrogen assisted di-vacancy formation becomes more favorable. It is suggested that the formation would be preceded by VH cluster formation.

Formation of vacancy clusters in tungsten crystals under hydrogen-rich condition

International Nuclear Information System (INIS)

Kato, Daiji; Iwakiri, Hirotomo; Morishita, Kazunori

2011-01-01

Di-vacancy formation assisted by hydrogen trapping is studied in terms of nucleation free-energies evaluated with density functional theory. Calculations give binding energies for single hydrogen atom as first- and second-nearest-neighbor of di-vacancies of 1.80 and 2.15 eV, respectively, which are significantly larger than that for mono-vacancies. At elevated atomic concentrations of interstitial hydrogen atoms, evaluated nucleation free-energies indicate that the hydrogen assisted di-vacancy formation becomes more favorable. It is suggested that the formation would be preceded by VH cluster formation.

Accumulation of zirconium phosphate by a Serratia sp.: a benign system for the removal of radionuclides from aqueous flows.

Science.gov (United States)

Mennan, Claire; Paterson-Beedle, Marion; Macaskie, Lynne E

2010-10-01

Metal phosphate deposited enzymatically on Serratia sp. has been used successfully for the removal of radionuclides from aqueous flows. Previous studies using biogenic hydrogen uranyl phosphate (HUP) on Serratia sp. biofilm showed removal of 100% of (90)Sr, (137)Cs, and (60)Co via their intercalation into biogenic HUP crystals. Zirconium phosphates (ZrP) offer a potential non-toxic and non-radioactive alternative to HUP for water decontamination. A method was developed for biomanufacturing ZrP. Biogenic ZrP removed ca. 100% of Sr(2+) and Co(2+) (0.5 mM) from solutions to a molar ratio at saturation of ca. 1:0.6 for both Zr:Sr and Zr:Co. The potential for drinking water decontamination via bio-ZrP is discussed with respect to bio-HUP and also other commercially available materials.

Conformational flexibility of avidin: the influence of biotin binding

International Nuclear Information System (INIS)

Soledad Celej, M.; Montich, Guillermo G.; Fidelio, Gerardo D.

2004-01-01

Ligand binding to proteins is a key process in cell biochemistry. The interaction usually induces modifications in the unfolding thermodynamic parameters of the macromolecule due to the coupling of unfolding and binding equilibria. In addition, these modifications can be attended by changes in protein structure and/or conformational flexibility induced by ligand binding. In this work, we have explored the effect of biotin binding on conformation and dynamic properties of avidin by using infrared spectroscopy including kinetics of hydrogen/deuterium exchange. Our results, along with previously thermodynamic published data, indicate a clear correlation between thermostability and protein compactness. In addition, our results also help to interpret the thermodynamic binding parameters of the exceptionally stable biotin:AVD complex

Phosphorus Binding Sites in Proteins: Structural Preorganization and Coordination

DEFF Research Database (Denmark)

Gruber, Mathias Felix; Greisen, Per Junior; Junker, Märta Caroline

2014-01-01

to individual structures that bind to phosphate groups; here, we investigate a total of 8307 structures obtained from the RCSB Protein Data Bank (PDB). An analysis of the binding site amino acid propensities reveals very characteristic first shell residue distributions, which are found to be influenced...... by the characteristics of the phosphorus compound and by the presence of cobound cations. The second shell, which supports the coordinating residues in the first shell, is found to consist mainly of protein backbone groups. Our results show how the second shell residue distribution is dictated mainly by the first shell...

Electrochemical and spectroscopic in situ techniques for the investigation of the phosphating of zinc coated steel

International Nuclear Information System (INIS)

Tomandl, A.

2003-05-01

In this work spectroscopic and electrochemical techniques were developed for the investigation of surface treatments used in steel industry. ICP-atomic emission spectroscopy (ICP-AES), Raman spectroscopy and the Quartz crystal microbalance (QCM) were applied to the investigation of the kinetics of phosphating as well as the properties of phosphate layers. Phosphating of zinc coated steel leads to the formation of a crystalline layer consisting of zinc phosphate and is employed to enhance paint adhesion and corrosion protection. For the high reaction rates necessary in industrial production lines, oxidation agents are added to the phosphating bathes to accelerate the reaction. The oxidation agents provide an additional reduction reaction beside the hydrogen formation and therefore decrease the number of gas bubbles, which would block the zinc surface and reduce the rate of phosphating. With addition of H2O2 or nitrates the rate of layer formation is distinctly increased. In a combined experiment of ICP-AES with QCM and potential transients, it was shown that the presence of these accelerators in the phosphating bath increases the rate of zinc dissolution and hence leads to a faster formation of the phosphate layer. In under paint corrosion of painted, zinc coated steel phosphate layers are exposed to a highly alkaline environment. The stability of a phosphate layer against alkaline attack is therefore essential for its performance in corrosion protection. To enhance the alkaline stability Mn and Ni are added to modern phosphating bathes. The incorporation of these elements reduces the dissolution rate in 0.1 M NaOH proportional to their concentration in the phosphate layer. The dissolution of Zn, P, Mn and Ni was determined quantitatively with ICP-AES. Raman spectroscopy showed the formation of a Mn-hydroxide layer during alkaline attack, which protects the phosphate layer and reduces further dissolution. On basis of these results the reaction of phosphate layers

Hydrogen atom addition to the surface of graphene nanoflakes: A density functional theory study

Science.gov (United States)

Tachikawa, Hiroto

2017-02-01

Polycyclic aromatic hydrocarbons (PAHs) provide a 2-dimensional (2D) reaction surface in 3-dimensional (3D) interstellar space and have been utilized as a model of graphene surfaces. In the present study, the reaction of PAHs with atomic hydrogen was investigated by means of density functional theory (DFT) to systematically elucidate the binding nature of atomic hydrogen to graphene nanoflakes. PAHs with n = 4-37 were chosen, where n indicates the number of benzene rings. Activation energies of hydrogen addition to the graphene surface were calculated to be 5.2-7.0 kcal/mol at the CAM-B3LYP/6-311G(d,p) level, which is almost constant for all PAHs. The binding energies of hydrogen atom were slightly dependent on the size (n): 14.8-28.5 kcal/mol. The absorption spectra showed that a long tail is generated at the low-energy region after hydrogen addition to the graphene surface. The electronic states of hydrogenated graphenes were discussed on the basis of theoretical results.

On the nature of hydrogen bonding between the phosphatidylcholine head group and water and dimethylsulfoxide

Science.gov (United States)

Dabkowska, Aleksandra P.; Lawrence, M. Jayne; McLain, Sylvia E.; Lorenz, Christian D.

2013-01-01

Molecular dynamics simulations are used to provide a detailed investigation of the hydrogen bond networks around the phosphatidylcholine (PC) head group in 1,2-dipropionyl-sn-glycero-3-phosphocholine in pure water, 10 mol.% and 30 mol.% dimethylsulfoxide (DMSO)-water solutions. Specifically, it is observed that DMSO replaces those water molecules that are within the first solvation shell of the choline, phosphate and ester groups of the PC head group, but are not hydrogen-bonded to the group. The effect of the presence of DMSO on the hydrogen bond network around the PC head groups of the lipid changes with the concentration of DMSO. In comparison to the hydrogen bond network observed in the pure water system, the number of hydrogen-bonded chains of solvent molecules increases slightly for the 10 mol.% DMSO system, while, in the 30 mol.% DMSO system, the number of hydrogen-bonded chains of solvent molecules decreases.

Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

International Nuclear Information System (INIS)

Brown, Craig M; Liu Yun; Yildirim, Taner; Peterson, Vanessa K; Kepert, Cameron J

2009-01-01

Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu 3 (1,3,5-benzenetricarboxylate) 2 ), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H 2 -metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H 2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H 2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

Energy Technology Data Exchange (ETDEWEB)

Brown, Craig M; Liu Yun; Yildirim, Taner [National Institute of Standards and Technology Center for Neutron Research, 100 Bureau Drive, MS 6102 (United States); Peterson, Vanessa K [Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW 2234 (Australia); Kepert, Cameron J [School of Chemistry, The University of Sydney, NSW 2006 (Australia)], E-mail: craig.brown@nist.gov

2009-05-20

Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu{sub 3}(1,3,5-benzenetricarboxylate){sub 2}), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H{sub 2}-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H{sub 2} molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H{sub 2} has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

Science.gov (United States)

Brown, Craig M.; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K.; Kepert, Cameron J.

2009-05-01

Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.

Arginine-phosphate salt bridges between histones and DNA: Intermolecular actuators that control nucleosome architecture

Science.gov (United States)

Yusufaly, Tahir I.; Li, Yun; Singh, Gautam; Olson, Wilma K.

2014-10-01

Structural bioinformatics and van der Waals density functional theory are combined to investigate the mechanochemical impact of a major class of histone-DNA interactions, namely, the formation of salt bridges between arginine residues in histones and phosphate groups on the DNA backbone. Principal component analysis reveals that the configurational fluctuations of the sugar-phosphate backbone display sequence-specific directionality and variability, and clustering of nucleosome crystal structures identifies two major salt-bridge configurations: a monodentate form in which the arginine end-group guanidinium only forms one hydrogen bond with the phosphate, and a bidentate form in which it forms two. Density functional theory calculations highlight that the combination of sequence, denticity, and salt-bridge positioning enables the histones to apply a tunable mechanochemical stress to the DNA via precise and specific activation of backbone deformations. The results suggest that selection for specific placements of van der Waals contacts, with high-precision control of the spatial distribution of intermolecular forces, may serve as an underlying evolutionary design principle for the structure and function of nucleosomes, a conjecture that is corroborated by previous experimental studies.

Exposure to tri-o-cresyl phosphate detected in jet airplane passengers.

Science.gov (United States)

Liyasova, Mariya; Li, Bin; Schopfer, Lawrence M; Nachon, Florian; Masson, Patrick; Furlong, Clement E; Lockridge, Oksana

2011-11-01

The aircraft cabin and flight deck ventilation are supplied from partially compressed unfiltered bleed air directly from the engine. Worn or defective engine seals can result in the release of engine oil into the cabin air supply. Aircrew and passengers have complained of illness following such "fume events". Adverse health effects are hypothesized to result from exposure to tricresyl phosphate mixed esters, a chemical added to jet engine oil and hydraulic fluid for its anti-wear properties. Our goal was to develop a laboratory test for exposure to tricresyl phosphate. The assay was based on the fact that the active-site serine of butyrylcholinesterase reacts with the active metabolite of tri-o-cresyl phosphate, cresyl saligenin phosphate, to make a stable phosphorylated adduct with an added mass of 80 Da. No other organophosphorus agent makes this adduct in vivo on butyrylcholinesterase. Blood samples from jet airplane passengers were obtained 24-48 h after completing a flight. Butyrylcholinesterase was partially purified from 25 ml serum or plasma, digested with pepsin, enriched for phosphorylated peptides by binding to titanium oxide, and analyzed by mass spectrometry. Of 12 jet airplane passengers tested, 6 were positive for exposure to tri-o-cresyl phosphate that is, they had detectable amounts of the phosphorylated peptide FGEpSAGAAS. The level of exposure was very low. No more than 0.05 to 3% of plasma butyrylcholinesterase was modified. None of the subjects had toxic symptoms. Four of the positive subjects were retested 3 to 7 months following their last airplane trip and were found to be negative for phosphorylated butyrylcholinesterase. In conclusion, this is the first report of an assay that detects exposure to tri-o-cresyl phosphate in jet airplane travelers. Copyright © 2011 Elsevier Inc. All rights reserved.

