Novel sulfonated poly (ether ether ketone)/phosphonic acid-functionalized titania nanohybrid membrane by an in situ method for direct methanol fuel cells

Science.gov (United States)

Wu, Hong; Cao, Ying; Li, Zhen; He, Guangwei; Jiang, Zhongyi

2015-01-01

Sulfonated poly (ether ether ketone)/phosphonic acid-functionalized titania nanohybrid membranes are prepared by an in situ method using titanium tetrachloride (TiCl4) as inorganic precursor and amino trimethylene phosphonic acid (ATMP) as modifier. Phosphonic acid-functionalized titania nanoparticles with a uniform particle size of ∼50 nm are formed and dispersed homogeneously in the SPEEK matrix with good interfacial compatibility. Accordingly, the nanohybrid membranes display remarkably enhanced proton conduction property due to the incorporation of additional sites for proton transport and the formation of well-connected channels by bridging the hydrophilic domains in SPEEK matrix. The nanohybrid membrane with 6 wt. % of phosphonic acid-functionalized titania nanoparticles exhibits the highest proton conductivity of 0.334 S cm-1 at 65 °C and 100% RH, which is 63.7% higher than that of pristine SPEEK membrane. Furthermore, the as-prepared nanohybrid membranes also show elevated thermal and mechanical stabilities as well as decreased methanol permeability.

Actinide phosphonate complexes in aqueous solutions

International Nuclear Information System (INIS)

Nash, K.L.

1993-01-01

Complexes formed by actinides with carboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids play a central role in both the basic and process chemistry of the actinides. Recent studies of f-element complexes with phosphonic acid ligands indicate that new ligands incorporating doubly ionizable phosphonate groups (-PO 3 H 2 ) have many properties which are unique chemically, and promise more efficient separation processes for waste cleanup and environmental restoration. Simple diphosphonate ligands form much stronger complexes than isostructural carboxylates, often exhibiting higher solubility as well. In this manuscript recent studies of the thermodynamics and kinetics of f-element complexation by 1,1 and 1,2 diphosphonic acid ligands are described

Room-Temperature Alternative to the Arbuzov Reaction: The Reductive Deoxygenation of Acyl Phosphonates

OpenAIRE

Kedrowski, Sean M. A.; Dougherty, Dennis A.

2010-01-01

The reductive deoxygenation of acyl phosphonates using a Wolff−Kishner-like sequence is described. This transformation allows direct access to alkyl phosphonates from acyl phosphonates at room temperature. The method can be combined with acyl phosphonate synthesis into a one pot, four-step procedure for the conversion of carboxylic acids into alkyl phosphonates. The methodology works well for a variety of aliphatic acids and shows a functional group tolerance similar to that of other hydrazon...

Synthesis of highly phosphonic acid functionalized benzene-bridged periodic mesoporous organosilicas for use as efficient dye adsorbents

International Nuclear Information System (INIS)

Deka, Juti Rani; Liu, Chia-Ling; Wang, Tzu-Hua; Chang, Wei-Chieh; Kao, Hsien-Ming

2014-01-01

Highlights: • Synthesis of highly phosphonic acid functionalized benzene-bridged PMOs. • Phosphonic acid loaded PMOs as adsorbent for cationic and anionic dyes. • Due to electrostatic interaction the adsorbent has high dye adsorption capacity. • π–π stacking interaction between benzene and dye enhances adsorption capacity. • Intraparticle diffusion played a dominant role in the adsorption process. - Abstract: Periodic mesoporous organosilicas (PMOs) with benzene bridging groups in the silica wall were functionalized with a tunable content of phosphonic acid groups. These bifunctional materials were synthesized by co-condensation of two different organosilane precursors, that is, 1,4-bis(triethoxysilyl)benzene (BTEB) and sodium 3-(trihydroxysilyl)propyl methyl phosphate (SPMP), under acidic conditions using nonionic surfactant Brij-S10 as template. The materials exhibited well-ordered mesostructures and were characterized by X-ray diffraction, nitrogen sorption, TEM, TGA, FTIR, and solid-state NMR measurements. The materials thus obtained were employed as adsorbents to remove different types of dyes, for example, cationic dyes methylene blue and phenosafranine, anionic orange II, and amphoteric rhodamine B, from aqueous solutions. The materials exhibited a remarkably high adsorption capacity than activated carbon due to their ordered mesostructures, a large number of phosphonic acid groups, and high surface areas. The adsorption was mainly governed by electrostatic interaction, but also involved π–π stacking interaction as well as hydrogen bonding. The adsorption kinetics can be better fitted by the pseudo-second order model. The adsorption process was controlled by the mechanisms of external mass transfer and intraparticle diffusion. The materials retained more than 97% dye removal efficiency after use for five consecutive cycles

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

Science.gov (United States)

Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

Synthesis of Ethylene diamine tetra methylene phosphonic acid EDTMP

International Nuclear Information System (INIS)

Assaad, Th.

2009-06-01

Ethylenediamine tetramethylene phosphonic acid (EDTMP) is one of the most widely used ligands which forms stable complexes with various radionuclides all of which have shown high bone affinity and other favorable pharmacological characteristics in biodistribution studies. The EDTMP is very important precursor in the preparation of radiopharmaceutical kits which is used in the applications for bone diagnosis and therapy was synthesized in one step with Mannich type reaction. The obtained product was fully characterized by its multi-nuclear NMR and IR spectroscopy. The purity of the product was confirmed by HPLC. (author)

Experimental and theoretical studies on extraction of actinides and lanthanides by alicyclic H-phosphonates

Energy Technology Data Exchange (ETDEWEB)

Annam, Suresh; Sivaramakrishna, Akella; Vijayakrishna, Kari [VIT Univ., Tamil Nadu (India). Dept. of Chemistry; Gopakumar, Gopinadhanpillai; Rao, C.V.S. Brahmmananda; Sivaraman, N. [Indira Gandhi Centre for Atomic Research (IGCAR), Tamil Nadu (India). Chemistry Group

2017-06-01

Three different alicyclic substituents H-phosphonates, namely, dicyclopentyl H-phosphonate, dicyclohexyl H-phosphonate and dimenthyl H-phosphonate were synthesized and used for liquid-liquid extraction of actinide elements (U, Am and Th) and lanthanide (Gd) in n-dodecane from nitric acid medium. The physicochemical properties of the extractants, such as density, viscosity, solubility were determined. At lower acidities, these H-phosphonates exhibit higher distribution values and the extraction following cation exchange mechanism through P-OH group of tri-coordinated phosphite form. At higher acidities (2N), the extraction is primarily via solvation mechanism through P=O group of penta-coordinated phosphonate form. Amongst the three H-phosphonates, examined dimenthyl H-phosphonate showed the best results for the actinide extraction. Density functional theory (DFT) calculations were applied to understand the electronic structure of the ligands and the metal complexes. The calculated large complexation energy of UO{sub 2}(NO{sub 3}){sub 2}.@2DMnHP is in agreement with the observed trend in experimental distribution ratio data.

Extraction of plutonium and uranium from oxalate bearing solutions using phosphonic acid

International Nuclear Information System (INIS)

Godbole, A.G.; Mapara, P.M.; Swarup, Rajendra

1995-01-01

A feasibility study on the solvent extraction of plutonium and uranium from solutions containing oxalic and nitric acids using a phosphonic acid extractant (PC88A) was made to explore the possibility of recovering Pu from these solutions. Batch experiments on the extraction of Pu(IV) and U(VI) under different parameters were carried out using PC88A in dodecane. The results indicated that Pu could be extracted quantitatively by PC88A from these solutions. A good separation of Pu from U could be achieved at higher temperatures. (author). 6 refs., 3 tabs

Study of ion exchange behaviour of some elements at phosphonic-acid cationite in diluted solutions of nitric acid

International Nuclear Information System (INIS)

Razbash, A.A.; Sevast'yanov, Yu.G.

1985-01-01

Ce(3, 4), Eu(3), Gd(3), Sm(3), Sc(3) distribution coefficients are determined in the macroporic phosphonic acid cationite KRF-20T-60 in nitric acid solutions in 0.1-2.0 M concentration interval using statistical method. A simple method of cerium-139 radionuclide extraction from the industrial lanthanum target is developed. The product yield made up more than 99%, specific activity - 2.37x10 9 Bq/mg, radiochemical purity - no less than 99.9%

Effect of time and deposition method on quality of phosphonic acid modifier self-assembled monolayers on indium zinc oxide

Energy Technology Data Exchange (ETDEWEB)

Sang, Lingzi [Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ 85721 (United States); Knesting, Kristina M. [Department of Chemistry, University of Washington, Seattle, WA 98195-1700 (United States); Bulusu, Anuradha [School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Sigdel, Ajaya K. [National Renewable Energy Laboratory, Golden, CO 80401 (United States); Giordano, Anthony J.; Marder, Seth R. [School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332-0400 (United States); Berry, Joseph J. [National Renewable Energy Laboratory, Golden, CO 80401 (United States); Graham, Samuel [School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Ginger, David S. [Department of Chemistry, University of Washington, Seattle, WA 98195-1700 (United States); Pemberton, Jeanne E., E-mail: pembertn@email.arizona.edu [Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ 85721 (United States)

2016-12-15

Highlights: • Deposition of phosphonic acid monolayers on oxides from ethanol solutions occurs by rapid adsorption within 10 s with slower equilibration complete in 48 h. • The slower equilibration step involves molecular reorientation and vacancy filling on the oxide surface. • Soak-free deposition by spray coating and microcontact printing do not provide reproducible, fully-covered, uniform monolayers without substrate etching. • Adjustments to exposure time, substrate temperature, and solution/substrate contact efficiency are necessary to optimize soak-free methods. - Abstract: Phosphonic acid (PA) self-assembled monolayers (SAMs) are utilized at critical interfaces between transparent conductive oxides (TCO) and organic active layers in organic photovoltaic devices (OPVs). The effects of PA deposition method and time on the formation of close-packed, high-quality monolayers is investigated here for SAMs fabricated by solution deposition, micro-contact printing, and spray coating. The solution deposition isotherm for pentafluorinated benzylphosphonic acid (F{sub 5}BnPA) on indium-doped zinc oxide (IZO) is studied using polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) at room temperature as a model PA/IZO system. Fast surface adsorption occurs within the first min; however, well-oriented high-quality SAMs are reached only after ∼48 h, presumably through a continual process of molecular adsorption/desorption and monolayer filling accompanied by molecular reorientation. Two other rapid, soak-free deposition techniques, micro-contact printing and spray coating, are also explored. SAM quality is compared for deposition of phenyl phosphonic acid (PPA), F{sub 13}-octylphosphonic acid (F{sub 13}OPA), and pentafluorinated benzyl phosphonic acid (F{sub 5}BnPA) by solution deposition, micro-contact printing and spray coating using PM-IRRAS. In contrast to micro-contact printing and spray coating techniques, 48–168 h solution

Effect of Time and Deposition Method on Quality of Phosphonic Acid Modifier Self-Assembled Monolayers on Indium Zinc Oxide

Energy Technology Data Exchange (ETDEWEB)

Sang, Lingzi; Knesting, Kristina M.; Bulusu, Anuradha; Sigdel, Ajaya K.; Giordano, Anthony J.; Marder, Seth R.; Berry, Joseph J.; Graham, Samuel; Ginger, David S.; Pemberton, Jeanne E.

2016-12-15

Phosphonic acid (PA) self-assembled monolayers (SAMs) are utilized at critical interfaces between transparent conductive oxides (TCO) and organic active layers in organic photovoltaic devices (OPVs). The effects of PA deposition method and time on the formation of close-packed, high-quality monolayers is investigated here for SAMs fabricated by solution deposition, micro-contact printing, and spray coating. The solution deposition isotherm for pentafluorinated benzylphosphonic acid (F5BnPA) on indium-doped zinc oxide (IZO) is studied using polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) at room temperature as a model PA/IZO system. Fast surface adsorption occurs within the first min; however, well-oriented high-quality SAMs are reached only after -48 h, presumably through a continual process of molecular adsorption/desorption and monolayer filling accompanied by molecular reorientation. Two other rapid, soak-free deposition techniques, micro-contact printing and spray coating, are also explored. SAM quality is compared for deposition of phenyl phosphonic acid (PPA), F13-octylphosphonic acid (F13OPA), and pentafluorinated benzyl phosphonic acid (F5BnPA) by solution deposition, micro-contact printing and spray coating using PM-IRRAS. In contrast to micro-contact printing and spray coating techniques, 48-168 h solution deposition at both room temperature and 70 degrees C result in contamination- and surface etch-free close-packed monolayers with good reproducibility. SAMs fabricated by micro-contact printing and spray coating are much less well ordered.

Novel quinolinone-phosphonic acid AMPA antagonists devoid of nephrotoxicity.

Science.gov (United States)

Cordi, Alex A; Desos, Patrice; Ruano, Elisabeth; Al-Badri, Hashim; Fugier, Claude; Chapman, Astrid G; Meldrum, Brian S; Thomas, Jean-Yves; Roger, Anita; Lestage, Pierre

2002-10-01

We reported previously the synthesis and structure-activity relationships (SAR) in a series of 2-(1H)-oxoquinolines bearing different acidic functions in the 3-position. Exploiting these SAR, we were able to identify 6,7-dichloro-2-(1H)-oxoquinoline-3-phosphonic acid compound 3 (S 17625) as a potent, in vivo active AMPA antagonist. Unfortunately, during the course of the development, nephrotoxicity was manifest at therapeutically effective doses. Considering that some similitude exists between S 17625 and probenecid, a compound known to protect against the nephrotoxicity and/or slow the clearance of different drugs, we decided to synthesise some new analogues of S 17625 incorporating some of the salient features of probenecid. Replacement of the chlorine in position 6 by a sulfonylamine led to very potent AMPA antagonists endowed with good in vivo activity and lacking nephrotoxicity potential. Amongst the compounds evaluated, derivatives 7a and 7s appear to be the most promising and are currently evaluated in therapeutically relevant stroke models.

Microwave-assisted hydrolysis of phosphonate diesters: an efficient protocol for the preparation of phosphonic acids

Czech Academy of Sciences Publication Activity Database

Jansa, Petr; Baszczyňski, Ondřej; Procházková, Eliška; Dračínský, Martin; Janeba, Zlatko

2012-01-01

Roč. 14, č. 8 (2012), s. 2282-2288 ISSN 1463-9262 R&D Projects: GA MV VG20102015046 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * DNA virus * retrovirus infections * cidofovir * organic-synthesis Subject RIV: CC - Organic Chemistry Impact factor: 6.828, year: 2012

Sol–gel synthesis of tantalum oxide and phosphonic acid-modified carbon nanotubes composite coatings on titanium surfaces

International Nuclear Information System (INIS)

Maho, Anthony; Detriche, Simon; Delhalle, Joseph; Mekhalif, Zineb

2013-01-01

Carbon nanotubes used as fillers in composite materials are more and more appreciated for the outstanding range of accessible properties and functionalities they generate in numerous domains of nanotechnologies. In the framework of biological and medical sciences, and particularly for orthopedic applications and devices (prostheses, implants, surgical instruments, …), titanium substrates covered by tantalum oxide/carbon nanotube composite coatings have proved to constitute interesting and successful platforms for the conception of solid and biocompatible biomaterials inducing the osseous regeneration processes (hydroxyapatite growth, osteoblasts attachment). This paper describes an original strategy for the conception of resistant and homogeneous tantalum oxide/carbon nanotubes layers on titanium through the introduction of carbon nanotubes functionalized by phosphonic acid moieties (-P(=O)(OH) 2 ). Strong covalent C-P bonds are specifically inserted on their external sidewalls with a ratio of two phosphonic groups per anchoring point. Experimental results highlight the stronger “tantalum capture agent” effect of phosphonic-modified nanotubes during the sol–gel formation process of the deposits compared to nanotubes bearing oxidized functions (-OH, -C=O, -C(=O)OH). Particular attention is also paid to the relative impact of the rate of functionalization and the dispersion degree of the carbon nanotubes in the coatings, as well as their wrapping level by the tantalum oxide matrix material. The resulting effect on the in vitro growth of hydroxyapatite is also evaluated to confirm the primary osseous bioactivity of those materials. Chemical, structural and morphological features of the different composite deposits described herein are assessed by X-ray photoelectron spectroscopy (XPS), scanning (SEM) and transmission (TEM) electronic microscopies, energy dispersive X-rays analysis (EDX) and peeling tests. Highlights: ► Formation of tantalum/carbon nanotube

Sol–gel synthesis of tantalum oxide and phosphonic acid-modified carbon nanotubes composite coatings on titanium surfaces

Energy Technology Data Exchange (ETDEWEB)

Maho, Anthony [Laboratory of Chemistry and Electrochemistry of Surfaces, University of Namur (FUNDP), Rue de Bruxelles 61, B-5000 Namur (Belgium); Fonds pour la Formation à la Recherche dans l' Industrie et dans l' Agriculture (FRIA), Rue d' Egmont 5, B-1000 Bruxelles (Belgium); Detriche, Simon; Delhalle, Joseph [Laboratory of Chemistry and Electrochemistry of Surfaces, University of Namur (FUNDP), Rue de Bruxelles 61, B-5000 Namur (Belgium); Mekhalif, Zineb, E-mail: zineb.mekhalif@fundp.ac.be [Laboratory of Chemistry and Electrochemistry of Surfaces, University of Namur (FUNDP), Rue de Bruxelles 61, B-5000 Namur (Belgium)

2013-07-01

Carbon nanotubes used as fillers in composite materials are more and more appreciated for the outstanding range of accessible properties and functionalities they generate in numerous domains of nanotechnologies. In the framework of biological and medical sciences, and particularly for orthopedic applications and devices (prostheses, implants, surgical instruments, …), titanium substrates covered by tantalum oxide/carbon nanotube composite coatings have proved to constitute interesting and successful platforms for the conception of solid and biocompatible biomaterials inducing the osseous regeneration processes (hydroxyapatite growth, osteoblasts attachment). This paper describes an original strategy for the conception of resistant and homogeneous tantalum oxide/carbon nanotubes layers on titanium through the introduction of carbon nanotubes functionalized by phosphonic acid moieties (-P(=O)(OH){sub 2}). Strong covalent C-P bonds are specifically inserted on their external sidewalls with a ratio of two phosphonic groups per anchoring point. Experimental results highlight the stronger “tantalum capture agent” effect of phosphonic-modified nanotubes during the sol–gel formation process of the deposits compared to nanotubes bearing oxidized functions (-OH, -C=O, -C(=O)OH). Particular attention is also paid to the relative impact of the rate of functionalization and the dispersion degree of the carbon nanotubes in the coatings, as well as their wrapping level by the tantalum oxide matrix material. The resulting effect on the in vitro growth of hydroxyapatite is also evaluated to confirm the primary osseous bioactivity of those materials. Chemical, structural and morphological features of the different composite deposits described herein are assessed by X-ray photoelectron spectroscopy (XPS), scanning (SEM) and transmission (TEM) electronic microscopies, energy dispersive X-rays analysis (EDX) and peeling tests. Highlights: ► Formation of tantalum

Assembly of phosphonic acids on GaN and AlGaN

Energy Technology Data Exchange (ETDEWEB)

Simpkins, B S; Stine, R; Theodore, N D; Pehrsson, P E [Chemistry Division, Naval Research Laboratory, Washington DC (United States); Hong, S [Thomas Jefferson High School, McClean, VA (United States); Maekinen, A J [Optical Sciences Division, Naval Research Laboratory, Washington, DC (United States); Mastro, M A; Eddy, C R Jr [Electronics Science and Technology Division, Naval Research Laboratory, Washington, DC (United States)

2010-01-13

Self-assembled monolayers of octadecylphosphonic acid and 16-phosphonohexadecanoic acid (PHDA) were formed on the semiconductor substrates gallium nitride (GaN) and aluminium gallium nitride (AlGaN). The presence of the molecular layers was verified through x-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. Structural information was acquired with infrared spectroscopy which verified the bonding orientation of the carboxyl-containing PHDA. The impact of the molecular layers on the channel conductivity and the surface electronic structure of an AlGaN/GaN heterostructure was measured. Our results indicate that pinning of the surface Fermi level prohibits modification of the channel conductivity by the layer. However, a surface dipole of {approx}0.8 eV is present and associated with both phosphonic acid layers. These results are of direct relevance to field-effect-based biochemical sensors and metal-semiconductor contact formation for this system and provide a fundamental basis for further applications of GaN and AlGaN technology in the fields of biosensing and microelectronics.