High-capacity hydrogen storage in Li-adsorbed g-C{sub 3}N{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Wei, Jianfeng; Huang, Chengxi; Wu, Haiping, E-mail: mrhpwu@njust.edu.cn; Kan, Erjun, E-mail: ekan@njust.edu.cn

2016-09-01

Since hydrogen is a kind of potential source of efficient and pollution-free energy, it has attracted great research interests in recent years. However, the lack of safe and efficient hydrogen storage materials has blocked the rapid development of hydrogen energy. Here, we explored the possibility of Li-decorated g-C{sub 3}N{sub 4} as a kind of potential hydrogen storage materials based on first-principles calculations. Our results demonstrated that the adsorption energy of Li atoms on g-C{sub 3}N{sub 4} is much larger than the cohesive energy of bulk Li. Importantly, we find that the binding energy of each H{sub 2} molecule is about 0.29 eV, which is quite suitable for hydrogen storage. Furthermore, the estimated hydrogen storage capacity is around 9.2 wt %, which beyonds the goal of DOE. Thus, we predicted that Li-decorated g-C{sub 3}N{sub 4} may act as the potential hydrogen storage materials. - Highlights: • We explored the possibility of Li-decorated g-C{sub 3}N{sub 4} as a kind of potential hydrogen storage material. • We demonstrated the binding energy of each H{sub 2} molecule is 0.29 eV, which is quite suitable for hydrogen storage materials. • The hydrogen storage capacity is estimated around 9.2 wt %.

Removal of phosphate from solution by adsorption and precipitation of calcium phosphate onto monohydrocalcite.

Science.gov (United States)

Yagi, Shintaro; Fukushi, Keisuke

2012-10-15

The sorption behavior and mechanism of phosphate on monohydrocalcite (CaCO(3)·H(2)O: MHC) were examined using batch sorption experiments as a function of phosphate concentrations, ionic strengths, temperatures, and reaction times. The mode of PO(4) sorption is divisible into three processes depending on the phosphate loading. At low phosphate concentrations, phosphate is removed by coprecipitation of phosphate during the transformation of MHC to calcite. The sorption mode at the low-to-moderate phosphate concentrations is most likely an adsorption process because the sorption isotherm at the conditions can be fitted reasonably with the Langmuir equation. The rapid sorption kinetics at the conditions is also consistent with the adsorption reaction. The adsorption of phosphate on MHC depends strongly on ionic strength, but slightly on temperature. The maximum adsorption capacities of MHC obtained from the regression of the experimental data to the Langmuir equation are higher than those reported for stable calcium carbonate (calcite or aragonite) in any conditions. At high phosphate concentrations, the amount of sorption deviates from the Langmuir isotherm, which can fit the low-to-moderate phosphate concentrations. Speciation-saturation analyses of the reacted solutions at the conditions indicated that the solution compositions which deviate from the Langmuir equation are supersaturated with respect to a certain calcium phosphate. The obtained calcium phosphate is most likely amorphous calcium phosphate (Ca(3)(PO(4))(2)·xH(2)O). The formation of the calcium phosphate depends strongly on ionic strength, temperature, and reaction times. The solubility of MHC is higher than calcite and aragonite because of its metastability. Therefore, the higher solubility of MHC facilitates the formation of the calcium phosphates more than with calcite and aragonite. Copyright © 2012 Elsevier Inc. All rights reserved.

Anelastic mechanical loss spectrometry of hydrogen in austenitic stainless steels

International Nuclear Information System (INIS)

Yagodzinskyy, Y.; Andronova, E.; Ivanchenko, M.; Haenninen, H.

2009-01-01

Atomic distribution of hydrogen, its elemental diffusion jumps and its interaction with dislocations in a number of austenitic stainless steels are studied with anelastic mechanical loss (AML) spectrometry in combination with the hydrogen thermal desorption method. Austenitic stainless steels of different chemical composition, namely, AISI 310, AISI 201, and AISI 301LN, as well as LDX 2101 duplex stainless steel are studied to clarify the role of different alloying elements on the hydrogen behavior. Activation analyses of the hydrogen Snoek-like peaks are performed with their decomposition to sets of Gaussian components. Fine structure of the composite hydrogen peaks is analyzed under the assumption that each component corresponds to diffusion transfer of hydrogen between octahedral positions with certain atomic compositions of the nearest neighbouring lattice sites. An additional component originating from hydrogen-dislocation interaction is considered. Binding energies for hydrogen-dislocation interaction are also estimated for the studied austenitic stainless steels.

Fundamental hydrogen interactions with beryllium : a magnetic fusion perspective.

Energy Technology Data Exchange (ETDEWEB)

Wampler, William R. (Sandia National Laboratories, Albuquerque, NM); Felter, Thomas E.; Whaley, Josh A.; Kolasinski, Robert D.; Bartelt, Norman Charles

2012-03-01

Increasingly, basic models such as density functional theory and molecular dynamics are being used to simulate different aspects of hydrogen recycling from plasma facing materials. These models provide valuable insight into hydrogen diffusion, trapping, and recombination from surfaces, but their validation relies on knowledge of the detailed behavior of hydrogen at an atomic scale. Despite being the first wall material for ITER, basic single crystal beryllium surfaces have been studied only sparsely from an experimental standpoint. In prior cases researchers used electron spectroscopy to examine surface reconstruction or adsorption kinetics during exposure to a hydrogen atmosphere. While valuable, these approaches lack the ability to directly detect the positioning of hydrogen on the surface. Ion beam techniques, such as low energy ion scattering (LEIS) and direct recoil spectroscopy (DRS), are two of the only experimental approaches capable of providing this information. In this study, we applied both LEIS and DRS to examine how hydrogen binds to the Be(0001) surface. Our measurements were performed using an angle-resolved ion energy spectrometer (ARIES) to probe the surface with low energy ions (500 eV - 3 keV He{sup +} and Ne{sup +}). We were able to obtain a 'scattering maps' of the crystal surface, providing insight on how low energy ions are focused along open surface channels. Once we completed a characterization of the clean surface, we dosed the sample with atomic hydrogen using a heated tungsten capillary. A distinct signal associated with adsorbed hydrogen emerged that was consistent with hydrogen residing between atom rows. To aid in the interpretation of the experimental results, we developed a computational model to simulate ion scattering at grazing incidence. For this purpose, we incorporated a simplified surface model into the Kalypso molecular dynamics code. This approach allowed us to understand how the incident ions interacted with the

Hydrogen-related effects in crystalline semiconductors

International Nuclear Information System (INIS)

Haller, E.E.

1988-08-01

Recent experimental and theoretical information regarding the states of hydrogen in crystalline semiconductors is reviewed. The abundance of results illustrates that hydrogen does not preferentially occupy a few specific lattice sites but that it binds to native defects and impurities, forming a large variety of neutral and electrically active complexes. The study of hydrogen passivated shallow acceptors and donors and of partially passivated multivalent acceptors has yielded information on the electronic and real space structure and on the chemical composition of these complexes. Infrared spectroscopy, ion channeling, hydrogen isotope substitution and electric field drift experiments have shown that both static trigonal complexes as well as centers with tunneling hydrogen exist. Total energy calculations indicate that the charge state of the hydrogen ion which leads to passivation dominates, i.e., H + in p-type and H/sup /minus// in n-type crystals. Recent theoretical calculations indicate that is unlikely for a large fraction of the atomic hydrogen to exist in its neutral state, a result which is consistent with the total absence of any Electron Paramagnetic Resonance (EPR) signal. An alternative explanation for this result is the formation of H 2 . Despite the numerous experimental and theoretical results on hydrogen-related effects in Ge and Si there remains a wealth of interesting physics to be explored, especially in compound and alloy semiconductors. 6 refs., 6 figs

Patterns of binding of aluminum-containing adjuvants to Haemophilus influenzae type b and meningococcal group C conjugate vaccines and components

Science.gov (United States)

Otto, Robert B.D.; Burkin, Karena; Amir, Saba Erum; Crane, Dennis T.; Bolgiano, Barbara

2015-01-01

The basis of Haemophilus influenzae type b (Hib) and Neisseria meningitidis serogroup C (MenC) glycoconjugates binding to aluminum-containing adjuvants was studied. By measuring the amount of polysaccharide and protein in the non-adsorbed supernatant, the adjuvant, aluminum phosphate, AlPO4, was found to be less efficient than aluminum hydroxide, Al(OH)3 at binding to the conjugates, at concentrations relevant to licensed vaccine formulations and when equimolar. At neutral pH, binding of TT conjugates to AlPO4 was facilitated through the carrier protein, with only weak binding of AlPO4 to CRM197 being observed. There was slightly higher binding of either adjuvant to tetanus toxoid conjugates, than to CRM197 conjugates. This was verified in AlPO4 formulations containing DTwP–Hib, where the adsorption of TT-conjugated Hib was higher than CRM197-conjugated Hib. At neutral pH, the anionic Hib and MenC polysaccharides did not appreciably bind to AlPO4, but did bind to Al(OH)3, due to electrostatic interactions. Phosphate ions reduced the binding of the conjugates to the adjuvants. These patterns of adjuvant adsorption can form the basis for future formulation studies with individual and combination vaccines containing saccharide-protein conjugates. PMID:26194164

Thermal decay of rhodopsin: role of hydrogen bonds in thermal isomerization of 11-cis retinal in the binding site and hydrolysis of protonated Schiff base.

Science.gov (United States)

Liu, Jian; Liu, Monica Yun; Nguyen, Jennifer B; Bhagat, Aditi; Mooney, Victoria; Yan, Elsa C Y

2009-07-01

Although thermal stability of the G protein-coupled receptor rhodopsin is directly related to its extremely low dark noise level and has recently generated considerable interest, the chemistry behind the thermal decay process of rhodopsin has remained unclear. Using UV-vis spectroscopy and HPLC analysis, we have demonstrated that the thermal decay of rhodopsin involves both hydrolysis of the protonated Schiff base and thermal isomerization of 11-cis to all-trans retinal. Examining the unfolding of rhodopsin by circular dichroism spectroscopy and measuring the rate of thermal isomerization of 11-cis retinal in solution, we conclude that the observed thermal isomerization of 11-cis to all-trans retinal happens when 11-cis retinal is in the binding pocket of rhodopsin. Furthermore, we demonstrate that solvent deuterium isotope effects are involved in the thermal decay process by decreasing the rates of thermal isomerization and hydrolysis, suggesting that the rate-determining step of these processes involves breaking hydrogen bonds. These results provide insight into understanding the critical role of an extensive hydrogen-bonding network on stabilizing the inactive state of rhodopsin and contribute to our current understanding of the low dark noise level of rhodopsin, which enables this specialized protein to function as an extremely sensitive biological light detector. Because similar hydrogen-bonding networks have also been suggested by structural analysis of two other GPCRs, beta1 and beta2 adrenergic receptors, our results could reveal a general role of hydrogen bonds in facilitating GPCR function.