Novel open-framework architectures in lanthanide phosphonates

Science.gov (United States)

Groves, John A.; Stephens, Nicholas F.; Wright, Paul A.; Lightfoot, Philip

2006-03-01

Two novel three-dimensional lanthanide coordination polymers have been prepared hydrothermally with the phosphonic acid N,N-piperazine bis(methylenephosphonic acid), H 2O 3PCH 2N(C 2H 4) 2NCH 2PO 3H 2 ( LH 4). The structures of Gd 2( LH 2) 3ṡ3H 2O (I) and Nd 2( LH 2) 3ṡ9H 2O (II) have been characterised by single crystal X-ray techniques. One-dimensional 'lanthanide-phosphate' chains are a key feature in both structures, although there are major structural differences between the chains, with (I) displaying octahedral GdO 6 coordination and (II) showing eight-coordinate NdO 8 polyhedra. In each case, three-dimensional connectivity is completed by coordination of the phosphonate group resulting in open framework structures encapsulating loosely bound water molecules. Isostructural Y 3+ and Yb 3+ analogues of (I) have been prepared, suggesting that cation size is a key factor in controlling the differing reaction products. In the case of Y 2( LH 2) 3ṡ5H 2O, isostructural to (I), it is shown that the extra-framework water molecules may be removed reversibly without framework collapse. Structural relationships to other known lanthanide phosphonates are discussed.

Tetrofuranose nucleoside phosphonic acids: Synthesis and properties

Czech Academy of Sciences Publication Activity Database

Poláková, Ivana; Buděšínský, Miloš; Točík, Zdeněk; Rosenberg, Ivan

2011-01-01

Roč. 76, č. 5 (2011), s. 503-536 ISSN 0010-0765 R&D Projects: GA AV ČR KAN200520801; GA ČR GA203/09/0820; GA MŠk(CZ) LC06061; GA MŠk(CZ) LC06077 Institutional research plan: CEZ:AV0Z40550506 Keywords : tetrofuranosyl phosphonate * nucleotide analogues * phosphonomethoxy nucleosides * sugar hydroxyphosphonates Subject RIV: CC - Organic Chemistry Impact factor: 1.283, year: 2011

Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)

International Nuclear Information System (INIS)

Yang Bingping; Prosvirin, Andrey V.; Zhao, Han-Hua; Mao, Jiang-Gao

2006-01-01

Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH 2 PO 3 H 2 ) 2 (H 4 L) afforded three new metal phosphonates, namely, Cu[NH(CH 2 PO 3 H) 2 ] 1, {Co[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 2 }.H 2 O 2 and Mn[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 3. When HO 2 C(CH 2 ) 3 N(CH 2 PO 3 H 2 ) 2 was used as the phosphonate ligand and 4,4'-bipy as the second metal linker, {Cu 4 [NH(CH 2 PO 3 ) 2 ] 2 (4,4'-bipy)(H 2 O) 4 }.9H 2 O 4 with a pillared layered architecture was obtained. The NH(CH 2 PO 3 ) 2 anion resulted from the cleavage of the HO 2 C(CH 2 ) 3 -group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu 2 O 2 dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO 6 octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 has a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4'-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers. -- Graphical abstract: Four new metal phosphonates, namely, Cu[NH(CH 2 PO 3 H) 2 ] 1, {Co[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 2 }.H 2 O 2, Mn[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 3 and {Cu 4 [NH(CH 2 PO 3 ) 2 ] 2 (4,4'-bipy)(H 2 O) 4 }.9H 2 O 4 have been synthesized and structurally characterized. Compound 1 has a linear chain structure, and compound 2 is layered. Compound 3 is

Corrosion protective performance of amino trimethylene phosphonic acid-metal complex layers fabricated on the cold-rolled steel substrate via one-step assembly

Science.gov (United States)

Yan, Ru; He, Wei; Zhai, Tianhua; Ma, Houyi

2018-06-01

Seeing that amino trimethylene phosphonic acid (ATMP) possesses very strong complexation ability to metal ions and the phosphonic acid group has good affinity for the oxidized iron surface, herein a simple and rapid film-forming method (one-step assembly method) was developed to construct the ATMP-Zn complex conversion layers (ATMP-Zn layers for short) on the cold-rolled steel (CRS) substrate. Zinc ions were found to participate in the formation process of ATMP-based composite film, which made the Zn-containing ATMP film significantly different in appearance, thickness, microstructure and film-forming mechanisms from the Zn-free ATMP film. There was mainly iron (ш) phosphonate in the Zn-free ATMP film, whereas there were Zn2+-ATMP complex and a certain amount of ZnO in the ATMP-Zn composite film. In addition, electrochemical test results clearly indicate that corrosion resistance of ATMP-Zn composite film was greatly enhanced due to the presence of Zn component. Moreover, the corrosion resistance performance could be controlled by adjusting film-forming time, pH and ATMP concentration in the film-forming solutions. The present study provides a new method for the design and fabrication of high-quality environmentally-friendly conversion layers.

Styrene-divinylbenzene copolymer grafted with phosphonic acid dialkylesters

Directory of Open Access Journals (Sweden)

SMARANDA ILIESCU

2004-12-01

Full Text Available The functionalization of a crosslinked chloromethylated polystyrene 8% divinylbenzene copolymer with phosphonic ester groups is detailed. The reacton conditions were studied in order to determine the optimal conditions for obtaining only diesters. A statistical method for the calculation of the fraction of repetive units for the inited and final resin is proposed.

Conformationally constrained nucleoside phosphonic acids - potent inhibitors of human mitochondrial and cytosolic 5'(3')-nucleotidases

Czech Academy of Sciences Publication Activity Database

Šimák, Ondřej; Pachl, Petr; Fábry, Milan; Buděšínský, Miloš; Jandušík, T.; Hnízda, Aleš; Skleničková, Radka; Petrová, Magdalena; Veverka, Václav; Řezáčová, Pavlína; Brynda, Jiří; Rosenberg, Ivan

2014-01-01

Roč. 12, č. 40 (2014), s. 7971-7982 ISSN 1477-0520 R&D Projects: GA ČR GA203/09/0820; GA ČR GA13-24880S; GA ČR GA13-26526S; GA MŠk(CZ) LK11205; GA AV ČR KAN200520801 Institutional support: RVO:61388963 ; RVO:68378050 Keywords : 5'(3')-nucleotidase * structure * inhibition * cdN * mdN * nucleoside * SAR * phosphonic acid Subject RIV: CC - Organic Chemistry Impact factor: 3.562, year: 2014

Determination of perfluoroalkyl carboxylic, sulfonic, and phosphonic acids in food.

Science.gov (United States)

Ullah, Shahid; Alsberg, Tomas; Vestergren, Robin; Berger, Urs

2012-11-01

A sensitive and accurate method was developed and validated for simultaneous analysis of perfluoroalkyl carboxylic acids, sulfonic acids, and phosphonic acids (PFPAs) at low picograms per gram concentrations in a variety of food matrices. The method employed extraction with acetonitrile/water and cleanup on a mixed-mode co-polymeric sorbent (C8 + quaternary amine) using solid-phase extraction. High-performance liquid chromatographic separation was achieved on a C18 column using a mobile phase gradient containing 5 mM 1-methyl piperidine for optimal chromatographic resolution of PFPAs. A quadrupole time-of-flight high-resolution mass spectrometer operating in negative ion mode was used as detector. Method detection limits were in the range of 0.002 to 0.02 ng g(-1) for all analytes. Sample preparation (extraction and cleanup) recoveries at a spiking level of 0.1 ng g(-1) to a baby food composite were in the range of 59 to 98 %. A strong matrix effect was observed in the analysis of PFPAs in food extracts, which was tentatively assigned to sorption of PFPAs to the injection vial in the solvent-based calibration standard. The method was successfully applied to a range of different food matrices including duplicate diet samples, vegetables, meat, and fish samples.

Phosphonate-hydroxyapatite hybrid compounds prepared by hydrothermal method

Energy Technology Data Exchange (ETDEWEB)

Agougui, H.; Aissa, A. [Laboratoire de Physico-Chimie des Materiaux, Faculte des sciences de Monastir, 5019 Monastir (Tunisia); Maggi, S. [CNR-IC Istituto di Cristallografia, via Amendola 122/O, 70126 Bari (Italy); Debbabi, M., E-mail: m.debbabi@yahoo.fr [Laboratoire de Physico-Chimie des Materiaux, Faculte des sciences de Monastir, 5019 Monastir (Tunisia)

2010-12-15

Calcium hydroxyapatite (CaHAp) was prepared in the presence of two alkylphosphonates, the tert-butyl phosphonic acid TBPOH and the 2-carboxyletylphosphonic acid 2-CEPA, by hydrothermal method at 120 deg. C for 15 h. The modification of hydroxyapatite by grafting organic moieties is confirmed by IR and NMR MAS ({sup 1}H and {sup 31}P) spectroscopy and chemical analysis. X-ray powder diffraction patterns show that the incorporation of organic moieties induces a significant loss of the material crystallinity and a clear increase of the unit cell lattice parameter a as function of 2-CEPA grafting rate. The specific surface area (SSA) increases with increasing phosphonate amount especially for 2-CEPA. All techniques show the lower reactivity of TBPOH due to the steric effects of tert-butyl, whereas the 2-CEPA with a linear chain and double acidic functions is more reactive and can replace the OH{sup -} groups of the apatitic structure.

Phosphonate-hydroxyapatite hybrid compounds prepared by hydrothermal method

International Nuclear Information System (INIS)

Agougui, H.; Aissa, A.; Maggi, S.; Debbabi, M.

2010-01-01

Calcium hydroxyapatite (CaHAp) was prepared in the presence of two alkylphosphonates, the tert-butyl phosphonic acid TBPOH and the 2-carboxyletylphosphonic acid 2-CEPA, by hydrothermal method at 120 deg. C for 15 h. The modification of hydroxyapatite by grafting organic moieties is confirmed by IR and NMR MAS ( 1 H and 31 P) spectroscopy and chemical analysis. X-ray powder diffraction patterns show that the incorporation of organic moieties induces a significant loss of the material crystallinity and a clear increase of the unit cell lattice parameter a as function of 2-CEPA grafting rate. The specific surface area (SSA) increases with increasing phosphonate amount especially for 2-CEPA. All techniques show the lower reactivity of TBPOH due to the steric effects of tert-butyl, whereas the 2-CEPA with a linear chain and double acidic functions is more reactive and can replace the OH - groups of the apatitic structure.

Preparation of polyvinyl alcohol graphene oxide phosphonate film and research of thermal stability and mechanical properties.

Science.gov (United States)

Li, Jihui; Song, Yunna; Ma, Zheng; Li, Ning; Niu, Shuai; Li, Yongshen

2018-05-01

In this article, flake graphite, nitric acid, peroxyacetic acid and phosphoric acid are used to prepare graphene oxide phosphonic and phosphinic acids (GOPAs), and GOPAs and polyvinyl alcohol (PVA) are used to synthesize polyvinyl alcohol graphene oxide phosphonate and phosphinate (PVAGOPs) in the case of faint acidity and ultrasound irradiation, and PVAGOPs are used to fabricate PVAGOPs film, and the structure and morphology of GOPAs, PVAGOPs and PVAGOPs film are characterized, and the thermal stability and mechanical properties of PVAGOPs film are investigated. Based on these, it has been proved that GOPAs consist of graphene oxide phosphonic acid and graphene oxide phosphinic acid, and there are CP covalent bonds between them, and PVAGOPs are composed of GOPAs and PVA, and there are six-member lactone rings between GOPAs and PVA, and the thermal stability and mechanical properties of PVAGOPs film are improved effectively. Copyright © 2018 Elsevier B.V. All rights reserved.

The inhibition of crystal growth of mirabilite in aqueous solutions in the presence of phosphonates

Science.gov (United States)

Vavouraki, A. I.; Koutsoukos, P. G.

2016-02-01

The formation of sodium sulfate decahydrate (Mirabilite) has been known to cause serious damages to structural materials both of modern and of historical buildings. Methods which can retard or completely suppress the development of mirabilte crystals are urgently needed especially as remedies or preventive measures for the preservation of the built cultural heritage. In the present work we present results on the effect of the presence of phosphonate compounds on the kinetics of crystal growth from aqueous supersaturated solutions at 18 °C using the seeded growth technique. The phosphonate compounds tested differed with respect to the number of ionizable phosphonate groups and with respect to the number of amino groups in the respective molecules. The crystal growth process was monitored by the temperature changes during the exothermic crystallization of mirabilite in the stirred supersaturated solutions. The crystal growth of mirabilite in the presence of: (1-hydroxyethylidene)-1, 1-diphosphonic acid (HEDP), amino tri (methylene phosphonic acid) (ATMP), hexamethylenediaminetetra (methylene)phosphonic acid (HTDMP), and diethylene triamine penta(methylene phosphonic acid)(DETPMP) over a range of concentrations between 0.1-5% w/w resulted in significant decrease of the rates of mirabilite crystal growth. All phosphonic compounds tested reduced the crystallization rates up to 60% in comparison with additive-free solutions. The presence of the test compounds did not cause changes of the mechanism of crystal growth which was surface diffusion controlled, as shown by the second order dependence of the rates of mirabilite crystal growth on the relative supersaturation. The excellent fit of the measured rates to a kinetic Langmuir-type model suggested that the activity of the tested inhibitors could be attributed to the adsorption and subsequent reduction of the active crystal growth sites of the seed crystals. In all cases, the inhibitory activity was reduced with

Preparation, characterization and application of N-methylene phosphonic acid chitosan grafted magnesia–zirconia stationary phase

Energy Technology Data Exchange (ETDEWEB)

Wang, Qing; Chen, Jie; Huang, Kun; Zhang, Xin; Xu, Li [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Shi, Zhi-guo, E-mail: shizg@whu.edu.cn [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

2015-01-07

Highlights: • N-methylene phosphonic acid chitosan grafted MgO–ZrO{sub 2} was prepared. • It exhibited superior HILIC chromatographic performance to the bare MgO–ZrO{sub 2}. • Monosaccharides, phospholipids and peptides were successfully separated. • It was a promising HILIC stationary phase. - Abstract: A hydrophilic stationary phase (SP) was prepared through grafting N-methylene phosphonic acid chitosan on magnesia–zirconia particles (P-CTS-MgO–ZrO{sub 2}) via Lewis acid–base interaction. The resulting material was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscope and nitrogen adsorption analysis. The chromatographic performance of P-CTS-MgO–ZrO{sub 2} was systemically evaluated by studying effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the novel SP provided hydrophilic, electrostatic-repulsion and ion-exchange interactions. Compared to the bare MgO–ZrO{sub 2}, P-CTS-MgO–ZrO{sub 2} exhibited superior peak shape, reasonable resolution and reduced analysis time in separation of basic analytes. Besides, remarkable resolving power of acids, i.e. six non-steroidal anti-inflammatory drugs which failed to be eluted from the bare MgO–ZrO{sub 2}, was obtained with the theoretical plate number (N/m) of 4653–31313, asymmetry factor <1.21 and the resolution of 1.6–3.4. Finally, P-CTS-MgO–ZrO{sub 2} SP was applied to separate monosaccharides, phospholipids and peptides. P-CTS-MgO–ZrO{sub 2} was a promising hydrophilic SP for wide applications.

Metal phosphonate hybrid mesostructures: environmentally friendly multifunctional materials for clean energy and other applications.

Science.gov (United States)

Ma, Tian-Yi; Yuan, Zhong-Yong

2011-10-17

The synthesis of porous hybrid materials has been extended to mesoporous non-silica-based organic-inorganic hybrid materials, in which mesoporous metal phosphonates represent an important family. By using organically bridged polyphosphonic acids as coupling molecules, the homogeneous incorporation of a considerable number of organic functional groups into the metal phosphonate hybrid framework has been realized. Small amounts of organic additives and the pH value of the reaction solution have a large impact on the morphology and textural properties of the resultant hybrid mesoporous metal phosphonate solids. Cationic and nonionic surfactants can be used as templates for the synthesis of ordered mesoporous metal phosphonates. The materials are used as efficient adsorbents for heavy metal ions, CO₂, and aldehydes, as well as in the separation of polycyclic aromatic hydrocarbons. They are also useful photocatalysts under UV and simulated solar light irradiation for organic dye degradation. Further functionalization of the synthesized mesoporous hybrids makes them oxidation and acid catalysts, both with impressive performances in the fields of sustainable energy and environment. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phosphonates as alternative to tributyl phosphate for the separation of actinides from fission products

International Nuclear Information System (INIS)

Vyas, Chirag K.; Joshirao, Pranav M.; Manchanda, Vijay K.; Rao, C.V.S. Brahmmananda; Jayalakshmi, S.