Phosphate Recovery From Sewage Sludge Containing Iron Phosphate

NARCIS (Netherlands)

Wilfert, P.K.

2018-01-01

The scope of this thesis was to lay the basis for a phosphate recovery technology that can be applied on sewage sludge containing iron phosphate. Such a technology should come with minimal changes to the existing sludge treatment configuration while keeping the use of chemicals or energy as small as

Carbon-tuned bonding method significantly enhanced the hydrogen storage of BN-Li complexes.

Science.gov (United States)

Deng, Qing-ming; Zhao, Lina; Luo, You-hua; Zhang, Meng; Zhao, Li-xia; Zhao, Yuliang

2011-11-01

Through first-principles calculations, we found doping carbon atoms onto BN monolayers (BNC) could significantly strengthen the Li bond on this material. Unlike the weak bond strength between Li atoms and the pristine BN layer, it is observed that Li atoms are strongly hybridized and donate their electrons to the doped substrate, which is responsible for the enhanced binding energy. Li adsorbed on the BNC layer can serve as a high-capacity hydrogen storage medium, without forming clusters, which can be recycled at room temperature. Eight polarized H(2) molecules are attached to two Li atoms with an optimal binding energy of 0.16-0.28 eV/H(2), which results from the electrostatic interaction of the polarized charge of hydrogen molecules with the electric field induced by positive Li atoms. This practical carbon-tuned BN-Li complex can work as a very high-capacity hydrogen storage medium with a gravimetric density of hydrogen of 12.2 wt%, which is much higher than the gravimetric goal of 5.5 wt % hydrogen set by the U.S. Department of Energy for 2015.

Influence of screening effect on hydrogen passivation of hole silicon

International Nuclear Information System (INIS)

Aleksandrov, O.V.

2002-01-01

The simulation of hole silicon passivation during hydrogen diffusion with account of hydrogen-acceptor pairs formation, internal electrical field and screening effect has been carried out. Screening by free carriers of hydrogen and acceptor ions results in shortening their interaction radii and slacking the concentration dependence of hydrogen diffusivity at high level of silicon doping. The consistency of simulated and experimental profiles of holes and hydrogen-acceptor pairs is reached in a broad band of doping levels from 4 x 10 14 to 1.2 x 10 20 cm -3 at the pair binding energy of 0.70-0.79 eV while the radius of the Coulomb interaction of hydrogen and boron ions is equal to 35 A under low doping and decrease with increasing doping level [ru

Ophthalmic acid accumulation in an Escherichia coli mutant lacking the conserved pyridoxal 5'-phosphate-binding protein YggS.

Science.gov (United States)

Ito, Tomokazu; Yamauchi, Ayako; Hemmi, Hisashi; Yoshimura, Tohru

2016-12-01

Escherichia coli YggS is a highly conserved pyridoxal 5'-phosphate (PLP)-binding protein whose biochemical function is currently unknown. A previous study with a yggS-deficient E. coli strain (ΔyggS) demonstrated that YggS controls l-Ile- and l-Val-metabolism by modulating 2-ketobutyrate (2-KB), l-2-aminobutyrate (l-2-AB), and/or coenzyme A (CoA) availability in a PLP-dependent fashion. In this study, we found that ΔyggS accumulates an unknown metabolite as judged by amino acid analyses. LC/MS and MS/MS analyses of the compound with propyl chloroformate derivatization, and co-chromatography analysis identified this compound as γ-l-glutamyl-l-2-aminobutyryl-glycine (ophthalmic acid), a glutathione (GSH) analogue in which the l-Cys moiety is replaced by l-2-AB. We also determine the metabolic consequence of the yggS mutation. Absence of YggS initially increases l-2-AB availability, and then causes ophthalmic acid accumulation and CoA limitation in the cell. The expression of a γ-glutamylcysteine synthetase and a glutathione synthetase in a ΔyggS background causes high-level accumulation of ophthalmic acid in the cells (∼1.2 nmol/mg cells) in a minimal synthetic medium. This opens the possibility of a first fermentative production of ophthalmic acid. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

2,3-diphosphoglycerate phosphatase activity of phosphoglycerate mutase: stimulation by vanadate and phosphate

International Nuclear Information System (INIS)

Stankiewicz, P.J.; Gresser, M.J.; Tracey, A.S.; Hass, L.F.

1987-01-01

The binding of inorganic vanadate (V/sub i/) to rabbit muscle phosphoglycerate mutase (PGM), studied by using 51 V nuclear magnetic resonance spectroscopy, shows a sigmoidal dependence on vanadate concentration with a stoichiometry of four vanadium atoms per PGM molecule at saturating [V/sub i/]. The data are consistent with binding of one divanadate ion to each of the two subunits of PGM in a noncooperative manner with an intrinsic dissociation constant of 4 x 10 -6 M. The relevance of this result to other studies which have shown that the V/sub i/-stimulated 2,3-diphosphoglycerate (2,3-DPG) phosphatase activity of PGM has a sigmoidal dependence on [V/sub i/] with a Hill coefficient of 2.0 is discussed. At pH 7.0, inorganic phosphate has little effect on the 2,3-DPG phosphatase activity of PGM, even at concentrations as high as 50 mM. Similarly, 25 μM V/sub i/ has little effect on the phosphatase activity. However, in the presence of 25 μM V/sub i/, a phosphate concentration of 20 mM increases the phosphatase activity by more than 3-fold. This behavior is rationalized in terms of activation of the phosphatase activity by a phosphate/vanadate mixed anhydride. This interpretation is supported by the observation of strong activation of the phosphatase activity by inorganic pyrophosphate. A molecular mechanism for the observed effects of vanadate is proposed, and the relevance of this study to the possible use of vanadate as a therapeutic agent for the treatment of sickle cell anemia is discussed

A Biomimetic Approach to New Adsorptive Hydrogen Storage Metal-Organic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Zhou, Hongcai J [Texas A& M University

2015-08-12

In the past decades, there has been an escalation of interest in the study of MOFs due to their fascinating structures and intriguing application potentials. Their exceptionally high surface areas, uniform yet tunable pore sizes, and well-defined adsorbate-MOF interaction sites make them suitable for hydrogen storage. Various strategies to increase the hydrogen capacity of MOFs, such as constructing pore sizes comparable to hydrogen molecules, increasing surface area and pore volume, utilizing catenation, and introducing coordinatively unsaturated metal centers (UMCs) have been widely explored to increase the hydrogen uptake of the MOFs. MOFs with hydrogen uptake approaching the DOE gravimetric storage goal under reasonable pressure but cryo- temperature (typically 77 K) were achieved. However, the weak interaction between hydrogen molecules and MOFs has been the major hurdle limiting the hydrogen uptake of MOFs at ambient temperature. Along the road, we have realized both high surface area and strong interaction between framework and hydrogen are equally essential for porous materials to be practically applicable in Hydrogen storage. Increasing the isosteric heats of adsorption for hydrogen through the introduction of active centers into the framework could have great potential on rendering the framework with strong interaction toward hydrogen. Approaches on increasing the surface areas and improving hydrogen affinity by optimizing size and structure of the pores and the alignment of active centers around the pores in frameworks have been pursued, for example: (a) the introduction of coordinatively UMC (represents a metal center missing multiple ligands) with potential capability of multiple dihydrogen-binding (Kubas type, non-dissociative) per UMC, (b) the design and synthesis of proton-rich MOFs in which a + H3 binds dihydrogen just like a metal ion does, and (c) the preparation of MOFs and PPNs with well aligned internal electric fields. We believe the

ATP-binding Cassette (ABC) Transport System Solute-binding Protein-guided Identification of Novel d-Altritol and Galactitol Catabolic Pathways in Agrobacterium tumefaciens C58*

Science.gov (United States)

Wichelecki, Daniel J.; Vetting, Matthew W.; Chou, Liyushang; Al-Obaidi, Nawar; Bouvier, Jason T.; Almo, Steven C.; Gerlt, John A.

2015-01-01

Innovations in the discovery of the functions of uncharacterized proteins/enzymes have become increasingly important as advances in sequencing technology flood protein databases with an exponentially growing number of open reading frames. This study documents one such innovation developed by the Enzyme Function Initiative (EFI; U54GM093342), the use of solute-binding proteins for transport systems to identify novel metabolic pathways. In a previous study, this strategy was applied to the tripartite ATP-independent periplasmic transporters. Here, we apply this strategy to the ATP-binding cassette transporters and report the discovery of novel catabolic pathways for d-altritol and galactitol in Agrobacterium tumefaciens C58. These efforts resulted in the description of three novel enzymatic reactions as follows: 1) oxidation of d-altritol to d-tagatose via a dehydrogenase in Pfam family PF00107, a previously unknown reaction; 2) phosphorylation of d-tagatose to d-tagatose 6-phosphate via a kinase in Pfam family PF00294, a previously orphan EC number; and 3) epimerization of d-tagatose 6-phosphate C-4 to d-fructose 6-phosphate via a member of Pfam family PF08013, another previously unknown reaction. The epimerization reaction catalyzed by a member of PF08013 is especially noteworthy, because the functions of members of PF08013 have been unknown. These discoveries were assisted by the following two synergistic bioinformatics web tools made available by the Enzyme Function Initiative: the EFI-Enzyme Similarity Tool and the EFI-Genome Neighborhood Tool. PMID:26472925

Binding of hydrocarbons and other extremely weak ligands to transition metal complexes that coordinate hydrogen: Investigation of cis-interactions and delocalized bonding involving sigma bonds

International Nuclear Information System (INIS)

Kubas, G.J.; Eckert, J.; Luo, X.L.

1997-01-01

This is the final report of a three-year Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). At the forefront of chemistry are efforts to catalytically transform the inert C-H bonds in alkanes to more useful products using metal compounds. The goal is to observe binding and cleavage of alkane C-H bonds on metals or to use related silane Si-H bonding as models, analogous to the discovery of hydrogen (H 2 ) binding to metals. Studies of these unique sigma complexes (M hor-ellipsis H-Y; Y double-bond H, Si, C) will aid in developing new catalysts or technologies relevant to DOE interest, e.g., new methods for tritium isotope separation. Several transition metals (Mo, W, Mn, and Pt) were found to reversibly bind and cleave H 2 , silanes, and halocarbons. The first metal-SiH 4 complexes, thus serving as a model for methane reactions. A second goal is to study the dynamics and energetics of H-Y bonds on metals by neutron scattering, and evidence for interactions between bound H-Y and nearby H atoms on metal complexes has been found

Incorporation of phosphate into glycogen by glycogen synthase.

Science.gov (United States)

Contreras, Christopher J; Segvich, Dyann M; Mahalingan, Krishna; Chikwana, Vimbai M; Kirley, Terence L; Hurley, Thomas D; DePaoli-Roach, Anna A; Roach, Peter J

2016-05-01

The storage polymer glycogen normally contains small amounts of covalently attached phosphate as phosphomonoesters at C2, C3 and C6 atoms of glucose residues. In the absence of the laforin phosphatase, as in the rare childhood epilepsy Lafora disease, the phosphorylation level is elevated and is associated with abnormal glycogen structure that contributes to the pathology. Laforin therefore likely functions in vivo as a glycogen phosphatase. The mechanism of glycogen phosphorylation is less well-understood. We have reported that glycogen synthase incorporates phosphate into glycogen via a rare side reaction in which glucose-phosphate rather than glucose is transferred to a growing polyglucose chain (Tagliabracci et al. (2011) Cell Metab13, 274-282). We proposed a mechanism to account for phosphorylation at C2 and possibly at C3. Our results have since been challenged (Nitschke et al. (2013) Cell Metab17, 756-767). Here we extend the evidence supporting our conclusion, validating the assay used for the detection of glycogen phosphorylation, measurement of the transfer of (32)P from [β-(32)P]UDP-glucose to glycogen by glycogen synthase. The (32)P associated with the glycogen fraction was stable to ethanol precipitation, SDS-PAGE and gel filtration on Sephadex G50. The (32)P-signal was not affected by inclusion of excess unlabeled UDP before analysis or by treatment with a UDPase, arguing against the signal being due to contaminating [β-(32)P]UDP generated in the reaction. Furthermore, [(32)P]UDP did not bind non-covalently to glycogen. The (32)P associated with glycogen was released by laforin treatment, suggesting that it was present as a phosphomonoester. The conclusion is that glycogen synthase can mediate the introduction of phosphate into glycogen, thereby providing a possible mechanism for C2, and perhaps C3, phosphorylation. Copyright © 2016 Elsevier Inc. All rights reserved.

Phosphate-a poison for humans?

Science.gov (United States)

Komaba, Hirotaka; Fukagawa, Masafumi

2016-10-01

Maintenance of phosphate balance is essential for life, and mammals have developed a sophisticated system to regulate phosphate homeostasis over the course of evolution. However, due to the dependence of phosphate elimination on the kidney, humans with decreased kidney function are likely to be in a positive phosphate balance. Phosphate excess has been well recognized as a critical factor in the pathogenesis of mineral and bone disorders associated with chronic kidney disease, but recent investigations have also uncovered toxic effects of phosphate on the cardiovascular system and the aging process. Compelling evidence also suggests that increased fibroblastic growth factor 23 and parathyroid hormone levels in response to a positive phosphate balance contribute to adverse clinical outcomes. These insights support the current practice of managing serum phosphate in patients with advanced chronic kidney disease, although definitive evidence of these effects is lacking. Given the potential toxicity of excess phosphate, the general population may also be viewed as a target for phosphate management. However, the widespread implementation of dietary phosphate intervention in the general population may not be warranted due to the limited impact of increased phosphate intake on mineral metabolism and clinical outcomes. Nonetheless, the increasing incidence of kidney disease or injury in our aging society emphasizes the potential importance of this issue. Further work is needed to more completely characterize phosphate toxicity and to establish the optimal therapeutic strategy for managing phosphate in patients with chronic kidney disease and in the general population. Copyright © 2016 International Society of Nephrology. Published by Elsevier Inc. All rights reserved.

Nucleation, growth and evolution of calcium phosphate films on calcite.

Science.gov (United States)

Naidu, Sonia; Scherer, George W

2014-12-01

Marble, a stone composed of the mineral calcite, is subject to chemically induced weathering in nature due to its relatively high dissolution rate in acid rain. To protect monuments and sculpture from corrosion, we are investigating the application of thin layers of hydroxyapatite (HAP) onto marble. The motivation for using HAP is its low dissolution rate and crystal and lattice compatibility with calcite. A mild, wet chemical synthesis route, in which diammonium hydrogen phosphate salt was reacted with marble, alone and with cationic and anionic precursors under different reaction conditions, was used to produce inorganic HAP layers on marble. Nucleation and growth on the calcite substrate was studied, as well as metastable phase evolution, using scanning electron microscopy, grazing incidence X-ray diffraction, and atomic force microscopy. Film nucleation was enhanced by surface roughness. The rate of nucleation and the growth rate of the film increased with cationic (calcium) and anionic (carbonate) precursor additions. Calcium additions also influenced phase formation, introducing a metastable phase (octacalcium phosphate) and a different phase evolution sequence. Copyright © 2014 Elsevier Inc. All rights reserved.

Transcription of lncRNA prt, clustered prt RNA sites for Mmi1 binding, and RNA polymerase II CTD phospho-sites govern the repression of pho1 gene expression under phosphate-replete conditions in fission yeast.

Science.gov (United States)

Chatterjee, Debashree; Sanchez, Ana M; Goldgur, Yehuda; Shuman, Stewart; Schwer, Beate

2016-07-01

Expression of fission yeast Pho1 acid phosphatase is repressed during growth in phosphate-rich medium. Repression is mediated by transcription of the prt locus upstream of pho1 to produce a long noncoding (lnc) prt RNA. Repression is also governed by RNA polymerase II CTD phosphorylation status, whereby inability to place a Ser7-PO4 mark (as in S7A) derepresses Pho1 expression, and inability to place a Thr4-PO4 mark (as in T4A) hyper-represses Pho1 in phosphate replete cells. Here we find that basal pho1 expression from the prt-pho1 locus is inversely correlated with the activity of the prt promoter, which resides in a 110-nucleotide DNA segment preceding the prt transcription start site. CTD mutations S7A and T4A had no effect on the activity of the prt promoter or the pho1 promoter, suggesting that S7A and T4A affect post-initiation events in prt lncRNA synthesis that make it less and more repressive of pho1, respectively. prt lncRNA contains clusters of DSR (determinant of selective removal) sequences recognized by the YTH-domain-containing protein Mmi1. Altering the nucleobase sequence of two DSR clusters in the prt lncRNA caused hyper-repression of pho1 in phosphate replete cells, concomitant with increased levels of the prt transcript. The isolated Mmi1 YTH domain binds to RNAs with single or tandem DSR elements, to the latter in a noncooperative fashion. We report the 1.75 Å crystal structure of the Mmi1 YTH domain and provide evidence that Mmi1 recognizes DSR RNA via a binding mode distinct from that of structurally homologous YTH proteins that recognize m(6)A-modified RNA. © 2016 Chatterjee et al.; Published by Cold Spring Harbor Laboratory Press for the RNA Society.

In-silico analysis of amotosalen hydrochloride binding to CD-61 of platelets

International Nuclear Information System (INIS)

Chaudhary, H.T.

2016-01-01

To determine the docking of Amotosalen hydrochloride (AH) at CD-61 of platelets, and to suggest the cause of bleeding in AH treated platelets transfusion. Study Design: Descriptive study. Place and Duration of Study: Medical College, Taif University, Taif, Saudi Arabia, from October 2014 to May 2015. Methodology: The study was carried out in-silico. PDB (protein data bank) code of Tirofiban bound to CD-61 was 2vdm. CD-61 was docked with Tirofiban using online docking tools, i.e. Patchdock and Firedock. Then, Amotosalen hydrochloride and CD-61 were also docked. Best docking poses to active sites of 2vdm were found. Ligplot of interactions of ligands and CD-61 were obtained. Then comparison of hydrogen bonds, hydrogen bond lengths, and hydrophobic bonds of 2vdm molecule and best poses of docking results were done. Patchdock and Firedock results of best poses were also analysed using SPSS version 16. Results: More amino acids were involved in hydrogen and hydrophobic bonds in Patchdock and Firedock docking of Amotosalen hydrochloride with CD-61 than Patchdock and Firedock docking of CD-61 with Tirofiban. The binding energy was more in latter than former. Conclusion: Amotosalen hydrochloride binds to the active site of CD-61 with weaker binding force. Haemorrhage seen in Amotosalen hydrochloride-treated platelets might be due to binding of Amotosalen hydrochloride to CD-61. (author)

Triphenyl phosphate allergy from spectacle frames

DEFF Research Database (Denmark)

Carlsen, L; Andersen, K E; Egsgaard, Helge

1986-01-01

A case of triphenyl phosphate allergy from spectacle frames is reported. Patch tests with analytical grade triphenyl phosphate, tri-m-cresyl phosphate, and tri-p-cresyl phosphate in the concentrations 5%, 0.5% and 0.05% pet. showed positive reactions to 0.05% triphenyl phosphate and 0.5% tri......-m-cresyl phosphate, but no reaction to tri-p-cresyl phosphate. Gas chromatography of the tricresyl phosphate 5% pet. patch test material supplied from Trolab showed that it contained a mixture of a wide range of triaryl phosphates, including 0.08% triphenyl phosphate which is above the threshold for detecting...

Effect of medium acidity on the thermodynamics and kinetics of the reaction of pyridoxal 5'-phosphate with isoniazid in an aqueous solution

Science.gov (United States)

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.

Metal hydride electrode and nickel hydrogen storage battery; Suiso kyuzo gokin denkyoku oyobi nikkeru-suiso chikudenchi

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, Y.; Tamagawa, H. [Shin-Kobe Electric Machinery Co. Ltd., Tokyo (Japan); Ikawa, A.; Muranaka, R. [Hitachi Ltd., Ibaraki (Japan). Hitachi Research Lab.

1996-04-16

Water soluble polymers such as cellulose derivatives and polyvinylalcohol have been used conventionally as binders for metal hydride electrode used for nickel-hydrogen storage batteries. The shortcomings of those binders, however, are low flexibility, and poor binding property for hydrogen absorbing alloy powder and the conductive supporting substrate. This invention relates to the use of ethylene-vinyl copolymer with less than -10{degree}C Tg as the binder for hydrogen absorbing alloy powder. It is desirable that the ethylene-vinylacetate copolymer is selected out of ethylene-vinyl acetate-acryl copolymer and ethylene-vinyl acetate-long chain vinyl ester copolymer, and that the addition is larger than 0.1wt% and less than 1wt% against the weight of hydrogen absorbing alloy in the electrode. The use of this binder results in strong binding of hydrogen absorbing alloy powder to the conductive supporting substrate, providing flexibility as well. 4 figs., 5 tabs.

Sequence specificity and biological consequences of drugs that bind covalently in the minor groove of DNA

International Nuclear Information System (INIS)

Hurley, L.H.; Needham-VanDevanter, D.R.