2015-01-01

The present work investigates the role of increase in the basicity of organophosphorus extractant (dialkylalkyl phosphonates) on the uptake of actinides and fission products vis-a-vis tributyl phosphate (TBP), currently employed as a universal extractant. Two dialkylalkyl phosphonates viz. dibutylpropyl phosphonate (DBPrP) and dibutylpentyl phosphonate (DBPeP) were synthesized, characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Eu(III) and Tc(VII) in nitric acid medium ranging from 0.01-6 M. It was observed that increasing the basicity of the phosphoryl oxygen enhanced the uptake of the actinides and the distribution coefficient values were significantly larger as compared to TBP. The limiting organic concentration (LOC) value was estimated for Th(IV) for these extractants and compared with the TBP system. The separation factors of actinides with phosphonates over Tc(VII) are distinctly better than that with TBP.

Obtention of Samarium and Gadolinium concentrates by solvent extraction using mono-2-ethylhexyl ester of 2-ethylhexyl phosphonic acid

International Nuclear Information System (INIS)

Miranda Junior, Pedro

1996-01-01

The rare earth chlorides solution employed in this study, which is constituted by medium and heavy fractions, is derived from monazite processing accomplished by NUCLEMON-Mineroquimica (SP). This solution shows an acidity about 1.18 M and 189 g/L of rare earth oxides, containing as main constituents: Sm(34.55%), Gd(23.85%), Dy (6.82%), and Y (24.45%). It was used, as organic phase, 2-ethylhexyl phosphonic acid, mono-2-ethylhexylester diluted to 1 M in isododecane. (author)

Adsorbed States of phosphonate derivatives of N-heterocyclic aromatic compounds, imidazole, thiazole, and pyridine on colloidal silver: comparison with a silver electrode.

Science.gov (United States)

Podstawka, Edyta; Olszewski, Tomasz K; Boduszek, Bogdan; Proniewicz, Leonard M

2009-09-03

Here, we report a systematic surface-enhanced Raman spectroscopy (SERS) study of the structures of phosphonate derivatives of the N-heterocyclic aromatic compounds imidazole (ImMeP ([hydroxy(1H-imidazol-5-yl)methyl]phosphonic acid) and (ImMe)(2)P (bis[hydroxy-(1H-imidazol-4-yl)-methyl]phosphinic acid)), thiazole (BAThMeP (butylaminothiazol-2-yl-methyl)phosphonic acid) and BzAThMeP (benzylaminothiazol-2-yl-methyl)phosphonic acid)), and pyridine ((PyMe)(2)P (bis[(hydroxypyridin-3-yl-methyl)]phosphinic acid)) adsorbed on nanometer-sized colloidal particles. We compared these structures to those on a roughened silver electrode surface to determine the relationship between the adsorption strength and the geometry. For example, we showed that all of these biomolecules interact with the colloidal surface through aromatic rings. However, for BzAThMeP, a preferential interaction between the benzene ring and the colloidal silver surface is observed more so than that between the thiazole ring and this substrate. The PC(OH)C fragment does not take part in the adsorption process, and the phosphonate moiety of ImMeP and (ImMe)(2)P, being removed from the surface, only assists in this process.

Effects of radiation, acid, and base on the extractant dihexyl-[(diethylcarbamoyl)methyl] phosphonate

International Nuclear Information System (INIS)

Bahner, C.T.; Shoun, R.R.; McDowell, W.J.

1981-11-01

The effects of exposure to gamma radiation ( 60 Co) and of contact with acidic and basic aqueous solutions on dihexyl[(diethylcarbamoyl)methyl]phosphonate (DHDECMP) were studied. Gamma radiation decomposes DHDECMP into a variety of products. The most troublesome of those are the acidic compounds that cause problems in stripping the actinides and lanthanides from the extractant at low acid concentrations. The rate of degradation of DHDECMP by radiation is about the same or only slightly higher than that of tri-n-butyl phosphate (TBP). It is relatively easy to remove the radiation-produced impurities by equilibration (scrubbing) with sodium carbonate or sodium hydroxide or by column chromatographic methods. The hydrolysis of DHDECMP in contact with aqueous solutions containing less than 3 M HNO 3 is not more severe than that of TBP under the same conditions but is significant above that acid concentration. Hydrolysis of DHDECMP in contact with aqueous sodium hydroxide solution does occur, but it should not pose an important problem with the short contact times such as those anticipated for the removal of the radiation-induced degradation products by caustic scrubbing. Results of various chromatographic tests to characterize the degradation products of DHDECMP are also given

Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

Science.gov (United States)

Chary, Bathoju Chandra; Kim, Sunggak

2013-09-25

Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides

KAUST Repository

Paniagua, Sergio A.; Giordano, Anthony J.; Smith, O’ Neil L.; Barlow, Stephen; Li, Hong; Armstrong, Neal R.; Pemberton, Jeanne E.; Bredas, Jean-Luc; Ginger, David; Marder, Seth R.

2016-01-01

Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface - the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology - significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared. © 2016 American Chemical Society.

Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides

KAUST Repository

Paniagua, Sergio A.

2016-05-26

Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface - the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology - significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared. © 2016 American Chemical Society.

Isosteric phosphonate pyrrolidine-based dinucleoside monophosphate analogues

Czech Academy of Sciences Publication Activity Database

Vaněk, Václav; Buděšínský, Miloš; Kavenová, Ivana; Rinnová, Markéta; Rosenberg, Ivan

2003-01-01

Roč. 22, 5/8 (2003), s. 1065-1067 ISSN 1525-7770. [International Roundtable Nucleosides, Nucleotides and Nucleic Acids /15./. Leuven, 10.09.2002-14.09.2002] R&D Projects: GA ČR GA203/01/1166; GA AV ČR IAA4055101 Institutional research plan: CEZ:AV0Z4055905 Keywords : pyrrolidine-based phosphonate nucleotides * ApA analogues * triplex Subject RIV: CC - Organic Chemistry Impact factor: 0.813, year: 2003

Copper-Catalyzed Synthesis of Mixed Alkyl Aryl Phosphonates

NARCIS (Netherlands)

Fañanás-Mastral, Martín; Feringa, Ben L

2014-01-01

Copper-catalysis allows the direct oxygenarylation of dialkyl phosphonates with diaryliodonium salts. This novel methodology proceeds with a wide range of phosphonates and phosphoramidates under mild conditions and gives straightforward access to valuable mixed alkyl aryl phosphonates in very good

Removal of phosphonates from industrial wastewater with UV/FeII, Fenton and UV/Fenton treatment.

Science.gov (United States)

Rott, Eduard; Minke, Ralf; Bali, Ulusoy; Steinmetz, Heidrun

2017-10-01

Phosphonates are an important group of phosphorus-containing compounds due to their increasing industrial use and possible eutrophication potential. This study involves investigations into the methods UV/Fe II , Fenton and UV/Fenton for their removal from a pure water matrix and industrial wastewaters. It could be shown that the degradability of phosphonates by UV/Fe II (6 kWh/m 3 ) in pure water crucially depended on the pH and was higher the less phosphonate groups a phosphonate contains. The UV/Fe II method is recommended in particular for the treatment of concentrates with nitrogen-free phosphonates, only little turbidity and a low content of organic compounds. Using Fenton reagent, the degradation of polyphosphonates was relatively weak in a pure water matrix (Fenton method (6 kWh/m 3 ), those phosphonates with the smallest numbers of phosphonate groups were easier degraded as well at pH 3.5 in a pure water matrix (o-PO 4 3- formation rates of up to 80%). Despite an incomplete transformation of organically bound phosphorus to o-PO 4 3- with Fenton reagent in an organically highly polluted wastewater (max. 15%), an almost total removal of the total P occurred. The most efficient total P elimination rates were achieved in accordance with the following Fenton implementation: reaction → sludge separation (acidic) → neutralization of the supernatant → sludge separation (neutral). Accordingly, a neutralization directly after the reaction phase led to a lower total P removal extent. Copyright © 2017 Elsevier Ltd. All rights reserved.

Recent advances in H-phosphonate chemistry. Part 1. H-phosphonate esters: synthesis and basic reactions.

Science.gov (United States)

Sobkowski, Michal; Kraszewski, Adam; Stawinski, Jacek

2015-01-01

This review covers recent progress in the preparation of H-phosphonate mono- and diesters, basic studies on mechanistic and stereochemical aspects of this class of phosphorus compounds, and their fundamental chemistry in terms of transformation of P-H bonds into P-heteroatom bonds. Selected recent applications of H-phosphonate derivatives in basic organic phosphorus chemistry and in the synthesis of biologically important phosphorus compounds are also discussed.

A novel glucose biosensor based on phosphonic acid-functionalized silica nanoparticles for sensitive detection of glucose in real samples

International Nuclear Information System (INIS)

Zhao, Wenbo; Fang, Yi; Zhu, Qinshu; Wang, Kuai; Liu, Min; Huang, Xiaohua; Shen, Jian

2013-01-01

An effective strategy for preparation amperometric biosensor by using the phosphonic acid-functionalized silica nanoparticles (PFSi NPs) as special modified materials is proposed. In such a strategy, glucose oxidase (GOD) was selected as model protein to fabricate glucose biosensor in the presence of phosphonic acid-functionalized silica nanoparticles (PFSi NPs). The PFSi NPs were first modified on the surface of glassy carbon (GC) electrode, then, GOD was adsorbed onto the PFSi NPs film by drop-coating. The PFSi NPs were characterized by transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) spectra. The interaction of PFSi NPs with GOD was investigated by the circular dicroism spectroscopy (CD). The results showed PFSi NPs could essentially maintain the native conformation of GOD. The direct electron transfer of GOD on (PFSi NPs)/GCE electrode exhibited excellent electrocatalytic activity for the oxidation of glucose. The proposed biosensor modified with PFSi NPs displayed a fast amperometric response (5 s) to glucose, a good linear current–time relation over a wide range of glucose concentrations from 5.00 × 10 −4 to 1.87 × 10 −1 M, and a low detection limit of 2.44 × 10 −5 M (S/N = 3). Moreover, the biosensor can be used for assessment of the concentration of glucose in many real samples (relative error < 3%). The GOD biosensor modified with PFSi NPs will have essential meaning and practical application in future that attributed to the simple method of fabrication and good performance

Increasing the Fill Factor of Inverted P3HT:PCBM Solar Cells Through Surface Modification of Al-Doped ZnO via Phosphonic Acid-Anchored C60 SAMs

DEFF Research Database (Denmark)

Stubhan, Tobias; Salinas, Michael; Ebel, Alexander

2012-01-01

The influence of aluminum-doped zinc oxide (AZO) electron extraction layers modified with self-assembled monolayers (SAMs) on inverted polymer solar cells is investigated. It is found that AZO modification with phosphonic acid-anchored Fullerene–SAMs leads to a reduction of the series resistance,...

Oxygen isotope signature of UV degradation of glyphosate and phosphonoacetate: Tracing sources and cycling of phosphonates

Energy Technology Data Exchange (ETDEWEB)

Sandy, Edward H. [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Department of Chemistry, University of Sierra Leone, Freetown (Sierra Leone); Blake, Ruth E., E-mail: ruth.blake@yale.edu [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Chang, Sae Jung [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Jun, Yao, E-mail: yaojun@ustb.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Yu, Chan [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China)

2013-09-15

Highlights: • Phosphonate (phon) hydrolysis by UVR (1.2 kW) attained ≥90% completion in 84 h. • Isotope study reveals both ambient H{sub 2}O and O{sub 2} involvements in phon C-P bond cleavage. • Mechanistic models proposed for phon C-P bond cleavage based on O-isotope analysis. • Model equations used to calculate δ{sup 18}O{sub P-org} of original phon P-moiety-useful as a tracer. • Study shows relevance in tracing phon sources and cycling in the environment. -- Abstract: The degradation of phosphonates in the natural environment constitutes a major route by which orthophosphate (Pi) is regenerated from organic phosphorus and recently implicated in marine methane production, with ramifications to environmental pollution issues and global climate change concerns. This work explores the application of stable oxygen isotope analysis in elucidating the C-P bond cleavage mechanism(s) of phosphonates by UV photo-oxidation and for tracing their sources in the environment. The two model phosphonates used, glyphosate and phosphonoacetic acid were effectively degraded after exposure to UV irradiation. The isotope results indicate the involvement of both ambient water and atmospheric oxygen in the C-P bond cleavage and generally consistent with previously posited mechanisms of UV-photon excitation reactions. A model developed to calculate the oxygen isotopic composition of the original phosphonate P-moiety, shows both synthetic phosphonates having distinctly lower values compared to naturally derived organophosphorus compounds. Such mechanistic models, based on O-isotope probing, are useful for tracing the sources and reactions of phosphonates in the environment.

Prolinol-based nucleoside phosphonic acids: new isosteric conformationally flexible nucleotide analogues

Czech Academy of Sciences Publication Activity Database

Vaněk, Václav; Buděšínský, Miloš; Rinnová, Markéta; Rosenberg, Ivan

2009-01-01

Roč. 65, č. 4 (2009), s. 862-876 ISSN 0040-4020 R&D Projects: GA ČR GA203/05/0827; GA MŠk(CZ) LC06077; GA MŠk LC512; GA MŠk(CZ) LC06061 Institutional research plan: CEZ:AV0Z40550506 Keywords : nucleotide analogues * phosphonates * prolinol derivatives * N- alkylation Subject RIV: CC - Organic Chemistry Impact factor: 3.219, year: 2009

Synthesis and configurational analysis of phosphonate cavitands

NARCIS (Netherlands)

Jacopozzi, Paola; Dalcanale, Enrico; Spera, Silvia; Chrisstoffels, L.A.J.; Reinhoudt, David; Lippmann, Tino; Mann, Gerhard

1998-01-01

Synthesis, separation and configurational analysis of phosphonated and partially phosphonated cavitands derived from resorcinarenes are described. The configuration of all diastereomers has been elucidated by their 1H, 31P NMR spectra and 13C relaxation times. In all cases the course of the bridging

Phosphorus sorption on marine carbonate sediment: phosphonate as model organic compounds.

Science.gov (United States)

Huang, Xiao-Lan; Zhang, Jia-Zhong

2011-11-01

Organophosphonate, characterized by the presence of a stable, covalent, carbon to phosphorus (C-P) bond, is a group of synthetic or biogenic organophosphorus compounds. The fate of these organic phosphorus compounds in the environment is not well studied. This study presents the first investigation on the sorption of phosphorus (P) in the presence of two model phosphonate compounds, 2-aminothylphosphonoic acid (2-AEP) and phosphonoformic acid (PFA), on marine carbonate sediments. In contrast to other organic P compounds, no significant inorganic phosphate exchange was observed in seawater. P was found to adsorb on the sediment only in the presence of PFA, not 2-AEP. This indicated that sorption of P from phosphonate on marine sediment was compound specific. Compared with inorganic phosphate sorption on the same sediments, P sorption from organic phosphorus is much less in the marine environment. Further study is needed to understand the potential role of the organophosphonate compounds in biogeochemical cycle of phosphorus in the environment. Copyright © 2011 Elsevier Ltd. All rights reserved.

Phosphonate removal from discharged circulating cooling water using iron-carbon micro-electrolysis.

Science.gov (United States)

Zhou, Zhen; Qiao, Weimin; Lin, Yangbo; Shen, Xuelian; Hu, Dalong; Zhang, Jianqiao; Jiang, Lu-Man; Wang, Luochun

2014-01-01

Phosphonate is a commonly used corrosion and scale inhibitor for a circulating cooling water (CCW) system. Its discharge could cause eutrophication of receiving waters. The iron-carbon (Fe/C) micro-electrolysis technology was used to degrade and remove phosphonate from discharged CCW. The influences of initial pH, Fe/C ratio (FCR) and temperature on phosphonate removal were investigated in a series of batch tests and optimized by response surface methodology. The quadratic model of phosphonate removal was obtained with satisfactory degrees of fitness. The optimum conditions with total phosphorus removal efficiency of 95% were obtained at pH 7.0, FCR of 1.25, and temperature of 45 °C. The phosphonate removal mechanisms were also studied. Phosphonate removal occurred predominantly via two consecutive reactive phases: the degradation of phosphonate complexes (Ca-phosphonate) and the precipitation of Fe/C micro-electrolysis products (PO₄(3-), Ca²⁺ and Fe³⁺).

Pyrene-Phosphonate Conjugate: Aggregation-Induced Enhanced Emission, and Selective Fe3+ Ions Sensing Properties

Directory of Open Access Journals (Sweden)

Sachin D. Padghan

2017-08-01

Full Text Available A new pyrene-phosphonate colorimetric receptor 1 has been designed and synthesized in a one-step process via amide bond formation between pyrene butyric acid chloride and phosphonate-appended aniline. The pyrene-phosphonate receptor 1 showed aggregation-induced enhanced emission (AIEE properties in water/acetonitrile (ACN solutions. Dynamic light scattering (DLS characterization revealed that the aggregates of receptor 1 at 80% water fraction have an average size of ≈142 nm. Field emission scanning electron microscopy (FE-SEM analysis confirmed the formation of spherical aggregates upon solvent evaporation. The sensing properties of receptor 1 were investigated by UV-vis, fluorescence emission spectroscopy, and other optical methods. Among the tested metal ions, receptor 1 is capable of recognizing the Fe3+ ion selectively. The changes in spectral measurements were explained on the basis of complex formation. The composition of receptor 1 and Fe3+ ions was determined by using Job’s plot and found to be 1:1. The receptor 1–Fe3+ complex showed a reversible UV-vis response in the presence of EDTA.