1986-01-01

DNA ligands which bind within the minor groove of DNA exhibit varying degrees of sequence selectivity. Factors which contribute to nucleotide sequence recognition by minor groove ligands have been extensively investigated. Electrostatic interactions, ligand and DNA dehydration energies, hydrophobic interactions and steric factors all play significant roles in sequence selectivity in the minor groove. Interestingly, ligand recognition of nucleotide sequence in the minor groove does not involve significant hydrogen bonding. This is in sharp contrast to cellular enzyme and protein recognition of nucleotide sequence, which is achieved in the major groove via specific hydrogen bond formation between individual bases and the ligand. The ability to read nucleotide sequence via hydrogen bonding allows precise binding of proteins to specific DNA sequences. Minor groove ligands examined to date exhibit a much lower sequence specificity, generally binding to a subset of possible sequences, rather than a single sequence. 19 refs., 7 figs

Quasi-particle energies and optical excitations of hydrogenated and fluorinated germanene.

Science.gov (United States)

Shu, Huabing; Li, Yunhai; Wang, Shudong; Wang, Jinlan

2015-02-14

Using density functional theory, the G0W0 method and Bethe-Salpeter equation calculations, we systematically explore the structural, electronic and optical properties of hydrogenated and fluorinated germanene. The hydrogenated/fluorinated germanene tends to form chair and zigzag-line configurations and its electronic and optical properties show close geometry dependence. The chair hydrogenated/fluorinated and zigzag-line fluorinated germanene are direct band-gap semiconductors, while the zigzag-line hydrogenated germanene owns an indirect band-gap. Moreover, the quasi-particle corrections are significant and strong excitonic effects with large exciton binding energies are observed. Moreover, the zigzag-line hydrogenated/fluorinated germanene shows highly anisotropic optical responses, which may be used as a good optical linear polarizer.

A DFT investigation on group 8B transition metal-doped silicon carbide nanotubes for hydrogen storage application

Science.gov (United States)

Tabtimsai, Chanukorn; Ruangpornvisuti, Vithaya; Tontapha, Sarawut; Wanno, Banchob

2018-05-01

The binding of group 8B transition metal (TMs) on silicon carbide nanotubes (SiCNT) hydrogenated edges and the adsorption of hydrogen molecule on the pristine and TM-doped SiCNTs were investigated using the density functional theory method. The B3LYP/LanL2DZ method was employed in all calculations for the considered structural, adsorption, and electronic properties. The Os atom doping on the SiCNT is found to be the strongest binding. The hydrogen molecule displays a weak interaction with pristine SiCNT, whereas it has a strong interaction with TM-doped SiCNTs in which the Os-doped SiCNT shows the strongest interaction with the hydrogen molecule. The improvement in the adsorption abilities of hydrogen molecule onto TM-doped SiCNTs is due to the protruding structure and the induced charge transfer between TM-doped SiCNT and hydrogen molecule. These observations point out that TM-doped SiCNTs are highly sensitive toward hydrogen molecule. Moreover, the adsorptions of 2-5 hydrogen molecules on TM-doped SiCNT were also investigated. The maximum storage number of hydrogen molecules adsorbed on the first layer of TM-doped SiCNTs is 3 hydrogen molecules. Therefore, TM-doped SiCNTs are suitable to be sensing and storage materials for hydrogen gas.

Formation and characterization of iron-binding phosphorylated human-like collagen as a potential iron supplement

International Nuclear Information System (INIS)

Deng, Jianjun; Chen, Fei; Fan, Daidi; Zhu, Chenhui; Ma, Xiaoxuan; Xue, Wenjiao

2013-01-01

Iron incorporated into food can induce precipitation and unwanted interaction with other components in food. Iron-binding proteins represent a possibility to avoid these problems and other side effects, as the iron is protected. However, there are several technical problems associated with protein–iron complex formation. In this paper, the iron-binding phosphorylated human-like collagen (Fe-G6P-HLC) was prepared under physiological conditions through phosphorylated modification. One molecule of Fe-G6P-HLC possesses about 24 atoms of Fe. Spectroscopy analysis, differential scanning calorimetry (DSC) and equilibrium dialysis techniques were employed to investigate the characteristics of the Fe-G6P-HLC. The binding sites (n b ) and apparent association constant (K app ) between iron and phosphorylated HLC were measured at n b = 23.7 and log K app = 4.57, respectively. The amount of iron (Fe 2+ sulfate) binding to phosphorylated HLC was found to be a function of pH and phosphate content. In addition, the solubility and thermal stability of HLC were not significantly affected. The results should facilitate the utilization of HLC as a bioactive iron supplement in the food and medical industry and provide an important theoretical evidence for the application of HLC chelates. - Highlights: • The iron-binding phosphorylated human-like collagen (Fe-G6P-HLC) was prepared. • One molecule of Fe-G6P-HLC possesses about 24 atoms of Fe. • The binding properties could be modulated through alterations in pH and phosphate content presented in HLC. • A novel strategy for preparing iron-binding proteins was provided

Influence of screening effect on hydrogen passivation of hole silicon

CERN Document Server

Aleksandrov, O V

2002-01-01

The simulation of hole silicon passivation during hydrogen diffusion with account of hydrogen-acceptor pairs formation, internal electrical field and screening effect has been carried out. Screening by free carriers of hydrogen and acceptor ions results in shortening their interaction radii and slacking the concentration dependence of hydrogen diffusivity at high level of silicon doping. The consistency of simulated and experimental profiles of holes and hydrogen-acceptor pairs is reached in a broad band of doping levels from 4 x 10 sup 1 sup 4 to 1.2 x 10 sup 2 sup 0 cm sup - sup 3 at the pair binding energy of 0.70-0.79 eV while the radius of the Coulomb interaction of hydrogen and boron ions is equal to 35 A under low doping and decrease with increasing doping level

A Pyranose-2-Phosphate Motif Is Responsible for Both Antibiotic Import and Quorum-Sensing Regulation in Agrobacterium tumefaciens.

Directory of Open Access Journals (Sweden)

Abbas El Sahili

2015-08-01

Full Text Available Periplasmic binding proteins (PBPs in association with ABC transporters select and import a wide variety of ligands into bacterial cytoplasm. They can also take up toxic molecules, as observed in the case of the phytopathogen Agrobacterium tumefaciens strain C58. This organism contains a PBP called AccA that mediates the import of the antibiotic agrocin 84, as well as the opine agrocinopine A that acts as both a nutrient and a signalling molecule for the dissemination of virulence genes through quorum-sensing. Here, we characterized the binding mode of AccA using purified agrocin 84 and synthetic agrocinopine A by X-ray crystallography at very high resolution and performed affinity measurements. Structural and affinity analyses revealed that AccA recognizes an uncommon and specific motif, a pyranose-2-phosphate moiety which is present in both imported molecules via the L-arabinopyranose moiety in agrocinopine A and the D-glucopyranose moiety in agrocin 84. We hypothesized that AccA is a gateway allowing the import of any compound possessing a pyranose-2-phosphate motif at one end. This was structurally and functionally confirmed by experiments using four synthetic compounds: agrocinopine 3'-O-benzoate, L-arabinose-2-isopropylphosphate, L-arabinose-2-phosphate and D-glucose-2-phosphate. By combining affinity measurements and in vivo assays, we demonstrated that both L-arabinose-2-phosphate and D-glucose-2-phosphate, which are the AccF mediated degradation products of agrocinopine A and agrocin 84 respectively, interact with the master transcriptional regulator AccR and activate the quorum-sensing signal synthesis and Ti plasmid transfer in A. tumefaciens C58. Our findings shed light on the role of agrocinopine and antibiotic agrocin 84 on quorum-sensing regulation in A. tumefaciens and reveal how the PBP AccA acts as vehicle for the importation of both molecules by means of a key-recognition motif. It also opens future possibilities for the

A Pyranose-2-Phosphate Motif Is Responsible for Both Antibiotic Import and Quorum-Sensing Regulation in Agrobacterium tumefaciens.

Science.gov (United States)

El Sahili, Abbas; Li, Si-Zhe; Lang, Julien; Virus, Cornelia; Planamente, Sara; Ahmar, Mohammed; Guimaraes, Beatriz G; Aumont-Nicaise, Magali; Vigouroux, Armelle; Soulère, Laurent; Reader, John; Queneau, Yves; Faure, Denis; Moréra, Solange

2015-08-01

Periplasmic binding proteins (PBPs) in association with ABC transporters select and import a wide variety of ligands into bacterial cytoplasm. They can also take up toxic molecules, as observed in the case of the phytopathogen Agrobacterium tumefaciens strain C58. This organism contains a PBP called AccA that mediates the import of the antibiotic agrocin 84, as well as the opine agrocinopine A that acts as both a nutrient and a signalling molecule for the dissemination of virulence genes through quorum-sensing. Here, we characterized the binding mode of AccA using purified agrocin 84 and synthetic agrocinopine A by X-ray crystallography at very high resolution and performed affinity measurements. Structural and affinity analyses revealed that AccA recognizes an uncommon and specific motif, a pyranose-2-phosphate moiety which is present in both imported molecules via the L-arabinopyranose moiety in agrocinopine A and the D-glucopyranose moiety in agrocin 84. We hypothesized that AccA is a gateway allowing the import of any compound possessing a pyranose-2-phosphate motif at one end. This was structurally and functionally confirmed by experiments using four synthetic compounds: agrocinopine 3'-O-benzoate, L-arabinose-2-isopropylphosphate, L-arabinose-2-phosphate and D-glucose-2-phosphate. By combining affinity measurements and in vivo assays, we demonstrated that both L-arabinose-2-phosphate and D-glucose-2-phosphate, which are the AccF mediated degradation products of agrocinopine A and agrocin 84 respectively, interact with the master transcriptional regulator AccR and activate the quorum-sensing signal synthesis and Ti plasmid transfer in A. tumefaciens C58. Our findings shed light on the role of agrocinopine and antibiotic agrocin 84 on quorum-sensing regulation in A. tumefaciens and reveal how the PBP AccA acts as vehicle for the importation of both molecules by means of a key-recognition motif. It also opens future possibilities for the rational design of

One pot synthesis of chitosan grafted quaternized resin for the removal of nitrate and phosphate from aqueous solution.