Hydrothermal syntheses, characterizations and crystal structures of a new lead(II) carboxylate-phosphonate with a double layer structure and a new nickel(II) carboxylate-phosphonate containing a hydrogen-bonded 2D layer with intercalation of ethylenediamines

International Nuclear Information System (INIS)

Song, J.-L.; Mao, J.-G.; Sun, Y.-Q.; Zeng, H.-Y.; Kremer, R.K.; Clearfield, Abraham

2004-01-01

Hydrothermal reactions of N,N-bis(phosphonomethyl)aminoacetic acid (HO 2 CCH 2 N(CH 2 PO 3 H 2 ) 2 ) with metal(II) salts afforded two new metal carboxylate-phosphonates, namely, Pb 2 [O 2 CCH 2 N(CH 2 PO 3 )(CH 2 PO 3 H)]·H 2 O (1) and {NH 3 CH 2 CH 2 NH 3 }{Ni[O 2 CCH 2 N(CH 2 PO 3 H) 2 ](H 2 O) 2 } 2 (2). Among two unique lead(II) ions in the asymmetric unit of complex 1, one is five coordinated by five phosphonate oxygen atoms from 5 ligands, whereas the other one is five-coordinated by a tridentate chelating ligand (1 N and 2 phosphonate O atoms) and two phosphonate oxygen atoms from two other ligands. The carboxylate group of the ligand remains non-coordinated. The bridging of above two types of lead(II) ions through phosphonate groups resulted in a double layer with the carboxylate group of the ligand as a pendant group. These double layers are further interlinked via hydrogen bonds between the carboxylate groups into a 3D network. The nickel(II) ion in complex 2 is octahedrally coordinated by a tetradentate chelating ligand (two phosphonate oxygen atoms, one nitrogen and one carboxylate oxygen atoms) and two aqua ligands. These {Ni[O 2 CCH 2 N(CH 2 PO 3 H) 2 ][H 2 O] 2 } - anions are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form a hydrogen bonded 2D layer. The 2H-protonated ethylenediamine cations are intercalated between two layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Results of magnetic measurements for complex 2 indicate that there is weak Curie-Weiss behavior with θ=-4.4 K indicating predominant antiferromagnetic interaction between the Ni(II) ions. Indication for magnetic low-dimension magnetism could not be detected

Catalytic phosphonation of high performance polymers and POSS. Novel components for polymer blend and nanocomposite fuel cell membranes

Energy Technology Data Exchange (ETDEWEB)

Bock, T.R.

2006-10-15

Aim of this thesis was the preparation and evaluation of phosphonated high performance (HP) polyelectrolytes and polyhedral oligomeric silsesquioxanes (POSS) for polyelectrolyte membrane fuel cell (PEMFC) application. Brominated derivatives of the commercial high performance (HP) polymers poly(ethersulfone) (PES), poly(etheretherketone) (PEEK), poly(phenylsulfone) (PPSu), poly(sulfone) (PSU) and of octaphenyl-POSS of own production were phosphonated by Ni-catalysed Arbuzov reaction. Phosphonated PSU was cast into pure and blend films with sulfonated PEEK (s-PEEK) to investigate H+-conductivity, water uptake and film morphology. Blend films' properties were referenced to films containing unmodified blend partners. Solution-compounding of phosphonated octaphenyl-POSS and s-PEEK was used to produce novel nanocomposite films. An in-situ zirconisation method was assessed as convenient strategy for novel ionically crosslinked membranes of enhanced swelling resistance. Dibromo isocyanuric acid (DBI) and N-bromo succinimide (NBS) as brominating agents allowed polymer analogous preparation of the novel brominated PES and PEEK with precise reaction control. A random distribution of functional groups, i.e. polyelectrolytes' microstructural homogeneity was revealed as decisive factor concerning solubility of phosphonated PSU. Brominated phT8 was prepared with Br2 by a high temperature approach in tetrachloroethane (TCE). Brominated polymers were phosphonated by Ni-catalysis in non-coordinating high temperature solvents, such as diphenylether, benzophenone and diphenylsulfone without notable solvent influence. The lack of solvent - catalyst complexes and high reaction temperatures of 180-200 C led to halogen-free phosphonates with unprecedented high functionalities. Polymer analogous application of P(OSiMe3)3 offered a novel direct access to easily cleavable disilyl ester derivatives. These were obtained from PEEK and PSU in near quantitative yields at NiCl2-loads as

Sustainable Catalytic Process for Synthesis of Triethyl Citrate Plasticizer over Phosphonated USY Zeolite

Directory of Open Access Journals (Sweden)

Kakasaheb Y. Nandiwaleand

2016-10-01

Full Text Available Fruits wastage is harmful to health and environment concerning spreading diseases and soil pollution, respectively. To avoid this issue, use of citrus fruit waste for the production of citric acid (CA is one of viable mean to obtain value added chemicals. Moreover, synthesis of triethyl citrate (TEC, a non-toxic plasticizer by esterification of CA with ethanol over heterogeneous catalyst would be renewable and sustainable catalytic process. In this context, parent Ultrastable Y (USY and different percentage phosphonated USY (P-USY zeolites were used for the synthesis of TEC in a closed batch reactor, for the first time. The synthesized catalysts were characterized by N2-adsorption desorption isotherm, powder X-ray diffraction (XRD and NH3 temperature programmed desorption (TPD. Effect of reaction conditions, such as the molar ratio of ethanol to CA (5:1 - 20:1, the catalyst to CA ratio (0.05 - 0.25 and reaction temperature (363-403 K, were studied in view to maximizing CA conversion and TEC yield. Phosphonated USY catalysts were found to be superior in activity (CA conversion and TEC yield than parent USY, which is attributed to the increased in total acidity with phosphonation. Among the studied catalysts, the P2USY (2% phosphorous loaded on USY was found to be an optimum catalyst with 99% CA conversion and 82% TEC yield, which is higher than the reported values. This study opens new avenues of research demonstrating principles of green chemistry such as easy separable and reusable catalyst, non-toxic product, bio-renewable synthetic route, milder operating parameters and waste minimization. Copyright © 2016 BCREC GROUP. All rights reserved Received: 12nd October 2015; Revised: 22nd December 2015; Accepted: 29th January 2016 How to Cite: Nandiwale, K.Y., Bokade, V.V. (2016. Sustainable Catalytic Process for Synthesis of Triethyl Citrate Plasticizer over Phosphonated USY Zeolite. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 292

Design, synthesis, and activity of 2,3-diphosphoglycerate analogs as allosteric modulators of hemoglobin O2 affinity.

Science.gov (United States)

Kassa, Tigist W; Zhang, Ning; Palmer, Andre F; Matthews, Jason Shastri

2013-04-01

Four phosphonate derivates of 2,3-diphosphoglycerate (2,3-DPG), in which the phosphate group is replaced by a methylene or difluoromethylene, were successfully synthesized for use as allosteric modulators of hemoglobin (Hb) O2 affinity. The syntheses were accomplished in four steps and the reagents were converted to their potassium salts to allow for effective binding with Hb in aqueous media. O2 equilibrium measurements of the chemically modified Hbs exhibited P50 values in the range 8.9-12.8 with Hill coefficients in the range of 1.5-2.4.

The development of Sm-153 EDTMP (ethylene diamine tetramethylene phosphonic acid), a bone seeking radiotherapeutic agent

International Nuclear Information System (INIS)

Rehir Dahalan; Wan Anuar Wan Awang; Shaaban Kassim

1997-01-01

Diagnostic radiopharmaceuticals have been the workhorse of nuclear medicine since it began in the early fifties, with the exception of radioiodine, which was also a therapeutic radiopharmaceutical. Over the years, significant advancement in the design of the diagnostic radiopharmaceuticals, have enabled optimum delivery of, the gamma emitting radionuclide to the target organs, whilst minimizing the dose to the non-target organs. This technology was utilized in this work, to deliver destructive beta emitting radionuclide to target cancerous tissues with the hope of slowing down or completely ablating its growth. This work had been in the production of Sm-153 using the MINT research reactor (MINTRR) and labeling it to the ethylene diamine tetramethylene phosphonic acid (EDTMP) ligand, a bone seeking complex. The results of this work have established the optimum labeling conditions and showed the biodistribution of the Sm-153 EDTMP complex in the rat

The Influence of Lactic Acid Concentration on the Separation of Light Rare Earth Elements by Continuous Liquid-Liquid Extraction with 2-Ethylhexyl Phosphonic Acid Mono-2-ethylhexyl Ester

Science.gov (United States)

de Carvalho Gomes, Rafael; Seruff, Luciana Amaral; Scal, Maira Labanca Waineraich; Vera, Ysrael Marrero

2018-02-01

The separation of rare earth elements (REEs) using solvent extraction adding complexing agents appears to be an alternative to saponification of the extractant. We evaluated the effect of lactic acid concentration on didymium (praseodymium and neodymium) and lanthanum extraction with 2-ethylhexyl phosphonic acid mono-2-ethyl hexyl ester [HEH(EHP)] as extractant. First, we investigated in batch experiments the separation of lanthanum (La) and didymium (Pr and Nd) using McCabe-Thiele diagrams to estimate the number of extraction stages when the feed solution was or was not conditioned with lactic acid. Additionally, we conducted continuous liquid-liquid extraction experiments and evaluated the influence of lactic acid concentration on the REE extraction and separation. The tests showed that the extraction percentage of REEs and the separation factor Pr/La increased when the lactic acid concentration increased, but the didymium purity decreased. Lanthanum, praseodymium, and neodymium extraction rate were 23.0, 89.7, and 99.2 pct, respectively, with 1:1 aqueous/organic volume flow rate and feed solution doped with 0.52 mol L-1 lactic acid. The highest didymium purity reached was 92.0 pct with 0.26 mol L-1 lactic acid concentration.

Design and Synthesis of Fluorescent Acyclic Nucleoside Phosphonates as Potent Inhibitors of Bacterial Adenylate Cyclases

Czech Academy of Sciences Publication Activity Database

Břehová, Petra; Šmídková, Markéta; Skácel, Jan; Dračínský, Martin; Mertlíková-Kaiserová, Helena; Velasquez, M. P. S.; Watts, V. J.; Janeba, Zlatko

2016-01-01

Roč. 11, č. 22 (2016), s. 2534-2546 ISSN 1860-7179 R&D Projects: GA MV VG20102015046; GA MŠk LO1302 Institutional support: RVO:61388963 Keywords : adenylate cyclase toxin * acyclic nucleoside phosphonates * anthranilic acid Subject RIV: CC - Organic Chemistry Impact factor: 3.225, year: 2016

The efficient synthesis of 2-arylpyrimidine acyclic nucleoside phosphonates using Liebeskind-Srogl cross-coupling reaction

Czech Academy of Sciences Publication Activity Database

Břehová, Petra; Česnek, Michal; Dračínský, Martin; Holý, Antonín; Janeba, Zlatko

2011-01-01

Roč. 67, č. 38 (2011), s. 7379-7385 ISSN 0040-4020 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : Liebeskind-Srogl cross - coupling * acyclic nucleoside phosphonates * pyrimidines * arylboronic acids * microwave Subject RIV: CC - Organic Chemistry Impact factor: 3.025, year: 2011

Increasing the fill factor of inverted P3HT:PCBM solar cells through surface modification of Al-doped ZnO via phosphonic acid-anchored C60 SAMs

Energy Technology Data Exchange (ETDEWEB)

Stubhan, Tobias [Institute of Materials for Electronics and Energy Technology (I-MEET), Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Salinas, Michael; Halik, Marcus [Organic Materials and Devices (OMD)-Institute of Polymer Materials, University Erlangen-Nuremberg, Erlangen (Germany); Ebel, Alexander; Hirsch, Andreas [Institute for Organic Chemistry II, Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Krebs, Frederick C. [Risoe National Laboratory for Sustainable Energy, Technical University of Denmark, Roskilde (Denmark); Brabec, Christoph J. [Institute of Materials for Electronics and Energy Technology (I-MEET), Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Bavarian Center for Applied Energy Research (ZAE Bayern), Erlangen (Germany)

2012-05-15

The influence of aluminum-doped zinc oxide (AZO) electron extraction layers modified with self-assembled monolayers (SAMs) on inverted polymer solar cells is investigated. It is found that AZO modification with phosphonic acid-anchored Fullerene-SAMs leads to a reduction of the series resistance, while increasing the parallel resistance. This results in an increased efficiency from 2.9 to 3.3%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Supercritical fluid extraction of uranium and thorium from nitric acid medium using organophosphorous compounds

Energy Technology Data Exchange (ETDEWEB)

Pitchaiah, K.C.; Sujatha, K.; Rao, C.V.S. Brahmmananda; Subramaniam, S.; Sivaraman, N.; Rao, P.R. Vasudeva [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2015-06-01

In recent years, Supercritical Fluid Extraction (SFE) technique has been widely used for the extraction of metal ions. In the present study, extraction of uranium from nitric acid medium was investigated using supercritical carbon dioxide (Sc-CO{sub 2}) containing various organophosphorous compounds such as trialkyl phosphates e.g. tri-iso-amyl phosphate (TiAP), tri-sec-butyl phosphate (TsBP) and tri-n-butyl phosphate (TBP), dialkylalkyl phosphonates, e.g. diamylamyl phosphonate (DAAP) and dibutyl butyl phosphonate (DBBP), dialkyl hydrogen phosphonates, e.g. dioctyl hydrogen phosphonate (DOHP), dioctylphosphineoxide (DOPO), trioctyl phosphine oxide (TOPO), n-octylphenyl N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO) and di-2-ethyl-hexyl phosphoric acid (HDEHP). Some of these ligands have been investigated for the first time in the supercritical phase for the extraction of uranium. The extraction efficiency of uranium was studied with TiAP, DAAP and DBBP as a function of nitric acid concentration; the kinetics of the equilibration period (static extraction) and transportation of the metal complex (dynamic extraction) was investigated. The influence of pressure and temperature on the extraction behaviour of uranium with DAAP was studied from 4 N HNO{sub 3}. The extraction efficiency of uranium from 4 N nitric acid medium was found to increase in the order of phosphates < phosphonates < HDEHP < TOPO < CMPO. In the case of phosphates and phosphonates, the maximum extraction of uranium was found to be from 4 N HNO{sub 3} medium. The acidic extractants, HDEHP and DOHP showed relatively higher extraction at lower acidities. The relative extraction of uranium and thorium from their mixture was also examined using Sc-CO{sub 2} containing phosphates, phosphonates and TOPO. The ligand, TsBP provided better fractionation between uranium and thorium compared to trialkyl phosphates, dialkyl alkyl phosphonates and TOPO.

Phosphonic acids aid composition adjustment in the synthesis of Cu_2_+_xZn_1_−_xSnSe_4_−_y nanoparticles

International Nuclear Information System (INIS)

Ibáñez, Maria; Berestok, Taisiia; Dobrozhan, Oleksandr; LaLonde, Aaron; Izquierdo-Roca, Victor; Shavel, Alexey; Pérez-Rodríguez, Alejandro; Snyder, G. Jeffrey; Cabot, Andreu

2016-01-01

The functional properties of quaternary I_2–II–IV–VI_4 nanomaterials, with potential interest in various technological fields, are highly sensitive to compositional variations, which is a challenging parameter to adjust. Here we demonstrate the presence of phosphonic acids to aid controlling the reactivity of the II element monomer to be incorporated in quaternary Cu_2ZnSnSe_4 nanoparticles and thus to provide a more reliable way to adjust the final nanoparticle metal ratios. Furthermore, we demonstrate the composition control in such multivalence nanoparticles to allow modifying charge carrier concentrations in nanomaterials produced from the assembly of these building blocks.

Equilibrium Studies on the Extraction of Yttrium from Chloride Medium by Mono (2-Ethylhexyl) 2-Ethylhexyl Phosphonic Acid (Ion quest 801)

International Nuclear Information System (INIS)

Zaki, E.E.; Ismail, Z.H.; Aly, H.F.; Sabet, S.A.

2008-01-01

Since 90 Y is one of the useful radioisotopes in nuclear medicine, liquid-liquid extraction of yttrium from chloride medium has been studied under various conditions using neutralized and un-neutralized mono (2-ethylhexyl) 2-ethylhexyl phosphonic acid (EHEHPA) as an extractant. Effect of reagent concentration, ph of the aqueous medium, metal ion concentration and nature of the diluent on the extraction process has been carried out. Effect of temperature was studied and thermodynamic parameters were evaluated. Yttrium extracted in organic phase was stripped with various reagents. The stoichiometry of the extracted species of yttrium was determined on the basis of slope analysis of experimental results. Equilibrium equations of the extraction process have been estimated and verified

Pitting corrosion of copper in aqueous solutions containing phosphonic acid as an inhibitor. Hosuhon san wo inhibita toshite fukumu suiyoekichu ni okeru do no koshiku ni tsuite

Energy Technology Data Exchange (ETDEWEB)

Yamada, Y. (Muroran Univ., Hokkaido (Japan). Graduate School); Seri, O.; Tagashira, K. (Muroran Univ., Hokkaido (Japan)); Nagata, K. (Sumitomo Light Metal Co. Ltd., Tokyo (Japan). Technical Research Lab.)

1993-09-15

Phosphonic acid-based inhibitors that are poured into cooling water for copper-tube circulation systems for open heat-accumulators were studied on their influence on pitting corrosion of copper. Amino trimethylene phosphonic acid (ATMP) dissolved into distilled water to 50 ppm was used for the immersion corrosion test. The corrosion-proof effect of additives such as ZnSO4, benzotriazole (BTA) was tested too. 0.5 mm thick phosphate-treated copper plates with a hole of 5 mm in diameter were used as test specimens. Pitting corrosion on the copper plate occurred when ATMP, BTA and ZnSO4 coexisted. It was proved that SO4 [sup 2-] is essential since Na2SO4 in stead of ZnSO4 induced also corrosion. The pitting took place when 0.6 ppm or more of SO4 [sup 2-] was present in a BTA-added ATMP solution. It was observed that the pitting is prone to occur with increase of SO4 [sup 2-] and the number of pitting increases. The following relationship is established when pitting corrosion occurs; E[sub b] [le] E[sub corr], where the former is a potential value at which current density shows a steep increase and the latter is an average value of spontaneous electrode potential showing a plateau. 8 refs., 11 figs., 1 tab.

Synthesis and Properties of a Novel Type of Acyclic Nucleoside Phosphonates: 2-(Purin-9-yl)ethoxyphenylphosphonic Acids

Czech Academy of Sciences Publication Activity Database

Hocková, Dana; Dračínský, Martin; Holý, Antonín

-, č. 15 (2010), s. 2885-2892 ISSN 1434-193X R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : nucleotides * phosphonates * cross-coupling Subject RIV: CC - Organic Chemistry Impact factor: 3.206, year: 2010

Fluoride-Mediated Dephosphonylation of α-Diazo-β-carbonyl Phosphonates.

Science.gov (United States)

Phatake, Ravindra S; Mullapudi, Venkannababu; Wakchaure, Vivek C; Ramana, Chepuri V

2017-01-20

The possibility of fluoride-mediated selective dephosphonylation of α-diazo-β-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting α-diazocarbonyl intermediates undergo a (3 + 2)-cycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess α-diazo-β-carbonyl phosphonates) or Michael addition (with conjugated olefins).

Acid-base properties of complexes with three-dimensional polyligands. Complexes with three-dimensional polyphosphoric acids

International Nuclear Information System (INIS)

Kopylova, V.D.; Bojko, Eh.T.; Saldadze, K.M.

1985-01-01

By the method of potentiometric titration acid-base properties of uranyl (2) complexes with three-dimensional polyphosphoric acids, KRF-8p, KF-1, KF-7 prepared by phosphorylation of copolymer of styrene and divinylbenzene or saponification of the copolymers of di-2,2'-chloroethyl ester of vinylphosphonic acid with divinyl benzene are studied. It is shown that in case of formation in the phase of three-dimensional polyphosphoric acids of UO 2 2+ complexes with the growth of bond covalence of metal ion-phosphonic group the acidjty of the second hydroxyl of the phosphonic group increases

On the stereochemistry of C3'-O-P-CH2-O-C4'' phosphonate internucleotide bond, a phosphate isostere

Czech Academy of Sciences Publication Activity Database

Točík, Zdeněk; Buděšínský, Miloš; Barvík Jr., I.; Rosenberg, Ivan

-, č. 52 (2008), s. 427-428 ISSN 0261-3166. [Joint Symposium of the International Roundtable on Nucleosides, Nucleotides and Nucleic Acids /18./ and the International Symposium on Nucleic Acid Chemistry /35./. Kyoto, 08.09.2008-12.09.2008] R&D Projects: GA MŠk(CZ) LC06061 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonate oligonucleotide stereochemistry Subject RIV: CC - Organic Chemistry

Complexation of 188Re-phosphonates: in vitro and in vivo studies

International Nuclear Information System (INIS)

Faintuch, B.L.; Muramoto, E.; Faintuch, S.

2003-01-01

MDP (methylenediphosphonate) and HEDP (hydroxyethylidene diphosphonate), both disphosphonates, and EDTMP (ethylenediamine tetramethylene phosphonic acid), a tetraphosphonate ligand, have been previously labeled with 188 Re for use in metastatic bone-pain palliation. The aim of this study was a comparison between the three complexes 188 Re-MDP, 188 Re-HEDP and 188 Re-EDTMP concerning the complexation conditions, in order to achieve maximum yield, stability and bone uptake. Methods: MDP was dissolved in water and HEDP and EDTMP were dissolved in NaOH 1 N followed by reduction of pH with HCl 1 N. To all mixtures stannous chloride and 188 ReO 4 - were added in a nitrogen atmosphere. The preparations were heated in boiling water bath for 15 min. Yield as well as radiochemical stability was estimated by ITLC. Different concentrations of phosphonates and stannous chloride were evaluated. Biodistribution studies in Swiss mice were done for the three 188 Re-phosphonates that presented the best radiochemical yield. The optimal ligand concentration for maximum complexation was 85.2 mM for MDP, 72.8 mM for HEDP and 45.8 mM for EDTMP. The best amount of SnCl 2 .2H 2 O was 1.5 mg/mL for 188 Re-HEDP and 1 mg/mL for both 188 Re-MDP and 188 Re-EDTMP. In these conditions the three complexes showed a complexation rate above 95%. Reasonable radiochemical stability for 24 hours was achieved by 188 Re-EDTMP when employing ascorbic acid. All products showed a great uptake by the kidneys. 188 Re-EDTMP had the greatest uptake by femur (3.1 ± 0.2% ID/g) followed by 188 Re-MDP (1.2 ± 0.1% ID/g) and 188 Re-HEDP (1.0 ± 0.1% ID/g), 4 hours post injection. 188 Re-EDTMP displayed a femur bone/muscle ratio of 28.5, 188 Re-MDP 4.9 and 188 Re-HEDP 4.9. In conclusion 188 Re-EDTMP demonstrated the best potential as a radiopharmaceutical for bone cancer pain relief, encouraging further dosimetric studies and clinical trials. (orig.)

Synthesis, self-assembly and lipoplex formulation of two novel cyclic phosphonate lipids

Directory of Open Access Journals (Sweden)

JenniferYeh

2013-05-01

Full Text Available Background: Synthetic cationic lipids hold much potential as gene packaging and delivery agents for the treatment of inherited and acquired life threatening diseases, such as cancer, AIDS, cardiovascular diseases, and certain autoimmune disorders. Methods: We report the synthesis, self-assembly as characterized by critical micelle concentrations and plasmid DNA gel retardation using two novel cyclic, phosphonate cationic lipids 2a and 2b, which were synthesized by derivatizing two diastereomeric macrocyclic phosphonates 1a and 1b with a 2-carbon hydroxylamine linker, N, N-dimethylethanolamine (3. Results: The production of cyclic phosphonate lipids 2a and 2b in 73% and 60% yields, respectively, was achieved using classical synthetic methods involving nucleophilic substitution at the phosphorus centre. Conclusions: The synthesis, aggregation and DNA binding properties of these novel cyclic phosphonate lipids suggest that they may have utility serving as gene packaging and delivery agents.

Metastatic Bone Pain Palliation using 177Lu-Ethylenediaminetetramethylene Phosphonic Acid

International Nuclear Information System (INIS)

Alavi, Mehrosadat; Omidvari, Shapour; Mehdizadeh, Alireza; Jalilian, Amir R.; Bahrami-Samani, Ali

2015-01-01

177 Lu-ethylenediaminetetramethylene phosphonic acid (EDTMP) is presently suggested as an excellent bone seeking radionuclide for developing metastatic bone pain (MBP) palliation agent owing to its suitable nuclear decay characteristics. To find the exact dosage and its efficiency, this clinical study was performed on the human being, using 177 Lu-EDTMP for MBP palliation. 177 Lu-EDTMP was prepared by Iran, atomic energy organization. Thirty consecutive patients with determined tumors, incontrollable MBP, and positive bone scan at 4 weeks before the beginning of the study participated in this study in the nuclear medicine ward. 177 Lu-EDTMP in the form of sterile slow IV injection was administered with a dose of 29.6 MBq/kg. Short form of brief pain inventory questionnaire was used to evaluate the efficiency of the intervention. Questionnaires were filled out by an expert nuclear physician every 2 weeks while the cell blood count was also checked every 2 weeks up to 12 weeks for evaluation of bone marrow suppression and hematological toxicity. Furthermore, whole body scan was done at days 1, 3, and 7. Twenty-five patients showed a significant pain relief since 2 weeks after the injection, and continued until the end of the follow up period (12 weeks). There were no significant early complications such as bone marrow suppression, hematological toxicity, and no systemic adverse effects. No complication was observed in renal function. Twenty one patients showed flare phenomenon that was started after the 12.2 ± 1.78 h lasting for 38.4 ± 23.08. Sixteen patients (53%) were completely treated; nine patients (30%) showed a partial response, and five patients (17%) had no response to treatment. Total response to treatment was achieved in 25 patients (83%). At the end of the evaluation, no bone marrow suppression or hematologic toxicity was observed. 177 Lu-EDTMP has shown suitable physical and biological properties with good results in long term bone pain relief for

Metastatic Bone Pain Palliation using (177)Lu-Ethylenediaminetetramethylene Phosphonic Acid.

Science.gov (United States)

Alavi, Mehrosadat; Omidvari, Shapour; Mehdizadeh, Alireza; Jalilian, Amir R; Bahrami-Samani, Ali

2015-01-01

(177)Lu-ethylenediaminetetramethylene phosphonic acid (EDTMP) is presently suggested as an excellent bone seeking radionuclide for developing metastatic bone pain (MBP) palliation agent owing to its suitable nuclear decay characteristics. To find the exact dosage and its efficiency, this clinical study was performed on the human being, using (177)Lu-EDTMP for MBP palliation. (177)Lu-EDTMP was prepared by Iran, atomic energy organization. Thirty consecutive patients with determined tumors, incontrollable MBP, and positive bone scan at 4 weeks before the beginning of the study participated in this study in the nuclear medicine ward. (177)Lu-EDTMP in the form of sterile slow IV injection was administered with a dose of 29.6 MBq/kg. Short form of brief pain inventory questionnaire was used to evaluate the efficiency of the intervention. Questionnaires were filled out by an expert nuclear physician every 2 weeks while the cell blood count was also checked every 2 weeks up to 12 weeks for evaluation of bone marrow suppression and hematological toxicity. Furthermore, whole body scan was done at days 1, 3, and 7. Twenty-five patients showed a significant pain relief since 2 weeks after the injection, and continued until the end of the follow up period (12 weeks). There were no significant early complications such as bone marrow suppression, hematological toxicity, and no systemic adverse effects. No complication was observed in renal function. Twenty one patients showed flare phenomenon that was started after the 12.2 ± 1.78 h lasting for 38.4 ± 23.08. Sixteen patients (53%) were completely treated; nine patients (30%) showed a partial response, and five patients (17%) had no response to treatment. Total response to treatment was achieved in 25 patients (83%). At the end of the evaluation, no bone marrow suppression or hematologic toxicity was observed. (177)Lu-EDTMP has shown suitable physical and biological properties with good results in long term bone pain relief for

Metastatic Bone Pain Palliation using 177Lu-Ethylenediaminetetramethylene Phosphonic Acid

Science.gov (United States)

Alavi, Mehrosadat; Omidvari, Shapour; Mehdizadeh, Alireza; Jalilian, Amir R.; Bahrami-Samani, Ali

2015-01-01

177Lu-ethylenediaminetetramethylene phosphonic acid (EDTMP) is presently suggested as an excellent bone seeking radionuclide for developing metastatic bone pain (MBP) palliation agent owing to its suitable nuclear decay characteristics. To find the exact dosage and its efficiency, this clinical study was performed on the human being, using 177Lu-EDTMP for MBP palliation. 177Lu-EDTMP was prepared by Iran, atomic energy organization. Thirty consecutive patients with determined tumors, incontrollable MBP, and positive bone scan at 4 weeks before the beginning of the study participated in this study in the nuclear medicine ward. 177Lu-EDTMP in the form of sterile slow IV injection was administered with a dose of 29.6 MBq/kg. Short form of brief pain inventory questionnaire was used to evaluate the efficiency of the intervention. Questionnaires were filled out by an expert nuclear physician every 2 weeks while the cell blood count was also checked every 2 weeks up to 12 weeks for evaluation of bone marrow suppression and hematological toxicity. Furthermore, whole body scan was done at days 1, 3, and 7. Twenty-five patients showed a significant pain relief since 2 weeks after the injection, and continued until the end of the follow up period (12 weeks). There were no significant early complications such as bone marrow suppression, hematological toxicity, and no systemic adverse effects. No complication was observed in renal function. Twenty one patients showed flare phenomenon that was started after the 12.2 ± 1.78 h lasting for 38.4 ± 23.08. Sixteen patients (53%) were completely treated; nine patients (30%) showed a partial response, and five patients (17%) had no response to treatment. Total response to treatment was achieved in 25 patients (83%). At the end of the evaluation, no bone marrow suppression or hematologic toxicity was observed. 177Lu-EDTMP has shown suitable physical and biological properties with good results in long term bone pain relief for patients

Relative binding affinity of carboxylate-, phosphonate-, and bisphosphonate-functionalized gold nanoparticles targeted to damaged bone tissue

Energy Technology Data Exchange (ETDEWEB)

Ross, Ryan D. [Rush University Medical Center, Department of Anatomy and Cell Biology (United States); Cole, Lisa E.; Roeder, Ryan K., E-mail: rroeder@nd.edu [University of Notre Dame, Department of Aerospace and Mechanical Engineering Bioengineering Graduate Program (United States)

2012-10-15

Functionalized Au NPs have received considerable recent interest for targeting and labeling cells and tissues. Damaged bone tissue can be targeted by functionalizing Au NPs with molecules exhibiting affinity for calcium. Therefore, the relative binding affinity of Au NPs surface functionalized with either carboxylate (l-glutamic acid), phosphonate (2-aminoethylphosphonic acid), or bisphosphonate (alendronate) was investigated for targeted labeling of damaged bone tissue in vitro. Targeted labeling of damaged bone tissue was qualitatively verified by visual observation and backscattered electron microscopy, and quantitatively measured by the surface density of Au NPs using field-emission scanning electron microscopy. The surface density of functionalized Au NPs was significantly greater within damaged tissue compared to undamaged tissue for each functional group. Bisphosphonate-functionalized Au NPs exhibited a greater surface density labeling damaged tissue compared to glutamic acid- and phosphonic acid-functionalized Au NPs, which was consistent with the results of previous work comparing the binding affinity of the same functionalized Au NPs to synthetic hydroxyapatite crystals. Targeted labeling was enabled not only by the functional groups but also by the colloidal stability in solution. Functionalized Au NPs were stabilized by the presence of the functional groups, and were shown to remain well dispersed in ionic (phosphate buffered saline) and serum (fetal bovine serum) solutions for up to 1 week. Therefore, the results of this study suggest that bisphosphonate-functionalized Au NPs have potential for targeted delivery to damaged bone tissue in vitro and provide motivation for in vivo investigation.

C-H Phosphonation of Pyrrolopyrimidines: Synthesis of Substituted 7-and 9-Deazapurine-8-phosphonate Derivatives

Czech Academy of Sciences Publication Activity Database

Sabat, Nazarii; Poštová Slavětínská, Lenka; Klepetářová, Blanka; Hocek, Michal

2016-01-01

Roč. 81, č. 19 (2016), s. 9507-9514 ISSN 0022-3263 R&D Projects: GA ČR(CZ) GA16-00178S; GA MŠk(CZ) LO1304 Institutional support: RVO:61388963 Keywords : cross - coupling reactions * acyclic nucleoside phosphonates * biological activity Subject RIV: CC - Organic Chemistry Impact factor: 4.849, year: 2016

Synthesis of tritium labelled phosphonate analogues of sphinganine-1-phosphate

International Nuclear Information System (INIS)

Schick, Andreas; Schwarzmann, Guenter; Kolter, Thomas; Sandhoff, Konrad

1997-01-01

Tritiated phosphonate analogues 9 and 10 are prepared as analogues of sphinganine-1-phosphate 4. The key step in this synthesis is the catalytic tritiation of the triple bond in reduction of the protected diethyl-3-(S)-tert.-butoxycarbonylamino -4-hydroxy-5-tridecinyl-1-phosphonate by means of sodium boro[ 3 H]hydride as tritium source. These compounds are synthesized to study their metabolic stability and to evaluate their biological properties. (author)

The First Synthesis and Anti-retroviral Activity of 5',5'-Difluoro-3'-Hydroxy-Apiosyl Nucleoside Cyclomonophosphonic Acid Analogs

Energy Technology Data Exchange (ETDEWEB)

Kim, Seyeon; Hong, Joon Hee [Chosun University, Gwangju (Korea, Republic of)

2016-04-15

The first synthesis of novel 5',5'-difluoro-30-hydroxy apiose nucleoside cyclomonophosphonic acid analogs was performed as potent anti-retroviral agents. Phosphonation was performed by direct displacement of a triflate intermediate with diethyl(lithiodifluoromethyl) phosphonate to give the corresponding(α, α-difluoroalkyl) phosphonate. Condensation successfully proceeded from a glycosyl donor with persilylated bases to yield the nucleoside phosphonate analogs. Deprotection of diethyl phosphonates provided the target nucleoside cyclomonophosphonic acid analogs. The synthesized nucleoside analogs were subjected to anti-viral screening against the human immunodeficiency virus-1 (HIV-1). Cytosine analogs show significant anti-HIV activity.

Anti-HIV therapy with AZT prodrugs: AZT phosphonate derivatives, current state and prospects.

Science.gov (United States)

Khandazhinskaya, Anastasiya; Matyugina, Elena; Shirokova, Elena

2010-06-01

AIDS, a disease caused by human immunodeficiency virus, was called 'plague of the twentieth century'. 3'-Azido-3'-deoxythymidine (AZT), the first compound approved for the treatment of HIV, is still a mandatory component of treatment schemes. However, its toxicity stimulated a search for new agents. This review presents the history and current state of the design of AZT prodrugs based on its phosphonate derivatives. Although every effort was made to include as many AZT structures bearing phosphonate residues and demonstrate the variety they offer, we also concentrated on the studies performed in our laboratory. Special attention was also paid to AZT 5'-H-phosphonate (phosphazide, Nikavir) approved in the Russian Federation as a drug for the prevention and treatment of HIV infection. The prodrug strategy applied to AZT phosphonate derivatives enriched chemistry, biology and medicine not only with new knowledge, methods and structures, but also with a new anti-HIV drug Nikavir. Currently, study of another phosphonate, AZT 5'-aminocarbonylphosphonate, is underway. Slow release of AZT following oral administration and penetration into cells, decreased toxicity and the lack of cumulative properties make the compounds of this group promising as extended-release forms of AZT.

Synthesis and Functionalization of Poly(ethylene oxide-b-ethyloxazoline) Diblock Copolymers with Phosphonate Ions

OpenAIRE

Chen, Alfred Yuen-Wei

2013-01-01

Poly(ethylene oxide) (PEO) and poly(2-ethyl-2-oxazoline) (PEOX) are biocompatible polymers that act as hydrophilic "stealth" drug carriers. As block copolymers, the PEOX group offers a wider variety of functionalization. The goal of this project was to synthesize a poly(ethylene oxide)-b-poly(2-ethyl-2-oxazoline) (PEO-b-PEOX) block copolymer and functionalize pendent groups of PEOX with phosphonic acid. This was achieved through cationic ring opening polymerization (CROP) of 2-...

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

Science.gov (United States)

Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

2015-11-15

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore. Copyright © 2015 Elsevier Ltd. All rights reserved.