Science.gov (United States)

Banu, H Thagira; Meenakshi, Sankaran

2017-11-01

The present study deals with the synthesis of chitosan quaternized resin for efficient removal of nitrate and phosphate from aqueous solution. The resin was characterized with FTIR, SEM with EDX and XRD. Batch method was carried out to optimize various parameters such as contact time, initial concentration of nitrate and phosphate, dosage, pH, co-anions and temperature on the adsorption capacity of the adsorbent. The adsorption process illustrated that the Freundlich isotherm and the pseudo-second order are the best fitted models for the sorption of both anions. The respective negative values of ΔH° and ΔG° revealed that the adsorption of both the anions were exothermic and spontaneous. The removal efficiency of nitrate and phosphate on chitosan quaternized resin were 78% and 90% respectively with 0.1g of adsorbent and the initial concentration as 100mg/L. Nitrate and phosphate anions adsorbed effectively on chitosan quaternized resin by replacing Cl - ions from quaternary site through electrostatic attraction as well as ion-exchange mechanism. Hydrogen bonding also played important role in adsorption process. Even after 7th regeneration cycle the adsorbent retained its adsorption capacity as 23.7mg/g and 30.4mg/g for both nitrate and phosphate respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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.

Feasibility of a tetracycline-binding method for detecting synovial fluid basic calcium phosphate crystals.

Science.gov (United States)

Rosenthal, Ann K; Fahey, Mark; Gohr, Claudia; Burner, Todd; Konon, Irina; Daft, Laureen; Mattson, Eric; Hirschmugl, Carol; Ryan, Lawrence M; Simkin, Peter

2008-10-01

Basic calcium phosphate (BCP) crystals are common components of osteoarthritis (OA) synovial fluid. Progress in understanding the role of these bioactive particles in clinical OA has been hampered by difficulties in their identification. Tetracyclines stain calcium phosphate mineral in bone. The aim of this study was to investigate whether tetracycline staining might be an additional or alternative method for identifying BCP crystals in synovial fluid. A drop of oxytetracycline was mixed with a drop of fluid containing synthetic or native BCP, calcium pyrophosphate dihydrate (CPPD), or monosodium urate (MSU) crystals and placed on a microscope slide. Stained and unstained crystals were examined by light microscopy, with and without a portable broad-spectrum ultraviolet (UV) pen light. A small set of characterized synovial fluid samples were compared by staining with alizarin red S and oxytetracycline. Synthetic BCP crystals in synovial fluid were quantified fluorimetrically using oxytetracycline. After oxytetracycline staining, synthetic and native BCP crystals appeared as fluorescent amorphous aggregates under UV light. Oxytetracycline did not stain CPPD or MSU crystals or other particulates. Oxytetracycline staining had fewer false-positive test results than did alizarin red S staining and could provide estimates of the quantities of synthetic BCP crystals in synovial fluid. With further validation, oxytetracycline staining may prove to be a useful adjunct or alternative to currently available methods for identifying BCP crystals in synovial fluid.

Enhancement of carotenoid and chlorophyll content of an edible freshwater alga (Kai: Cladophora sp. by supplementary inorganic phosphate and investigation of its biomass production

Directory of Open Access Journals (Sweden)

Siripen Traichaiyaporn

2012-01-01

Full Text Available Enhancement of the carotenoid and chlorophyll content of an edible freshwater alga (Kai:Cladophora sp. by supplementary inorganic phosphate in canteen wastewater was investigated. Themass cultivation of the alga was conducted at ambient temperature and light intensity in dilutedcanteen wastewater enhanced with dipotassium hydrogen phosphate at 5-20 mg L-1. An increase intotal carotenoid and chlorophyll was observed. However, it had no effect on biomass production. Asa result of the algal cultivation, there was a dramatic improvement in the quality of canteen wastewater.

Performance of pineapple slips inoculated with diazotrophic phosphate-solubilizing bacteria and rock phosphate

Directory of Open Access Journals (Sweden)

Lílian Estrela Borges Baldotto

2014-06-01

Full Text Available Besides fixing N2, some diazotrophic bacteria or diazotrophs, also synthesize organic acids and are able to solubilize rock phosphates, increasing the availability of P for plants. The application of these bacteria to pineapple leaf axils in combination with rock phosphate could increase N and P availability for the crop, due to the bacterial activity of biological nitrogen fixation and phosphate solubilization. The objectives of this study were: (i to select and characterize diazotrophs able to solubilize phosphates in vitro and (ii evaluate the initial performance of the pineapple cultivars Imperial and Pérola in response to inoculation with selected bacteria in combination with rock phosphate. The experiments were conducted at Universidade Estadual do Norte Fluminense Darcy Ribeiro, in 2009. In the treatments with bacteria the leaf contents of N, P and K were higher than those of the controls, followed by an increase in plant growth. These results indicate that the combined application of diazotrophic phosphate-solubilizing bacteria Burkholderia together with Araxá rock phosphate can be used to improve the initial performance of pineapple slips.

Experimental and in silico investigations of organic phosphates and phosphonates sorption on polymer-ceramic monolithic materials and hydroxyapatite.

Science.gov (United States)

Pietrzyńska, Monika; Zembrzuska, Joanna; Tomczak, Rafał; Mikołajczyk, Jakub; Rusińska-Roszak, Danuta; Voelkel, Adam; Buchwald, Tomasz; Jampílek, Josef; Lukáč, Miloš; Devínsky, Ferdinand

2016-10-10

A method based on experimental and in silico evaluations for investigating interactions of organic phosphates and phosphonates with hydroxyapatite was developed. This quick and easy method is used for determination of differences among organophosphorus compounds of various structures in their mineral binding affinities. Empirical sorption evaluation was carried out using liquid chromatography with tandem mass spectrometry or UV-VIS spectroscopy. Raman spectroscopy was used to confirm sorption of organic phosphates and phosphonates on hydroxyapatite. Polymer-ceramic monolithic material and bulk hydroxyapatite were applied as sorbent materials. Furthermore, a Polymer-ceramic Monolithic In-Needle Extraction device was used to investigate both sorption and desorption steps. Binding energies were computed from the fully optimised structures utilising Density Functional Theory (DFT) at B3LYP/6-31+G(d,p) level. Potential pharmacologic and toxic effects of the tested compounds were estimated by the Prediction of the Activity Spectra of Substances using GeneXplain software. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydrogen inhalation reduced epithelial apoptosis in ventilator-induced lung injury via a mechanism involving nuclear factor-kappa B activation

International Nuclear Information System (INIS)

Huang, Chien-Sheng; Kawamura, Tomohiro; Peng, Ximei; Tochigi, Naobumi; Shigemura, Norihisa; Billiar, Timothy R.; Nakao, Atsunori; Toyoda, Yoshiya

2011-01-01

Highlights: → Hydrogen is a regulatory molecule with antiinflammatory and antiapoptotic protective effects. → There is very limited information on the pathways regulated in vivo by the hydrogen. → Antiapoptotic abilities of hydrogen were explained by upregulation of the antiapoptotic gene. → NFκB activation during hydrogen treatment was correlated with elevated antiapoptotic protein. → NFκB activation associated with increase Bcl-2 may contribute to cytoprotection of hydrogen. -- Abstract: We recently demonstrated the inhalation of hydrogen gas, a novel medical therapeutic gas, ameliorates ventilator-induced lung injury (VILI); however, the molecular mechanisms by which hydrogen ameliorates VILI remain unclear. Therefore, we investigated whether inhaled hydrogen gas modulates the nuclear factor-kappa B (NFκB) signaling pathway. VILI was generated in male C57BL6 mice by performing a tracheostomy and placing the mice on a mechanical ventilator (tidal volume of 30 ml/kg or 10 ml/kg without positive end-expiratory pressure). The ventilator delivered either 2% nitrogen or 2% hydrogen in balanced air. NFκB activation, as indicated by NFκB DNA binding, was detected by electrophoretic mobility shift assays and enzyme-linked immunosorbent assay. Hydrogen gas inhalation increased NFκB DNA binding after 1 h of ventilation and decreased NFκB DNA binding after 2 h of ventilation, as compared with controls. The early activation of NFκB during hydrogen treatment was correlated with elevated levels of the antiapoptotic protein Bcl-2 and decreased levels of Bax. Hydrogen inhalation increased oxygen tension, decreased lung edema, and decreased the expression of proinflammatory mediators. Chemical inhibition of early NFκB activation using SN50 reversed these protective effects. NFκB activation and an associated increase in the expression of Bcl-2 may contribute, in part, to the cytoprotective effects of hydrogen against apoptotic and inflammatory signaling pathway

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

Science.gov (United States)

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.

Exfoliation of graphene flake from SiC substrate using hydrogen injection; a first-principle study

Science.gov (United States)

Lee, Bora; Han, Seungwu; Kim, Yong-Sung

2009-03-01

Recently there is an immense interest in studying graphene for investigating its unique electronic properties as well as practical applications to nanoscale devices. Up to now there are two methods to obtain graphene layers. The first one is a mechanical method in which the single graphene sheet is split off the bulk graphite crystals using adhesives. The other method is graphitization of SiC surfaces by annealing at elevated temperatures. Even though the latter approach can provide a graphene layer in a more controlled way, the exfoliation of the graphene layer still poses a big challenge. In this presentation, based on the first-principles results, we propose a novel exfoliation method using hydrogen. As a model system, the 6H-SiC(0001) 4x4 cell is used, which corresponds to the 3x3 graphene cell. We calculate the binding energy of single hydrogen atom in various places; above and below graphene surface and inside the first SiC layer. The binding energies of hydrogen are calculated for different coverages. It is found that at high coverages, the hydrogen atoms prefer to bind below the graphene surface, cutting the graphene-SiC bonds. This means that the graphene can be exfoliated in the hydrogen-rich environment. The detailed analysis including the electronic structures will be presented.

Patterns of binding of aluminum-containing adjuvants to Haemophilus influenzae type b and meningococcal group C conjugate vaccines and components.

Science.gov (United States)

Otto, Robert B D; Burkin, Karena; Amir, Saba Erum; Crane, Dennis T; Bolgiano, Barbara

2015-09-01

The basis of Haemophilus influenzae type b (Hib) and Neisseria meningitidis serogroup C (MenC) glycoconjugates binding to aluminum-containing adjuvants was studied. By measuring the amount of polysaccharide and protein in the non-adsorbed supernatant, the adjuvant, aluminum phosphate, AlPO4, was found to be less efficient than aluminum hydroxide, Al(OH)3 at binding to the conjugates, at concentrations relevant to licensed vaccine formulations and when equimolar. At neutral pH, binding of TT conjugates to AlPO4 was facilitated through the carrier protein, with only weak binding of AlPO4 to CRM197 being observed. There was slightly higher binding of either adjuvant to tetanus toxoid conjugates, than to CRM197 conjugates. This was verified in AlPO4 formulations containing DTwP-Hib, where the adsorption of TT-conjugated Hib was higher than CRM197-conjugated Hib. At neutral pH, the anionic Hib and MenC polysaccharides did not appreciably bind to AlPO4, but did bind to Al(OH)3, due to electrostatic interactions. Phosphate ions reduced the binding of the conjugates to the adjuvants. These patterns of adjuvant adsorption can form the basis for future formulation studies with individual and combination vaccines containing saccharide-protein conjugates. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Formulation of single super phosphate fertilizer from rock phosphate of Hazara, Pakistan

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Matiullah Khan

2012-05-01

Full Text Available Phosphorus deficiency is wide spread in soils of Pakistan. It is imperative to explore the potential and economics of indigenous Hazara rock phosphate for preparation of single super phosphate fertilizer. For the subject study rock phosphate was collected from Hazara area ground at 160 mesh level with 26% total P2O5 content for manual preparation of single super phosphate fertilizer. The rock phosphate was treated with various concentrations of sulfuric acid (98.9%, diluted or pure in the field. The treatments comprised of 20 and 35% pure acid and diluted with acid-water ratios of 1:5, 1:2, 1:1 and 2:1 v/v for acidulation at the rate of 60 liters 100 kg-1 rock phosphate. The amount was prior calculated in the laboratory for complete wetting of rock phosphate. A quantity of 150 kg rock phosphate was taken as treatment. The respective amount of acid was applied with the spray pump of stainless steel or poured with bucket. After proper processing, chemical analysis of the products showed a range of available P2O5 content from 9.56 to 19.24% depending upon the amount of acid and its dilution. The results reveal at that 1:1 dilutions gave the highest P2O5 content (19.24%, lowest free acid (6 % and 32% weight increase. The application of acid beyond or below this combination either pure or diluted gave hygroscopic product and higher free acids. The cost incurred upon the manual processing was almost half the prevailing rates in the market. These results lead to conclude that application of sulfuric acid at the rate of 60 liters 100 kg-1 with the dilution of 50% (v/v can yield better kind of SSP from Hazara rock phosphate at lower prices.