Phosphonic acids aid composition adjustment in the synthesis of Cu{sub 2+x}Zn{sub 1−x}SnSe{sub 4−y} nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Ibáñez, Maria; Berestok, Taisiia; Dobrozhan, Oleksandr [Catalonia Institute for Energy Research (IREC) (Spain); LaLonde, Aaron [California Institute of Technology, Materials Science (United States); Izquierdo-Roca, Victor; Shavel, Alexey; Pérez-Rodríguez, Alejandro [Catalonia Institute for Energy Research (IREC) (Spain); Snyder, G. Jeffrey [California Institute of Technology, Materials Science (United States); Cabot, Andreu, E-mail: acabot@irec.cat [Catalonia Institute for Energy Research (IREC) (Spain)

2016-08-15

The functional properties of quaternary I{sub 2}–II–IV–VI{sub 4} nanomaterials, with potential interest in various technological fields, are highly sensitive to compositional variations, which is a challenging parameter to adjust. Here we demonstrate the presence of phosphonic acids to aid controlling the reactivity of the II element monomer to be incorporated in quaternary Cu{sub 2}ZnSnSe{sub 4} nanoparticles and thus to provide a more reliable way to adjust the final nanoparticle metal ratios. Furthermore, we demonstrate the composition control in such multivalence nanoparticles to allow modifying charge carrier concentrations in nanomaterials produced from the assembly of these building blocks.

Flame retardant cotton fabrics by electron beam-induced polymerization of vinyl phosphonate oligomer

International Nuclear Information System (INIS)

Sawai, Takeshi; Ametani, Kazuo; Enomoto, Ichiro

1988-01-01

Vinyl phosphonate oligomer is presently used commercially as a cellulosic flame retardant in conjugation with N-methylol acrylamide, using a persulfate catalyst and a thermal cure. This combination can also be cured at room temperature with electron beams, as can the vinyl phosphonate alone. For the textile application, fixation of flame retardants by electron beams with low energy is one of the most promising applications. For the purpose of preparing flame resistant cotton fabrics such as bed sheets and pajamas, flame retardant curing of vinyl phosphonate oligomer on cotton fabrics was examined using electron beams from a self-sealed electron beam processor and gamma rays from a 60 Co source. A joint investigation was undertaken by the Tokyo Metropolitan Textile Research Institute and Tokyo Metropolitan Isotope Research Center to determine the feasibility of curing vinyl phosphonate oligomer on the cotton fabrics for textile finishing. (author)

Properties of poly(lactic acid nanocomposites based on montmorillonite, sepiolite and zirconium phosphonate

Directory of Open Access Journals (Sweden)

K. Fukushima

2012-11-01

Full Text Available Poly(lactic acid (PLA based nanocomposites based on 5 wt.% of an organically modified montmorillonite (CLO, unmodified sepiolite (SEP and organically modified zirconium phosphonate (ZrP were obtained by melt blending. Wide angle X-ray scattering (WAXS and scanning electron microscopy (SEM analysis showed a different dispersion level depending on the type and functionalisation of nanoparticles. Differenctial scanning calorimetric (DSC analysis showed that PLA was able to crystallize on heating, and that the addition of ZrP could promote extent of PLA crystallization, whereas the presence of CLO and SEP did not significantly affect the crystallization on heating and melting behaviour of PLA matrix. Dynamic Mechanical Thermoanalysis (DMTA results showed that addition of all nanoparticles brought considerable improvements in E' of PLA, resulting in a remarkable increase of elastic properties for PLA nanocomposites. The melt viscosity and dynamic shear moduli (G',G" of PLA nanocomposites were also enhanced significantly by the presence of CLO and SEP, and attributed to the formation of a PLA/nanoparticle interconnected structure within the polymer matrix. The oxygen permeability of PLA did not significantly vary upon addition of SEP and ZrP nanoparticles. Only addition of CLO led to about 30% decrease compared to PLA permeability, due to the good clay dispersion and clay platelet-like morphology. The characteristic high transparency of PLA in the visible region was kept upon addition of the nanoparticles. Based on these achievements, a high potential of these PLA nanocomposites in sustainable packaging applications could be envisaged.

Preparation and use of crystalline bis-monoorganic phosphonate and phosphate salts of tetravalent metals

Science.gov (United States)

Maya, L.

1980-06-26

A method of preparing and using the crystalline organic derivatives of the tetravalent metal phosphates and phosphonates provides for the contacting of an aqueous solution of a metal nitrate, with a solution of an organophosphorus acid for a period of time at room temperature that is sufficient for the formation of a metal phosphate product, and thereafter recovering said product. According to the invention, the product of the disclosed process is used in effecting analytical separations, such as ion exchange and chromatography.

Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins.

Science.gov (United States)

Forato, Florian; Liu, Hao; Benoit, Roland; Fayon, Franck; Charlier, Cathy; Fateh, Amina; Defontaine, Alain; Tellier, Charles; Talham, Daniel R; Queffélec, Clémence; Bujoli, Bruno

2016-06-07

Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate. Reactions giving rise to these products were modeled in homogeneous-phase studies. Nevertheless, each of the three modified surfaces effectively immobilized phosphopeptides and phosphopeptide tags fused to an affinity protein. Unexpectedly, the zirconium oxide/hydroxide modified surface, formed by treating the amine-coated slides with POCl3/Zr(4+), afforded better immobilization of the peptides and proteins and efficient capture of their targets.

Synthesis and applications of gem-bis-phosphonates, powerful complexing agents of metals

International Nuclear Information System (INIS)

Lecercle, D.

2007-12-01

This thesis was devoted to the development of new ways to prepare gem-bis-phosphonates compounds (BPs), and was carried out under the Program of Nuclear and Environmental Toxicology (ToxNuc-E). Two applications of these compounds have been investigated, the preparation of potent ligands of the uranyl ion for a target of decorporation, and the preparation of new anticancer compounds. The first of these applications was the consequence of work done in the laboratory, that have shown the strong uranium-binding properties of bis-phosphonic ligands. The in vivo tests performed on these compounds have shown the tendency of these ligands to cause liver accumulation of uranium, we wanted to address this problem by modifying the method of anchoring of the bis-phosphonates functions. To this end we have developed a new way to access to these compounds using a metal-carbenoid mediated poly-ols and poly-amines insertion, the metal-carbenoid species bearing the bis-phosphonate function. Regarding the preparation of BPs as anticancer agents, we have developed a new synthetic pathway using a phosphine catalyzed α-P addition of phosphorated pro-nucleophiles to alkynyl-phosphonates as a key step. This enabled us to prepare thirty compound whose activity was evaluated on two cell lines (A431 and HuH7). Five of these compounds possess an activity equivalent to that of the compound described as the most active, the Zoledronate. (author)

Nucleoside-O-Methyl-(H)-Phosphinates: Novel Monomers for the Synthesis of Methylphosphonate Oligonucleotides Using H-Phosphonate Chemistry.

Science.gov (United States)

Kostov, Ondřej; Páv, Ondřej; Rosenberg, Ivan

2017-09-18

This unit comprises the straightforward synthesis of protected 2'-deoxyribonucleoside-O-methyl-(H)-phosphinates in both 3'- and 5'-series. These compounds represent a new class of monomers compatible with the solid-phase synthesis of oligonucleotides using H-phosphonate chemistry and are suitable for the preparation of both 3'- and 5'-O-methylphosphonate oligonucleotides. The synthesis of 4-toluenesulfonyloxymethyl-(H)-phosphinic acid as a new reagent for the preparation of O-methyl-(H)-phosphinic acid derivatives is described. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

In Situ Investigation of the Adsorption of Styrene Phosphonic Acid on Cassiterite (110 Surface by Molecular Modeling

Directory of Open Access Journals (Sweden)

Guichen Gong

2017-09-01

Full Text Available Abstract: The flotation, adsorption and bonding mechanisms of styrene phosphonic acid (SPA to cassiterite were studied using microflotation tests, zeta potential measurements, solution chemistry analysis and density functional theory (DFT calculations in this paper. Flotation results demonstrated SPA was an excellent collector for cassiterite which could recover over 85% cassiterite particles with the pH range 4.3–6.06 and 40 mg/L SPA. Zeta potential measurements and solution chemistry analysis revealed the adsorption of SPA was mainly contributed by the chemisorption of the monoanions on cassiterite surfaces. Frontier molecular orbital theory analysis and adsorption energy calculation results proved the monoanion of SPA was able to replace the OH− on cassiterite surfaces. The adsorption structure optimization results confirmed the binuclear complex was the most favorable adsorption configuration of SPA on cassiterite (110 surface. Mulliken population calculations and density of states analysis indicated during the bonding process the Sn3 atom lost electrons to O3 atom, and the bonding interaction between O3 and Sn3 atoms was mainly from the contribution of the 2p orbital of O3 atom and the 5s and 5p orbitals of Sn3 atom.

Extraction studies of actinides by diamylbutyl phosphonate

International Nuclear Information System (INIS)

Brahmananda Rao, C.V.S.; Jayalakshmi, S.; Subramaniam, S.; Sabharwal, K.N.; Sivaraman, N.; Vasudeva Rao, P.R.

2014-01-01

The extraction ability of a monodentate organophosphorus extractant depends on the basicity of the phosphoryl oxygen atom and the nature of the substituents attached to the phosphorus atom. The basicity on the phosphoryl oxygen in the neutral organophosphorus extractant series increases in the order, phosphates 1 H, 13 C and 31 P NMR spectra. Extraction of U(VI) by 1.1 M DABP/n-dodecane as a function of nitric acid was studied using 233 U tracer. Th(IV) extraction behaviour as a function of nitric acid was studied using Arsenazo-III as chromogenic agent. 5 mL of the 1.1 M DABP solution in the diluent (n-dodecane) was equilibrated with 5mL of saturated thorium nitrate in an equilibration tube using a magnetic stirring bar. The organic and aqueous phases were analysed by complexometry using DTPA as titrant and xylenol orange as indicator. The LOC values were determined as a function of nitric acid concentration. The extraction of U(VI) and Th(IV) by 1.1M DABP along with TBP in n-dodecane at 303 K as a function of equilibrium nitric acid concentration are shown. The DABP shows higher distribution ratios for U(VI) and Th(IV) in the entire range of nitric acid concentrations studied compared to TBP. The steep rise in the distribution ratio is attributed to the higher basicity of phosphoryl group in phosphonates compared to the less basic nature of phosphates. The third phase formation of thorium as function of nitric acid concentration with 1.1 M DABP at 303 K are given. The LOC values for DABP system were higher throughout the nitric acid concentration compared to the TBP system. (author)

Synthesis and properties of ApA analogues with shortened phosphonate internucleotide linkage

Czech Academy of Sciences Publication Activity Database

Králíková, Šárka; Buděšínský, Miloš; Barvík, I.; Masojídková, Milena; Točík, Zdeněk; Rosenberg, Ivan

2011-01-01

Roč. 30, 7/9 (2011), s. 524-543 ISSN 1525-7770 R&D Projects: GA ČR GA202/09/0193; GA AV ČR KAN200520801; GA MŠk(CZ) LC06061 Institutional research plan: CEZ:AV0Z40550506 Keywords : alpha-hydroxy-phosphonate linkage * ApA analogues * phosphonate internucleotide bond * NMR conformational study Subject RIV: CC - Organic Chemistry Impact factor: 0.899, year: 2011

A synergistic combination of tetraethylorthosilicate and multiphosphonic acid offers excellent corrosion protection to AA1100 aluminum alloy

Science.gov (United States)

Dalmoro, Viviane; dos Santos, João H. Z.; Armelin, Elaine; Alemán, Carlos; Azambuja, Denise S.

2013-05-01

This work describes a new mechanism for the incorporation of organophosphonic acid into silane self-assembly monolayers, which has been used to protect AA1100 aluminum alloy. The protection improvement has been attributed to the fact that phosphonic structures promote the formation of strongly bonded and densely packed monolayer films, which show higher surface coverage and better adhesion than conventional silane systems. In order to evaluate the linking chemistry offered by phosphonic groups, two functionalized organophosphonic groups have been employed, 1,2-diaminoethanetetrakis methylenephosphonic acid (EDTPO) and aminotrimethylenephosphonic acid (ATMP), and combined with tetraethylorthosilicate (TEOS) films prepared by sol-gel synthesis. Results suggest that phosphonic acids may interact with the surface through a monodentate and bidentate coordination mode and, in addition, form one or more strong and stable linkages with silicon through non-hydrolysable bonds. Therefore, the incorporation of a very low concentration of phosphonic acids on TEOS solutions favors the complete coverage of the aluminum substrate during the silanization process, which is not possible using TEOS alone. The linking capacity of phosphonic acid has been investigated by FTIR-RA spectroscopy, SEM and EDX analysis, X-ray photoelectron spectroscopy (XPS), and quantum mechanical calculations. Finally, electrochemical impedance spectroscopy has been used to study the corrosion protection revealing that EDTPO-containing films afforded more protection to the AA1100 substrate than ATMP-containing films.

A synergistic combination of tetraethylorthosilicate and multiphosphonic acid offers excellent corrosion protection to AA1100 aluminum alloy

Energy Technology Data Exchange (ETDEWEB)

Dalmoro, Viviane [Instituto de Química, Universidade Federal do Rio Grande do Sul (UFRGS) Av. Bento Gonçalves 9500 - CEP 91501-970, Porto Alegre, RS (Brazil); Departament d’Enginyeria Química, ETSEIB, Universitat Politècnica de Catalunya (UPC), Avda. Diagonal 647, Barcelona E-08028 (Spain); Center for Research in Nano-Engineering (CRnE), Universitat Politècnica de Catalunya (UPC), Campus Sud, Edifici C’, C/Pasqual i Vila s/n, Barcelona E-08028 (Spain); Santos, João H.Z. dos [Instituto de Química, Universidade Federal do Rio Grande do Sul (UFRGS) Av. Bento Gonçalves 9500 - CEP 91501-970, Porto Alegre, RS (Brazil); Armelin, Elaine, E-mail: elaine.armelin@upc.edu [Departament d’Enginyeria Química, ETSEIB, Universitat Politècnica de Catalunya (UPC), Avda. Diagonal 647, Barcelona E-08028 (Spain); Center for Research in Nano-Engineering (CRnE), Universitat Politècnica de Catalunya (UPC), Campus Sud, Edifici C’, C/Pasqual i Vila s/n, Barcelona E-08028 (Spain); Alemán, Carlos, E-mail: carlos.aleman@upc.edu [Departament d’Enginyeria Química, ETSEIB, Universitat Politècnica de Catalunya (UPC), Avda. Diagonal 647, Barcelona E-08028 (Spain); Center for Research in Nano-Engineering (CRnE), Universitat Politècnica de Catalunya (UPC), Campus Sud, Edifici C’, C/Pasqual i Vila s/n, Barcelona E-08028 (Spain); and others

2013-05-15

This work describes a new mechanism for the incorporation of organophosphonic acid into silane self-assembly monolayers, which has been used to protect AA1100 aluminum alloy. The protection improvement has been attributed to the fact that phosphonic structures promote the formation of strongly bonded and densely packed monolayer films, which show higher surface coverage and better adhesion than conventional silane systems. In order to evaluate the linking chemistry offered by phosphonic groups, two functionalized organophosphonic groups have been employed, 1,2-diaminoethanetetrakis methylenephosphonic acid (EDTPO) and aminotrimethylenephosphonic acid (ATMP), and combined with tetraethylorthosilicate (TEOS) films prepared by sol–gel synthesis. Results suggest that phosphonic acids may interact with the surface through a monodentate and bidentate coordination mode and, in addition, form one or more strong and stable linkages with silicon through non-hydrolysable bonds. Therefore, the incorporation of a very low concentration of phosphonic acids on TEOS solutions favors the complete coverage of the aluminum substrate during the silanization process, which is not possible using TEOS alone. The linking capacity of phosphonic acid has been investigated by FTIR-RA spectroscopy, SEM and EDX analysis, X-ray photoelectron spectroscopy (XPS), and quantum mechanical calculations. Finally, electrochemical impedance spectroscopy has been used to study the corrosion protection revealing that EDTPO-containing films afforded more protection to the AA1100 substrate than ATMP-containing films.

A synergistic combination of tetraethylorthosilicate and multiphosphonic acid offers excellent corrosion protection to AA1100 aluminum alloy

International Nuclear Information System (INIS)

Dalmoro, Viviane; Santos, João H.Z. dos; Armelin, Elaine; Alemán, Carlos

2013-01-01

This work describes a new mechanism for the incorporation of organophosphonic acid into silane self-assembly monolayers, which has been used to protect AA1100 aluminum alloy. The protection improvement has been attributed to the fact that phosphonic structures promote the formation of strongly bonded and densely packed monolayer films, which show higher surface coverage and better adhesion than conventional silane systems. In order to evaluate the linking chemistry offered by phosphonic groups, two functionalized organophosphonic groups have been employed, 1,2-diaminoethanetetrakis methylenephosphonic acid (EDTPO) and aminotrimethylenephosphonic acid (ATMP), and combined with tetraethylorthosilicate (TEOS) films prepared by sol–gel synthesis. Results suggest that phosphonic acids may interact with the surface through a monodentate and bidentate coordination mode and, in addition, form one or more strong and stable linkages with silicon through non-hydrolysable bonds. Therefore, the incorporation of a very low concentration of phosphonic acids on TEOS solutions favors the complete coverage of the aluminum substrate during the silanization process, which is not possible using TEOS alone. The linking capacity of phosphonic acid has been investigated by FTIR-RA spectroscopy, SEM and EDX analysis, X-ray photoelectron spectroscopy (XPS), and quantum mechanical calculations. Finally, electrochemical impedance spectroscopy has been used to study the corrosion protection revealing that EDTPO-containing films afforded more protection to the AA1100 substrate than ATMP-containing films.

Phosphonate self-assembled monolayers on aluminum surfaces

International Nuclear Information System (INIS)

Hoque, E.; DeRose, J.A.; Hoffmann, P.; Mathieu, H.J.; Bhushan, B.; Cichomski, M.

2006-01-01

Substrates of aluminum (Al) deposited by physical vapor deposition onto Si substrates and then chemically reacted with perfluorodecylphosphonic acid (PFDP/Al/Si), decylphosphonic acid (DP/Al/Si), and octadecylphosphonic acid (ODP/Al/Si) were studied by x-ray photoelectron spectroscopy (XPS), contact angle measurements, atomic force microscopy (AFM), and friction force microscopy, a derivative of AFM, to characterize their surface chemical composition, roughness, and micro-/nanotribological properties. XPS analysis confirmed the presence of perfluorinated and nonperfluorinated alkylphosphonate molecules on the PFDP/Al/Si, DP/Al/Si, and ODP/Al/Si. The sessile drop static contact angle of pure water on PFDP/Al/Si was typically more than 130 deg. and on DP/Al/Si and ODP/Al/Si typically more than 125 deg. indicating that all phosphonic acid reacted Al/Si samples were very hydrophobic. The surface roughness for PFDP/Al/Si, DP/Al/Si, ODP/Al/Si, and bare Al/Si was approximately 35 nm as determined by AFM. The surface energy for PFDP/Al/Si was determined to be approximately 11 mN/m by the Zisman plot method compared to 21 and 20 mN/m for DP/Al/Si and ODP/Al/Si, respectively. Tribology involves the measure of lateral forces due to friction and adhesion between two surfaces. Friction, adhesion, and wear play important roles in the performance of micro-/nanoelectromechanical systems. PFDP/Al/Si gave the lowest adhesion and coefficient of friction values while bare Al/Si gave the highest. The adhesion and coefficient of friction values for DP/Al/Si and ODP/Al/Si were comparable

Phosphonate biosynthesis and catabolism: a treasure trove of unusual enzymology.