AutoSite: an automated approach for pseudo-ligands prediction—from ligand-binding sites identification to predicting key ligand atoms

Science.gov (United States)

Ravindranath, Pradeep Anand; Sanner, Michel F.

2016-01-01

Motivation: The identification of ligand-binding sites from a protein structure facilitates computational drug design and optimization, and protein function assignment. We introduce AutoSite: an efficient software tool for identifying ligand-binding sites and predicting pseudo ligand corresponding to each binding site identified. Binding sites are reported as clusters of 3D points called fills in which every point is labelled as hydrophobic or as hydrogen bond donor or acceptor. From these fills AutoSite derives feature points: a set of putative positions of hydrophobic-, and hydrogen-bond forming ligand atoms. Results: We show that AutoSite identifies ligand-binding sites with higher accuracy than other leading methods, and produces fills that better matches the ligand shape and properties, than the fills obtained with a software program with similar capabilities, AutoLigand. In addition, we demonstrate that for the Astex Diverse Set, the feature points identify 79% of hydrophobic ligand atoms, and 81% and 62% of the hydrogen acceptor and donor hydrogen ligand atoms interacting with the receptor, and predict 81.2% of water molecules mediating interactions between ligand and receptor. Finally, we illustrate potential uses of the predicted feature points in the context of lead optimization in drug discovery projects. Availability and Implementation: http://adfr.scripps.edu/AutoDockFR/autosite.html Contact: sanner@scripps.edu Supplementary information: Supplementary data are available at Bioinformatics online. PMID:27354702

Scaled Testing of Hydrogen Gas Getters for Transuranic Waste

International Nuclear Information System (INIS)

Kaszuba, J.; Mroz, E.; Haga, M.; Hollis, W. K.; Peterson, E.; Stone, M.; Orme, C.; Luther, T.; Benson, M.

2006-01-01

Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage and shipment containers. Hydrogen forms a flammable mixture with air over a wide range of concentrations (5% to 75%), and very low energy is needed to ignite hydrogen-air mixtures. For these reasons, the concentration of hydrogen in waste shipment containers (Transuranic Package Transporter-II or TRUPACT-II containers) needs to remain below the lower explosion limit of hydrogen in air (5 vol%). Accident scenarios and the resulting safety analysis require that this limit not be exceeded. The use of 'hydrogen getters' is being investigated as a way to prevent the build up of hydrogen in TRUPACT-II containers. Preferred getters are solid materials that scavenge hydrogen from the gas phase and chemically and irreversibly bind it into the solid state. In this study, two getter systems are evaluated: a) 1,4-bis (phenylethynyl)benzene or DEB, characterized by the presence of carbon-carbon triple bonds; and b) a proprietary polymer hydrogen getter, VEI or TruGetter, characterized by carbon-carbon double bonds. Carbon in both getter types may, in the presence of suitable precious metal catalysts such as palladium, irreversibly react with and bind hydrogen. With oxygen present, the precious metal may also eliminate hydrogen by catalyzing the formation of water. This reaction is called catalytic recombination. DEB and VEI performed satisfactorily in lab scale tests using small test volumes (ml-scale), high hydrogen generation rates, and short time spans of hours to days. The purpose of this study is to evaluate whether DEB and VEI perform satisfactorily in actual drum-scale tests with realistic hydrogen generation rates and time frames. The two getter systems were evaluated in test vessels comprised of a Gas Generation Test Program-style bell-jar and a drum equipped with a composite drum filter. The vessels were scaled to replicate the ratio between void space in the

Trapping of hydrogen isotopes in molybdenum and niobium predamaged by ion implantation

International Nuclear Information System (INIS)

Bottiger, J.; Picraux, S.T.; Rud, N.; Laursen, T.

1977-01-01

The trapping of hydrogen isotopes at defects in Mo and Nb have been studied. Ion beams of 11- and 18-keV He + , 55-keV O + and Ne + , and 500-keV Bi + were used to create defects. Subsequently H or D was injected at room temperature by use of molecular beams of 16-keV H + 2 and D + 2 . Appreciable enhancements were observed in the amount of H and D retained within the near-surface region of predamaged samples compared to samples with no prior damage. The total amount of D retained within the near-surface region was measured by means of the nuclear reaction D( 3 He,p) 4 He, and H depth profiles were measured via a resonance in the nuclear reaction 1 H( 19 F,αγ) 16 O. The H profiles correlate with the predicted predamaging ion profiles; however, appreciable tails to deeper depths for the hydrogen profiles are observed for the heavier predamaging ions. For a given predamage ion fluence, the amount of trapped deuterium increases linearly with incident deuterium fluence until a saturation in the enhancement is reached. The amount of deuterium trapped when saturation occurs increases with increasing predamage fluence. The experiments indicate that lighter ions, which create fewer primary displacements, are more effective per displacement in trapping hydrogen. An appreciable release of hydrogen is obtained upon annealing at 200 and 300 degreeC, and a preannealing experiment indicates this is due to detrapping rather than to any loss of traps. These temperatures suggest a much higher binding energy for the trapped hydrogen isotopes (approx.1.5 eV) than the available evidence gives for simple H-defect binding energies (approximately-less-than0.3 eV). The detailed trapping mechanism is not known. However, it is suggested on the basis of the high binding energies and the high concentrations of hydrogen which can be trapped that clusters of hydrogen may be formed

Integrated assessment of the phosphate industry

International Nuclear Information System (INIS)

Ryan, M.T.; Cotter, S.J.

1980-05-01

The phosphate industry in the United States includes three major activities, namely, mining and milling of phosphate rock, phosphate product manufacture, and phosphate product use. Phosphatic materials contain uranium, thorium, and their decay products in greater than background amounts. This assessment of the radiological impacts associated with the redistribution of radioactive components of phosphate materials may provide insight into the effects of uranium extraction from phosphate materials for use in the nuclear fuel cycle

Hydrogen storage alloy electrode and the nickel-hydrogen secondary battery using the electrode; Suiso kyuzo gokin denkyoku to sorewo mochiita nikkeru/suiso niji denchi

Energy Technology Data Exchange (ETDEWEB)

Ono, T. [Furukawa Electric Co. Ltd., Tokyo (Japan); Furukawa, J. [The Furukawa Battery Co. Ltd., Yokohama (Japan)

1997-02-14

With respect to the conventional nickel-hydrogen secondary battery, pulverization of the hydrogen storage alloy due to repetition of charging-discharging cycles can be prevented by using a fluorocarbon resin as a binder in manufacture of the hydrogen storage alloy electrode; however, the inner pressure increase of the battery in case of overcharging can not be fully controlled. The invention relates to control of the inner pressure increase of the nickel-hydrogen secondary battery in case of overcharging. As to the hydrogen storage alloy electrode, the compound comprising the hydrogen storage alloy powder as a main ingredient is supported by a current collector; further, the compound particularly comprises a fluororubber as a binder. The nickel-hydrogen secondary battery equipped with the hydrogen storage alloy electrode can control the inner pressure increase of the battery in case of overcharging, and lessen decrease of the battery capacity due to repetition of charging-discharging cycles over long time. The effects are dependent on the use of the fluororubber as a binder which has good flexibility, and strong binding capacity as well as water repellency. 1 tab.

Role of Phosphate Transport System Component PstB1 in Phosphate Internalization by Nostoc punctiforme.

Science.gov (United States)

Hudek, L; Premachandra, D; Webster, W A J; Bräu, L

2016-11-01

In bacteria, limited phosphate availability promotes the synthesis of active uptake systems, such as the Pst phosphate transport system. To understand the mechanisms that facilitate phosphate accumulation in the cyanobacterium Nostoc punctiforme, phosphate transport systems were identified, revealing a redundancy of Pst phosphate uptake systems that exists across three distinct operons. Four separate PstB system components were identified. pstB1 was determined to be a suitable target for creating phenotypic mutations that could result in the accumulation of excessive levels of phosphate through its overexpression or in a reduction of the capacity to accumulate phosphate through its deletion. Using quantitative real-time PCR (qPCR), it was determined that pstB1 mRNA levels increased significantly over 64 h in cells cultured in 0 mM added phosphate and decreased significantly in cells exposed to high (12.8 mM) phosphate concentrations compared to the level in cells cultured under normal (0.8 mM) conditions. Possible compensation for the loss of PstB1 was observed when pstB2, pstB3, and pstB4 mRNA levels increased, particularly in cells starved of phosphate. The overexpression of pstB1 increased phosphate uptake by N. punctiforme and was shown to functionally complement the loss of PstB in E. coli PstB knockout (PstB - ) mutants. The knockout of pstB1 in N. punctiforme did not have a significant effect on cellular phosphate accumulation or growth for the most part, which is attributed to the compensation for the loss of PstB1 by alterations in the pstB2, pstB3, and pstB4 mRNA levels. This study provides novel in vivo evidence that PstB1 plays a functional role in phosphate uptake in N. punctiforme IMPORTANCE: Cyanobacteria have been evolving over 3.5 billion years and have become highly adept at growing under limiting nutrient levels. Phosphate is crucial for the survival and prosperity of all organisms. In bacteria, limited phosphate availability promotes the

Improved Hydrogen Gas Getters for TRU Waste Transuranic and Mixed Waste Focus Area - Phase 2 Final Report

Energy Technology Data Exchange (ETDEWEB)

Stone, Mark Lee

2002-04-01

Alpha radiolysis of hydrogenous waste and packaging materials generates hydrogen gas in radioactive storage containers. For that reason, the Nuclear Regulatory Commission (NRC) limits the flammable gas (hydrogen) concentration in the Transuranic Package Transporter-II (TRUPACT-II) containers to 5 vol% of hydrogen in air, which is the lower explosion limit. Consequently, a method is needed to prevent the build up of hydrogen to 5 vol% during the storage and transport of the TRUPACT-II containers (up to 60 days). One promising option is the use of hydrogen getters. These materials scavenge hydrogen from the gas phase and irreversibly bind it in the solid phase. One proven getter is a material called 1,4-bis (phenylethynyl) benzene, or DEB. It has the needed binding rate and capacity, but some of the chemical species that might be present in the containers could interfere with its ability to remove hydrogen. This project is focused upon developing a protective polymeric membrane coating for the DEB getter material, which comes in the form of small, irregularly shaped particles. This report summarizes the experimental results of the second phase of the development of the materials.

Device to remove hydrogen isotopes from a gas phase

International Nuclear Information System (INIS)

Morlock, G.; Wiesemes, J.; Bachner, D.

1977-01-01

The device described here guarantees the selective removal of hydrogen isotopes from gas phases in order to prevent the occurence of explosive H 2 gas mixtures, or to separate off radioactive tritium in nuclear plants from the gas phase. It consists of a closed container whose walls are selectively penetrable by hydrogen isotopes. It is simultaneously filled compactly and presssure-resistant with a metal bulk (e.g. powder, sponges or the like of titanium or other hydrogen isotope binding metal). Walling and bulk are maintained at suitable working temperatures by means of a system according to the Peltier effect. The whole thing is safeguarded by protective walling. (RB) [de

A Conserved Two-Component Signal Transduction System Controls the Response to Phosphate Starvation in Bifidobacterium breve UCC2003.

NARCIS (Netherlands)

Alvarez-Martin, P.; Fernandez, M.; O'Connell-Motherway, M.; O'Connell, K.J.; Sauvageot, N.; Fitzgerald, G.F.; Macsharry, J.; Zomer, A.L.; Sinderen, D. van

2012-01-01

This work reports on the identification and molecular characterization of the two-component regulatory system (2CRS) PhoRP, which controls the response to inorganic phosphate (P(i)) starvation in Bifidobacterium breve UCC2003. The response regulator PhoP was shown to bind to the promoter region of

D-glucose-6-phosphate dehydrogenase (Entner-Doudoroff enzyme) from Pseudomonas fluorescens

International Nuclear Information System (INIS)

Lessmann, D.; Schimz, K.L.; Kurz, G.

1975-01-01

The existence of two different D-glucose-6-phosphate dehydrogenases in Pseudomonas fluorescens has been demonstrated. Based on their different specificity and their different metabolic regulation one enzyme is appointed to the Entner-Doudoroff pathway and the other to the hexose monophosphate pathway. A procedure is described for the isolation of that D-glucose-6-phosphate dehydrogenase which forms part of the Entner-Doudoroff pathway (Entner-Doudoroff enzyme). A 950-fold purification was achieved with an overall yield of 44%. The final preparation, having a specific activity of about 300μmol NADH formed per min per mg protein, was shown to be homogeneous. The molecular weight of the Entner-Doudoroff enzyme has been determined to be 220,000 by gel permeation chromatography, and that of the other enzyme (Zwischenferment) has been shown to be 265,000. The pI of the Entner-Doudoroff enzyme has been shown to be 5.24 and that of the Zwischenferment 4.27. The Entner-Doudoroff enzyme is stable in the range of pH 6 to 10.5 and shows its maximal acivity at pH 8.9. The Entner-Doudoroff enzyme showed specificity for NAD + as well as for NADP + and exhibited homotropic effects for D-glucose 6-phosphate. It is inhibited by ATP which acts as a negative allosteric effector. Other nucleoside triphosphates as well as ADP are also inhibitory. The enzyme catalyzes the transfer of the axial hydrogen at carbon-1 of β-D-glucopyranose 6-phosphate to the si face of carbon-4 of the nicotinamide ring and must be classified as B-side stereospecific dehydrogenase. (orig.) [de

Effects of education on low-phosphate diet and phosphate binder intake to control serum phosphate among maintenance hemodialysis patients: A randomized controlled trial

Directory of Open Access Journals (Sweden)

Eunsoo Lim

2018-03-01

Full Text Available Background : For phosphate control, patient education is essential due to the limited clearance of phosphate by dialysis. However, well-designed randomized controlled trials about dietary and phosphate binder education have been scarce. Methods : We enrolled maintenance hemodialysis patients and randomized them into an education group (n = 48 or a control group (n = 22. We assessed the patients' drug compliance and their knowledge about the phosphate binder using a questionnaire. Results : The primary goal was to increase the number of patients who reached a calcium-phosphorus product of lower than 55. In the education group, 36 (75.0% patients achieved the primary goal, as compared with 16 (72.7% in the control group (P = 0.430. The education increased the proportion of patients who properly took the phosphate binder (22.9% vs. 3.5%, P = 0.087, but not to statistical significance. Education did not affect the amount of dietary phosphate intake per body weight (education vs. control: -1.18 ± 3.54 vs. -0.88 ± 2.04 mg/kg, P = 0.851. However, the dietary phosphate-to-protein ratio tended to be lower in the education group (-0.64 ± 2.04 vs. 0.65 ± 3.55, P = 0.193. The education on phosphate restriction affected neither the Patient-Generated Subjective Global Assessment score (0.17 ± 4.58 vs. -0.86 ± 3.86, P = 0.363 nor the level of dietary protein intake (-0.03 ± 0.33 vs. -0.09 ± 0.18, P = 0.569. Conclusion : Education did not affect the calcium-phosphate product. Education on the proper timing of phosphate binder intake and the dietary phosphate-to-protein ratio showed marginal efficacy.

Zinc phosphate conversion coatings

Science.gov (United States)

Sugama, Toshifumi

1997-01-01

Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate .alpha.-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal.

Theoretical model for the hydrogen-material interaction as a basis for prediction of the material mechanical properties

International Nuclear Information System (INIS)

Indeitsev, D.A.; Polyanskiy, V.A.; Sukhanov, A.A.; Belyaev, A.A.

2009-01-01

The natural law concentration of hydrogen inside the materials has a distribution over the different binding energies. This distribution is changing under the mechanical tension. The model of interaction of the small hydrogen concentration with materials provides one with an instrument for modeling the materials fatigue and destruction, as well as the prediction of material properties during exploitation. The well-known models are of the phenomenological nature. However if one takes into account the physical mechanism then one obtains an accurate model and the instrument for the reliable prediction. The two-continuum model of the solid material is a substantiation for the present study. This model describes the interaction between the low concentration of hydrogen and the material. The redistribution of the hydrogen between the different binding energy levels is taken into account, too

CO hydrogenation to methanol on Cu–Ni catalysts

DEFF Research Database (Denmark)

Studt, Felix; Abild-Pedersen, Frank; Wu, Qiongxiao

2012-01-01

two descriptors, the carbon oxygen binding energies, are constructed. A micro-kinetic model of CO hydrogenation is developed and a volcano-shaped relation based on the two descriptors is obtained for methanol synthesis. A large number of bimetallic alloys with respect to the two descriptors...

Calcium Carbonate Phosphate Binding Ion Exchange Filtration and Accelerated Denitrification Improve Public Health Standards and Combat Eutrophication in Aquatic Ecosystems

OpenAIRE

Yanamadala, Vijay

2005-01-01

Cultural eutrophication, the process by which a lake becomes rich in dissolved nutrients as a result of point and nonpoint pollutant sources, is a major cause of the loss of natural lake ecosystems throughout the world. The process occurs naturally in all lakes, but phosphate-rich nutrient runoff from sources such as storm drains and agricultural runoff is a major cause of excess phosphate-induced eutrophication. Especially in Madrona Marsh, one of the last remaining vernal marshes in the gre...

A generalized allosteric mechanism for cis-regulated cyclic nucleotide binding domains.

Directory of Open Access Journals (Sweden)

Alexandr P Kornev

2008-04-01

Full Text Available Cyclic nucleotides (cAMP and cGMP regulate multiple intracellular processes and are thus of a great general interest for molecular and structural biologists. To study the allosteric mechanism of different cyclic nucleotide binding (CNB domains, we compared cAMP-bound and cAMP-free structures (PKA, Epac, and two ionic channels using a new bioinformatics method: local spatial pattern alignment. Our analysis highlights four major conserved structural motifs: 1 the phosphate binding cassette (PBC, which binds the cAMP ribose-phosphate, 2 the "hinge," a flexible helix, which contacts the PBC, 3 the beta(2,3 loop, which provides precise positioning of an invariant arginine from the PBC, and 4 a conserved structural element consisting of an N-terminal helix, an eight residue loop and the A-helix (N3A-motif. The PBC and the hinge were included in the previously reported allosteric model, whereas the definition of the beta(2,3 loop and the N3A-motif as conserved elements is novel. The N3A-motif is found in all cis-regulated CNB domains, and we present a model for an allosteric mechanism in these domains. Catabolite gene activator protein (CAP represents a trans-regulated CNB domain family: it does not contain the N3A-motif, and its long range allosteric interactions are substantially different from the cis-regulated CNB domains.

Modeling cell membrane transport: interaction of guanidinylated poly(propylene imine) dendrimers with a liposomal membrane consisting of phosphate-based lipids.

Science.gov (United States)

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.

Co-Occurring Atomic Contacts for the Characterization of Protein Binding Hot Spots

Science.gov (United States)

Liu, Qian; Ren, Jing; Song, Jiangning; Li, Jinyan

2015-01-01

A binding hot spot is a small area at a protein-protein interface that can make significant contribution to binding free energy. This work investigates the substantial contribution made by some special co-occurring atomic contacts at a binding hot spot. A co-occurring atomic contact is a pair of atomic contacts that are close to each other with no more than three covalent-bond steps. We found that two kinds of co-occurring atomic contacts can play an important part in the accurate prediction of binding hot spot residues. One is the co-occurrence of two nearby hydrogen bonds. For example, mutations of any residue in a hydrogen bond network consisting of multiple co-occurring hydrogen bonds could disrupt the interaction considerably. The other kind of co-occurring atomic contact is the co-occurrence of a hydrophobic carbon contact and a contact between a hydrophobic carbon atom and a π ring. In fact, this co-occurrence signifies the collective effect of hydrophobic contacts. We also found that the B-factor measurements of several specific groups of amino acids are useful for the prediction of hot spots. Taking the B-factor, individual atomic contacts and the co-occurring contacts as features, we developed a new prediction method and thoroughly assessed its performance via cross-validation and independent dataset test. The results show that our method achieves higher prediction performance than well-known methods such as Robetta, FoldX and Hotpoint. We conclude that these contact descriptors, in particular the novel co-occurring atomic contacts, can be used to facilitate accurate and interpretable characterization of protein binding hot spots. PMID:26675422