Science.gov (United States)

Peck, Spencer C; van der Donk, Wilfred A

2013-08-01

Natural product biosynthesis has proven a fertile ground for the discovery of novel chemistry. Herein we review the progress made in elucidating the biosynthetic pathways of phosphonate and phosphinate natural products such as the antibacterial compounds dehydrophos and fosfomycin, the herbicidal phosphinothricin-containing peptides, and the antimalarial compound FR-900098. In each case, investigation of the pathway has yielded unusual, and often unprecedented, biochemistry. Likewise, recent investigations have uncovered novel ways to cleave the CP bond to yield phosphate under phosphorus starvation conditions. These include the discovery of novel oxidative cleavage of the CP bond catalyzed by PhnY and PhnZ as well as phosphonohydrolases that liberate phosphate from phosphonoacetate. Perhaps the crown jewel of phosphonate catabolism has been the recent resolution of the longstanding problem of the C-P lyase responsible for reductively cleaving the CP bond of a number of different phosphonates to release phosphate. Taken together, the strides made on both metabolic and catabolic fronts illustrate an array of fascinating biochemistry. Copyright © 2013 Elsevier Ltd. All rights reserved.

3D-QSAR studies and molecular docking on [5-(4-amino-1 H-benzoimidazol-2-yl)-furan-2-yl]-phosphonic acid derivatives as fructose-1,6-biphophatase inhibitors

Science.gov (United States)

Lan, Ping; Xie, Mei-Qi; Yao, Yue-Mei; Chen, Wan-Na; Chen, Wei-Min

2010-12-01

Fructose-1,6-biphophatase has been regarded as a novel therapeutic target for the treatment of type 2 diabetes mellitus (T2DM). 3D-QSAR and docking studies were performed on a series of [5-(4-amino-1 H-benzoimidazol-2-yl)-furan-2-yl]-phosphonic acid derivatives as fructose-1,6-biphophatase inhibitors. The CoMFA and CoMSIA models using thirty-seven molecules in the training set gave r cv 2 values of 0.614 and 0.598, r 2 values of 0.950 and 0.928, respectively. The external validation indicated that our CoMFA and CoMSIA models possessed high predictive powers with r 0 2 values of 0.994 and 0.994, r m 2 values of 0.751 and 0.690, respectively. Molecular docking studies revealed that a phosphonic group was essential for binding to the receptor, and some key features were also identified. A set of forty new analogues were designed by utilizing the results revealed in the present study, and were predicted with significantly improved potencies in the developed models. The findings can be quite useful to aid the designing of new fructose-1,6-biphophatase inhibitors with improved biological response.

Inhibition of human thymidine phosphorylase by conformationally constrained pyrimidine nucleoside phosphonic acids and their "open-structure" isosteres

Czech Academy of Sciences Publication Activity Database

Kóšiová, Ivana; Šimák, Ondřej; Panova, Natalya; Buděšínský, Miloš; Petrová, Magdalena; Rejman, Dominik; Liboska, Radek; Páv, Ondřej; Rosenberg, Ivan

2014-01-01

Roč. 74, Mar 3 (2014), s. 145-168 ISSN 0223-5234 R&D Projects: GA ČR GA203/09/0820; GA ČR GA202/09/0193; GA ČR GA13-24880S; GA ČR GA13-26526S Institutional support: RVO:61388963 Keywords : phosphonate * conformationally constrained nucleotide analog * human thymidine phosphorylase * PBMC * bi-substrate-like inhibitor * Michael addition Subject RIV: CC - Organic Chemistry Impact factor: 3.447, year: 2014

Synthesis of difluorinated compounds starting from phosphonates

Czech Academy of Sciences Publication Activity Database

Alexandrova, Anastasia; Beier, Petr

2008-01-01

Roč. 102, č. 11 (2008), s. 1023-1023 ISSN 0009-2770. [Pokroky v organické, bioorganické a farmaceutické chemii /43./. 14.11.2008-16.11.2008, Liblice] Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonates * nucleophilic addition Subject RIV: CC - Organic Chemistry

Obtention of Samarium and Gadolinium concentrates by solvent extraction using mono-2-ethylhexyl ester of 2-ethylhexyl phosphonic acid; Obtencao de concentrados de samario e gadolinio via extracao por solventes com o ester mono-2-etilhexil do acido 2-etilhexilfosfonico

Energy Technology Data Exchange (ETDEWEB)

Miranda, Junior, Pedro

1996-07-01

The rare earth chlorides solution employed in this study, which is constituted by medium and heavy fractions, is derived from monazite processing accomplished by NUCLEMON-Mineroquimica (SP). This solution shows an acidity about 1.18 M and 189 g/L of rare earth oxides, containing as main constituents: Sm(34.55%), Gd(23.85%), Dy (6.82%), and Y (24.45%). It was used, as organic phase, 2-ethylhexyl phosphonic acid, mono-2-ethylhexylester diluted to 1 M in isododecane. (author)

Synthesis and characterization of calcium hydroxy and fluoroapatite functionalized with methyl phosphonic dichloride

Energy Technology Data Exchange (ETDEWEB)

Agougui, Hassen; Aissa, Abdallah [Laboratoire de Physico-Chimie des Materiaux, Faculte des Sciences de Monastir, 5019 Monastir (Tunisia); Debbabi, Mongi, E-mail: m.debbabi@yahoo.fr [Laboratoire de Physico-Chimie des Materiaux, Faculte des Sciences de Monastir, 5019 Monastir (Tunisia)

2012-11-15

Highlights: Black-Right-Pointing-Pointer Surface reactivity of apatites toward methyl phosphonic dichloride is tested. Black-Right-Pointing-Pointer Chemical analysis shows that hydroxyapatite is more reactive. Black-Right-Pointing-Pointer NMR spectra show the formation of Ca-O-P{sub org} and P{sub inorg}-O-P{sub org} bonds. Black-Right-Pointing-Pointer AFM indicated that the texture surface was changed by grafting. - Abstract: The nature of apatite-organic molecule interaction was the subject of many investigations. Grafting the organic molecule onto the inorganic support may precede through either formation of covalent bonds or ionic interaction between superficial hydroxyl on the apatite surface and organic functions. The hybrid materials obtained by functionalization of apatite surfaces with phosphonate moieties are of interest for their potential applications such in catalysis, chromatography and biomedical domain. In this scope, calcium hydroxyl and fluoroapatite (CaHAp and CaFAp) were prepared in the presence of the methyl phosphonic dichloride (MPO), by contact method in organic solvent at 25 Degree-Sign C for 2 days. The products are rigorously characterized by chemical analysis, infrared (IR), MAS-NMR spectroscopies, powder X-ray diffraction (XRD), atomic force microscopy (AFM) and specific surface area (SSA). The X-ray powder analysis showed that the crystallinity was sensibly affected by the presence of organic moieties. The IR spectroscopy showed new vibration modes appearing related to phosphonate groups essentially at 2930, 1315, 945, 764 and 514 cm{sup -1}. The {sup 31}P MAS NMR spectrum for hydroxy and fluoroapatite exhibits a single signal at 2.8 ppm. After reaction with (MPO) the spectra show the presence of new signals, assigned to the formation of organic-inorganic bond between the superficial hydroxyl groups of the apatite ({identical_to}CaOH) and ({identical_to}POH) and methyl phosphonic dichloride. The SSA decreases with increasing

Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

KAUST Repository

Li, Hui

2018-02-01

Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

KAUST Repository

Li, Hui; Sun, Ying; Yuan, Zhong-Yong; Zhu, Yun-Pei; Ma, Tianyi

2018-01-01

Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

New copper aryl phosphonates with auxiliary nitrogen ligands

Czech Academy of Sciences Publication Activity Database

Zima, Vítězslav; Svoboda, Jan; Yang, Y.-Ch.; Wang, S.-L.

2012-01-01

Roč. 14, č. 10 (2012), s. 3469-3477 ISSN 1466-8033 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : copper * phosphonates * structure Subject RIV: CA - Inorganic Chemistry Impact factor: 3.879, year: 2012

Analysis of perfluorinated phosponic acids and perfluorooctane sulfonic acid in water, sludge and sediment by LC-MS/MS

NARCIS (Netherlands)

Esperza, X.; Moyano, E.; de Boer, J.; Galceran, M.T.; van Leeuwen, S.P.J.

2011-01-01

Residues of perfluorinated phosphonic acids (PFPAs) and perfluorooctane sulfonic acid (PFOS) were investigated in various Dutch surface waters, sludge and sediments. For this purpose, a liquid chromatographic (LC) method was optimized by testing several columns with different mobile phases.

Synthesis and properties of ApA analogues with shortened phosphonate internucleotide linkage.

Science.gov (United States)

Králíková, Sárka; Buděšínský, Miloš; Barvík, Ivan; Masojídková, Milena; Točík, Zdeněk; Rosenberg, Ivan

2011-01-01

A complete series of the 2 '-5 ' and 3 '-5 ' regioisomeric types of r(ApA) and 2 '-d(ApA) analogues with the α-hydroxy-phosphonate C3 '-O-P-CH(OH)-C4 ″ internucleotide linkage, isopolar but non-isosteric with the phosphodiester one, were synthesized and their hybridization properties with polyU studied. Due to the chirality on the 5 '-carbon atom of the modified internucleotide linkage bearing phosphorus and hydroxy moieties, each regioisomeric type of ApA dimer is split into epimeric pairs. To examine the role of the 5 '-hydroxyl of the α-hydroxy-phosphonate moiety during hybridization, the appropriate r(ApA) analogues with 3 '(2 ')-O-P-CH(2)-C4 ″ linkage lacking the 5 '-hydroxyl were synthesized. Nuclear magnetic resonance (NMR) spectroscopy study on the conformation of the modified sugar-phosphate backbone, along with the hybridization measurements, revealed remarkable differences in the stability of complexes with polyU, depending on the 5 '-carbon atom configuration. Potential usefulness of the α-hydroxy-phosphonate linkage in modified oligoribonucleotides is discussed.

Acid monolayer functionalized iron oxide nanoparticle catalysts

Science.gov (United States)

Ikenberry, Myles

Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

Antiviral acyclic nucleoside phosphonates: New structures and prodrugs

Czech Academy of Sciences Publication Activity Database

Krečmerová, Marcela; Tichý, Tomáš; Pomeisl, Karel; Andrei, G.; Balzarini, J.; Snoeck, R.

2016-01-01

Roč. 1, č. 2 (2016), s. 37 [PharmaMed-2016. International Conference on Medicinal and Pharmaceutical Chemistry . 05.12.2016-07.12.2016, Dubai] R&D Projects: GA ČR(CZ) GA14-00522S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * prodrugs * antivirals * 5-azacytosine Subject RIV: CC - Organic Chemistry

Performance and Compatibility of Phosphonate-Based Superplasticizers for Concrete

Directory of Open Access Journals (Sweden)

Luigi Coppola

2017-07-01

Full Text Available The paper deals with the effectiveness of an innovative phosphonate-based superplasticizer (PNH for ready mixed concrete. Concrete specimens were manufactured by considering a constant initial workability, equal to 220 mm slump at the end of the mixing procedure. Workability was measured at 0, 30, and 60 min to evaluate the workability retention performances of the innovative superplasticizer. Compressive tests at 1, 7, and 28 days were carried out to evaluate the influence of the phosphonate-based superplasticizer on concrete setting and hardening. The concrete mixes were designed by considering 13 different cements to assess the superplasticizer-cement compatibility. The PNH-based admixture showed a better performance in terms of water reduction and workability retention with respect to napthalenesulphonate based admixtures (NSF; however, a higher dosage of PNH with respect to polycarboxylate ethers (PCEs was needed to get the same initial fluidity.

The supramolecular architecture of tris(naphthalene-1,5-diaminium) bis(5-aminonaphthalen-1-aminium) octakis[hydrogen (5-carboxypyridin-3-yl)phosphonate].

Science.gov (United States)

Wilk, Magdalena; Janczak, Jan; Videnova-Adrabinska, Veneta

2012-09-01

The asymmetric unit of the title compound, 3C(10)H(12)N(2)(2+)·2C(10)H(11)N(2)(+)·8C(6)H(5)NO(5)P(-), contains one and a half naphthalene-1,5-diaminium cations, in which the half-molecule has inversion symmetry, one 5-aminonaphthalen-1-aminium cation and four hydrogen (5-carboxypyridin-3-yl)phosphonate anions. The crystal structure is layered and consists of hydrogen-bonded anionic monolayers between which the cations are arranged. The acid monoanions are organized into one-dimensional chains along the [101] direction via hydrogen bonds established between the phosphonate sites. (C)O-H···N(py) hydrogen bonds (py is pyridine) crosslink the chains to form an undulating (010) monolayer. The cations serve both to balance the charge of the anionic network and to connect neighbouring layers via multiple hydrogen bonds to form a three-dimensional supramolecular architecture.

Disorder-derived, strong tunneling attenuation in bis-phosphonate monolayers

Science.gov (United States)

Pathak, Anshuma; Bora, Achyut; Liao, Kung-Ching; Schmolke, Hannah; Jung, Antje; Klages, Claus-Peter; Schwartz, Jeffrey; Tornow, Marc

2016-03-01

Monolayers of alkyl bisphosphonic acids (bisPAs) of various carbon chain lengths (C4, C8, C10, C12) were grown on aluminum oxide (AlO x ) surfaces from solution. The structural and electrical properties of these self-assembled monolayers (SAMs) were compared with those of alkyl monophosphonic acids (monoPAs). Through contact angle (CA) and Kelvin-probe (KP) measurements, ellipsometry, and infrared (IR) and x-ray photoelectron (XPS) spectroscopies, it was found that bisPAs form monolayers that are relatively disordered compared to their monoPA analogs. Current-voltage (J-V) measurements made with a hanging Hg drop top contact show tunneling to be the prevailing transport mechanism. However, while the monoPAs have an observed decay constant within the typical range for dense monolayers, β mono  =  0.85  ±  0.03 per carbon atom, a surprisingly high value, β bis  =  1.40  ±  0.05 per carbon atom, was measured for the bisPAs. We attribute this to a strong contribution of ‘through-space’ tunneling, which derives from conformational disorder in the monolayer due to strong interactions of the distal phosphonic acid groups; they likely form a hydrogen-bonding network that largely determines the molecular layer structure. Since bisPA SAMs attenuate tunnel currents more effectively than do the corresponding monoPA SAMs, they may find future application as gate dielectric modification in organic thin film devices.

Thermal and Dielectric Behavior Studies of Poly(Arylene Ether Sulfones with Sulfonated and Phosphonated Pendants

Directory of Open Access Journals (Sweden)

Shimoga D. Ganesh

2016-01-01

Full Text Available The present paper discusses the aspects of the synthesizing valeric acid based poly(ether sulfones with active carboxylic acid pendants (VALPSU from solution polymerization technique via nucleophilic displacement polycondensation reaction among 4,4′-dichlorodiphenyl sulfone (DCDPS and 4,4′-bis(4-hydroxyphenyl valeric acid (BHPA. The conditions necessary to synthesize and purify the polymer were investigated in some detail. The synthesized poly(ether sulfones comprise sulfone and ether linkages in addition to reactive carboxylic acid functionality; these active carboxylic acid functional groups were exploited to hold the phenyl sulphonic acid and phenyl phosphonic acid pendants. The phenyl sulphonic acid pendants in VALPSU were easily constructed by altering active carboxylic acid moieties by sulfanilic acid using N,N′-dicyclohexylcarbodiimide (DCC mediated mild synthetic route, whereas the latter one was built in two steps. Initially, polyphosphoric acid condensation with VALPSU by 4-bromoaniline and next straightforward palladium catalyzed synthetic route, in both of which acidic pendants are clenched by polymer backbone via amide linkage. Without impairing the primary polymeric backbone modified polymers were prepared by varying the stoichiometric ratios of respective combinations. All the polymers were physicochemically characterized and pressed into tablets; electrical contacts were established to study the dielectric properties. Finally, the influence of the acidic pendants on the dielectric properties was examined.

Structure and properties of polyaniline interacting with H-phosphonates

Czech Academy of Sciences Publication Activity Database

Bláha, Michal; Trchová, Miroslava; Bober, Patrycja; Morávková, Zuzana; Zujovic, Z. D.; Filippov, Sergey K.; Prokeš, J.; Pilař, Jan; Stejskal, Jaroslav

2017-01-01

Roč. 232, October (2017), s. 79-86 ISSN 0379-6779 R&D Projects: GA ČR(CZ) GA17-04109S Institutional support: RVO:61389013 Keywords : conducting polymers * polyaniline * H-phosphonate Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 2.435, year: 2016

Crystal structure and characterization of a novel layered copper-lithium phosphonate with antiferromagnetic intrachain Cu(II)···Cu(II) interactions

Energy Technology Data Exchange (ETDEWEB)

Abdelbaky, Mohammed S.M. [Departments of Physical and Analytical Chemistry and Organic and Inorganic Chemistry, University of Oviedo-CINN, 33006 Oviedo (Spain); Amghouz, Zakariae [Scientific and Technical Services, University of Oviedo-CINN, 33006 Oviedo (Spain); Department of Materials Science and Metallurgical Engineering, University of Oviedo, Campus Universitario, 33203 Gijón (Spain); Blanco, David Martínez [Scientific and Technical Services, University of Oviedo-CINN, 33006 Oviedo (Spain); García-Granda, Santiago; García, José R. [Departments of Physical and Analytical Chemistry and Organic and Inorganic Chemistry, University of Oviedo-CINN, 33006 Oviedo (Spain)

2017-04-15

Novel metal phosphonate [CuLi(PPA)] [H{sub 3}PPA=3-phosphonopropionic acid] was synthesized hydrothermally and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and thermogravimetric analysis. It crystallizes in the space group C2/c, with cell parameters a=21.617(2) Å, b=4.9269(2) Å, c=14.342(1) Å, β=132.3(2)°, and Z=8. Its framework is built up from a main trimer, acting as a secondary building unit (SBU), which is formed by vertex-shared between two (LiO{sub 4}) and one (Cu(1)O{sub 4}) polyhedra. These units repeat along b-axis forming infinite inorganic chains, these chains are in turn cross-linked by corner sharing with (Cu(2)O{sub 4}) polyhedra to produce inorganic layers lying in the bc-plane. The neighboring layers are connected through the PPA ligand, leading to a 3D pillared-layered structure. The topological analysis reveals that the compound exhibits 3,4,10-c net. Finally, magnetic susceptibility measurement of this compound over the temperature range of 2–300 K reveals the occurrence of weak antiferromagnetic intrachain interactions. - Graphical abstract: Hydrothermal synthesis and structural characterization of a novel lithium-copper phosphonate, formulated as [CuLi(PPA)] (H{sub 3}PPA=3-phosphonopropionic acid), have been reported. This compound has a 3D pillared-layered structure with 3,4,10-c net topology. The magnetic susceptibility data over the temperature range of 2–300 K reveals the occurrence of weak antiferromagnetic interactions. - Highlights: • Novel metal phosphonate, [CuLi(PPA)] (1), has been synthesized and characterized. • Compound 1 has a 3D pillared-layered structure with 3,4,10-c net topology. • Magnetic susceptibility data reveals the occurrence of weak antiferromagnetic interactions.

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

Energy Technology Data Exchange (ETDEWEB)

Rueff, Jean-Michel, E-mail: jean-michel.rueff@ensicaen.fr [Laboratoire CRISMAT, CNRS UMR 6508, ENSICAEN, 6 bd du Maréchal Juin, F-14050 Caen Cedex (France); Poienar, Maria [National Institute for Research and Development in Electrochemistry and Condensed Matter, Plautius Andronescu Str Nr. 1, 300224 Timisoara (Romania); Guesdon, Anne; Martin, Christine; Maignan, Antoine [Laboratoire CRISMAT, CNRS UMR 6508, ENSICAEN, 6 bd du Maréchal Juin, F-14050 Caen Cedex (France); Jaffrès, Paul-Alain [Université de Brest, Université Européenne de Bretagne, CNRS UMR 6521, CEMCA, SFR 148 ScInBios, 6 Avenue Victor Le Gorgeu, 29238 Brest (France)

2016-04-15

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

Interest of bone scintigraphy in the care of maxillary osteo-necroses induced by bis-phosphonates

International Nuclear Information System (INIS)

Agossa, Kevimy

2012-01-01

First cases of bis-phosphonates related osteonecrosis of jaws (BRONJ) have been described in 2003. Since then, this subject is one of the central concerns of several scientific communities, well beyond the oral sphere. The prevalence of BRONJ is evolving. Their etiology is not well established and the results of the treatments are inconstant. So many points that make the care to patients under bis-phosphonates really complex. Early diagnosis is essential in treatment outcome. So nuclear imaging including scintigraphy with technetium 99m seems to be helpful. It may allow detection before the onset of symptoms, facilitate localization of necrosis and it may be useful for the monitoring of such lesions after surgery. These are new applications for oncologist and dentist, in order to improve the management of patients treated by bis-phosphonates. (author) [fr

Formation of phosphonates and pyrophosphates in the reactions of ...

Indian Academy of Sciences (India)

Bu-4-Me-C6H2O)2P(O)]2O (8) could be isolated, although the reaction mixture showed several other compounds in the phosphorus NMR. A possible pathway for the formation of phosphonate salts is proposed. The X-ray crystal structures of 4, ...

Removal of Heavy Metals from Aqueous Solution Using Novel Nanoengineered Sorbents: Self-Assembled Carbamoylphosphonic Acids on Mesoporous Silica

International Nuclear Information System (INIS)

Yantasee, Wassana; Lin, Yuehe; Fryxell, Glen E.; Busche, Brad J.; Birnbaum, Jerome C.

2003-01-01

Self-assembled monolayers of carbamoylphosphonic acids (acetamide phosphonic acid and propionamide phosphonic acid) on mesoporous silica supports were studied as potential absorbents for heavy and transition metal ions in aqueous wastes. The adsorption capacity, selectivity, and kinetics of the materials in sequestering metal ions, including Cd2+, Co2+, Cu2+, Cr3+, Pb2+, Ni2+, Zn2+, and Mn2+, were measured in batch experiments with excess sodium ion. The solution pH ranged from 2.2 to 5.5. The kinetics study shows that the adsorption reached equilibrium in seconds, indicating that there is little resistance to mass transfer, intraparticle diffusion, and surface chemical reaction. The competitive adsorption study found the phosphonic acid-SAMMS to have an affinity for divalent metal ions in decreasing order of Pb2+ > Cu2+ > Mn2+ > Cd2+ > Zn2+ > Co2+ > Ni2+. The measured Cd2+ adsorption isotherm was of the Langmuirian type and had a saturation binding capacity of 0.32 mmol/g

Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

Science.gov (United States)

Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng

A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion ®117 membrane (5.04 × 10 -2 S cm -1). The highest proton conductivities 3.58 × 10 -2, 3.51 × 10 -2 and 2.61 × 10 -2 S cm -1 for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 × 10 -7 cm 2 s -1 which was 16 times lower than that of Nafion ®117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes.

Novel 2D or 3D alkaline-earth metal sulfonate-phosphonates based on [O 3S-C 2H 4-PO 3H] 2- ligand

Science.gov (United States)

Du, Zi-Yi; Wen, He-Rui; Xie, Yong-Rong

2008-11-01

Three novel alkaline-earth metal sulfonate-phosphonates based on [O 3S-C 2H 4-PO 3H] 2- ligand, namely, [Ca(O 3SC 2H 4PO 3H)(H 2O) 2] ( 1), [Sr(O 3SC 2H 4PO 3H)] ( 2) and [Ba 2(O 3SC 2H 4PO 3H) 2] ( 3), have been synthesized by hydrothermal reactions. They represent the first structurally characterized alkaline-earth metal complexes of phosphonic acid attached with a sulfonate group. The structure of compound 1 features a 2D layer based on 1D chains of [Ca 2(PO 3) 2] bridged by -CH 2-CH 2-SO 3- groups. Compounds 2 and 3 show pillar-layer architecture based on two different inorganic layers linked by -CH 2-CH 2- groups. The inorganic layer in compound 2 features a 1D chain of edge-sharing SrO 8 polyhedra whereas that in compound 3 features an edge-sharing Ba 2O 14 di-polyhedral unit which is further corner-shared with four neighboring ones. The [O 3S-C 2H 4-PO 3H] 2- ligand shows diverse coordination modes in the three alkaline-earth metal sulfonate-phosphonates.

Yield Improvement and Energy Savings Uing Phosphonates as Additives in Kraft pulping

Energy Technology Data Exchange (ETDEWEB)

Ulrike W. Tschirner; Timothy Smith

2007-03-31

Project Objective: Develop a commercially viable modification to the Kraft process resulting in energy savings, increased yield and improved bleachability. Evaluate the feasibility of this technology across a spectrum of wood species used in North America. Develop detailed fundamental understanding of the mechanism by which phosphonates improve KAPPA number and yield. Evaluate the North American market potential for the use of phosphonates in the Kraft pulping process. Examine determinants of customer perceived value and explore organizational and operational factors influencing attitudes and behaviors. Provide an economic feasibility assessment for the supply chain, both suppliers (chemical supply companies) and buyers (Kraft mills). Provide background to most effectively transfer this new technology to commercial mills.

Novel polymeric phosphonate scale inhibitors for improved squeeze treatment lifetimes

Energy Technology Data Exchange (ETDEWEB)

Jackson, G.E.; Poynton, N.; McLaughlin, K.; Clark, D.R.

1996-12-31

New patented chemistry has provided an exciting discovery which may be used to reduce costs in scale squeeze applications. Phosphomethylated polyamines (PMPAs) have been found to possess outstanding adsorption-desorption properties which generate long squeeze lifetimes. This paper describes the core-flood tests and modelling work, which highlight these properties, plus additional scale inhibition performance studies to demonstrate the all-round capabilities of this chemistry for squeeze treatments. An example of a PMPA is used to show the extremely viable adsorption and desorption isotherms. These illustrate the efficient way in which the desorption occurs to minimise the chemical in the returns with a benefit of reduced chemical content in the discharge. The PMPA also demonstrates that both polymer and phosphonate properties can be embraced in a single product (e.g. dual scale control mechanisms) confirming that this chemistry is a true polymeric phosphonate. 13 refs., 12 figs., 1 tab.

Botanicals and Phosphonate Show Potential to Replace Copper for Control of Potato Late Blight

Directory of Open Access Journals (Sweden)

Hans-Rudolf Forrer

2017-11-01

Full Text Available Potato late blight (PLB caused by Phytophthora infestans (Pi is the most harmful disease in potato production worldwide. In organic farming, copper is used despite its persistence in soil and toxicity to soil organisms. To replace copper, suspensions of powders from three promising botanicals, including bark of buckthorn (Frangula alnus, FA, roots of medicinal rhubarb (Rheum palmatum and galls of the nutgall tree (Galla chinensis, were tested in multi-year field experiments. The current study shows for the first time that botanicals could replace copper under field conditions and best PLB reduction on leaves was achieved with FA, reaching a level close to that of 2 to 3 kg copper per hectare and year. Better results than with copper were achieved with Phosfik® (Ph, a phosphonate-based product. For both FA and Ph, the mode of action is based on induced resistance, for Ph also on direct fungicidal effects. A disadvantage of Ph is the accumulation of residues in potato tubers. Nevertheless, two to three applications with 2 to 3 L/ha of Ph would be feasible to not exceed a minimal risk level (MLR of 20 mg/kg of phosphorous acid as proposed by the European Food Safety Authority. Due to an excellent environmental profile and a complex mode of action counteracting Pi resistance, phosphonate-based products would be most suitable for sustainable PLB management in integrated pest management (IPM programmes.

Bis-phosphonate sequestering agents. Synthesis and preliminary evaluation for in vitro and in vivo uranium(VI) chelation

Energy Technology Data Exchange (ETDEWEB)

Sawicki, M.; Lecercle, D.; Taran, F. [CEA Saclay, IBiTecS, Serv Chim Bioorgan et Marquage, F-91191 Gif Sur Yvette (France); Grillon, G.; Le Gall, B.; Serandour, A.L.; Poncy, J.L. [CEA, DSV, DRR, Lab Radiotoxicol, F-91680 Bruyeres Le Chatel (France); Bailly, T.; Burgada, R.; Lecouvey, M.; Challeix, V. [CNRS, Lab Chim Struct Biomol, UMR 7033, F-93017 Bobigny (France); Leydier, A.; Pellet-Rostaing, S. [Univ Lyon 1, ICBMS, UMR 5246, Lab Catalyse et Synth Organ, F-69622 Villeurbanne (France); Ansoborlo, E. [CEA, DEN, DRCP, CETAMA, VRH Marcoule, F-30207 Bagnols Sur Ceze (France)

2008-07-01

A library of bis-phosphonate-based ligands was prepared using solution-phase parallel synthesis and tested for its uranium-binding properties. With the help of a screening method, based on a chromo-phoric complex displacement procedure, 23 dipodal and tripodal chelates bearing bis-phosphonate chelating functions were found to display very high affinity for the uranyl ion and were selected for evaluation of their in vivo uranyl-removal efficacy. Among them, 11 ligands induced a huge modification of the uranyl biodistribution by deviating the metal from kidney and bones to liver. Among the other ligands, the most potent was the dipodal bis-phosphonate 3C which reduced the retention of uranyl and increased its excretion by around 10% of the injected metal. (authors)

Disorder-derived, strong tunneling attenuation in bis-phosphonate monolayers

International Nuclear Information System (INIS)

Pathak, Anshuma; Bora, Achyut; Tornow, Marc; Liao, Kung-Ching; Schwartz, Jeffrey; Schmolke, Hannah; Jung, Antje; Klages, Claus-Peter

2016-01-01

Monolayers of alkyl bisphosphonic acids (bisPAs) of various carbon chain lengths (C4, C8, C10, C12) were grown on aluminum oxide (AlO x ) surfaces from solution. The structural and electrical properties of these self-assembled monolayers (SAMs) were compared with those of alkyl monophosphonic acids (monoPAs). Through contact angle (CA) and Kelvin-probe (KP) measurements, ellipsometry, and infrared (IR) and x-ray photoelectron (XPS) spectroscopies, it was found that bisPAs form monolayers that are relatively disordered compared to their monoPA analogs. Current–voltage (J–V) measurements made with a hanging Hg drop top contact show tunneling to be the prevailing transport mechanism. However, while the monoPAs have an observed decay constant within the typical range for dense monolayers, β mono   =  0.85  ±  0.03 per carbon atom, a surprisingly high value, β bis   =  1.40  ±  0.05 per carbon atom, was measured for the bisPAs. We attribute this to a strong contribution of ‘through-space’ tunneling, which derives from conformational disorder in the monolayer due to strong interactions of the distal phosphonic acid groups; they likely form a hydrogen-bonding network that largely determines the molecular layer structure. Since bisPA SAMs attenuate tunnel currents more effectively than do the corresponding monoPA SAMs, they may find future application as gate dielectric modification in organic thin film devices. (paper)

Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng [Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

2008-10-15

A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion {sup registered} 117 membrane (5.04 x 10{sup -2} S cm{sup -1}). The highest proton conductivities 3.58 x 10{sup -2}, 3.51 x 10{sup -2} and 2.61 x 10{sup -2} S cm{sup -1} for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 x 10{sup -7} cm{sup 2} s{sup -1} which was 16 times lower than that of Nafion {sup registered} 117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes. (author)

Synthesis, kinetic evaluation, and utilization of a biotinylated dipeptide proline diphenyl phosphonate for the disclosure of dipeptidyl peptidase IV-like serine proteases.

Science.gov (United States)

Gilmore, Brendan F; Carson, Louise; McShane, Laura L; Quinn, Derek; Coulter, Wilson A; Walker, Brian

2006-08-18

In this study, we report on the synthesis, kinetic characterisation, and application of a novel biotinylated and active site-directed inactivator of dipeptidyl peptidase IV (DPP-IV). Thus, the dipeptide-derived proline diphenyl phosphonate NH(2)-Glu(biotinyl-PEG)-Pro(P)(OPh)(2) has been prepared by a combination of classical solution- and solid-phase methodologies and has been shown to be an irreversible inhibitor of porcine DPP-IV, exhibiting an over all second-order rate constant (k(i)/K(i)) for inhibition of 1.57 x 10(3) M(-1) min(-1). This value compares favourably with previously reported rates of inactivation of DPP-IV by dipeptides containing a P(1) proline diphenyl phosphonate grouping [B. Boduszek, J. Oleksyszyn, C.M. Kam, J. Selzler, R.E. Smith, J.C. Powers, Dipeptide phophonates as inhibitors of dipeptidyl peptidase IV, J. Med. Chem. 37 (1994) 3969-3976; B.F. Gilmore, J.F. Lynas, C.J. Scott, C. McGoohan, L. Martin, B. Walker, Dipeptide proline diphenyl phosphonates are potent, irreversible inhibitors of seprase (FAPalpha), Biochem, Biophys. Res. Commun. 346 (2006) 436-446.], thus demonstrating that the incorporation of the side-chain modified (N-biotinyl-3-(2-(2-(3-aminopropyloxy)-ethoxy)-ethoxy)-propyl) glutamic acid residue at the P(2) position is compatible with inhibitor efficacy. The utilisation of this probe for the detection of both purified dipeptidyl peptidase IV and the disclosure of a dipeptidyl peptidase IV-like activity from a clinical isolate of Porphyromonas gingivalis, using established electrophoretic and Western blotting techniques previously developed by our group, is also demonstrated.

Antiretrovirus activity of a novel class of acyclic pyrimidine nucleoside phosphonates

Czech Academy of Sciences Publication Activity Database

Balzarini, J.; Pannecouque, C.; De Clercq, E.; Aquaro, S.; Perno, C. F.; Egberink, H.; Holý, Antonín

2002-01-01

Roč. 46, č. 7 (2002), s. 2185-2193 ISSN 0066-4804 R&D Projects: GA ČR GV203/96/K001 Institutional research plan: CEZ:AV0Z4055905 Keywords : nucleoside phosphonates Subject RIV: CC - Organic Chemistry Impact factor: 4.215, year: 2002

Novel nucleotide analogues bearing (1H-1,2,3-triazol-4-yl)phosphonic acid moiety as inhibitors of Plasmodium and human 6-oxopurine phosphoribosyltransferases

Czech Academy of Sciences Publication Activity Database

Lukáč, Miloš; Hocková, Dana; Keough, D. T.; Guddat, L. W.; Janeba, Zlatko

2017-01-01

Roč. 73, č. 6 (2017), s. 692-702 ISSN 0040-4020 R&D Projects: GA ČR(CZ) GA16-06049S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * 6-oxopurine * hypoxanthine-guanine-(xanthine) phosphoribosyltransferase * copper(I)-catalyzed azide-alkyne cycloaddition Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.651, year: 2016

Hydrothermal synthesis, crystal structure and properties of a novel chain coordination polymer constructed by tetrafunctional phosphonate anions and cobalt ions

International Nuclear Information System (INIS)

Guan, Lei; Wang, Ying

2015-01-01

A novel cobalt phosphonate, [Co(HL)(H 2 O) 3 ] n (1) (L=N(CH 2 PO 3 H) 3 3− ) has been synthesized by hydrothermal reaction at 150 °C and structurally characterized by X-ray diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Complex 1 features a 1D chain structure with double-channel built from CoO 6 octahedra bridged together by the phosphonate groups. Each cobalt ion is octahedrally coordinated by three phosphonate oxygen atoms and three water molecules. The coordinated water molecules can form the hydrogen bonds with the phosphonate oxygen atoms to link the 1D chains, building a 2D layered structure, further resulting in a 3D network. The luminescence spectrum indicates an emission maximum at 435 nm. The magnetic susceptibility curve exhibits a dominant antiferromagnetic behavior with a weakly ferromagnetic component at low temperatures. - Graphical abstract: The connectivity between cobalt ions and the ligands results in a chain structure with a 1D double-channel structure, which is constructed by A-type subrings and B-type subrings. - Highlights: • The tetrafunctional phosphonate ligand was used as the ligand. • A novel chain structure can be formed by A-type rings and B-type rings. • Two types of rings can form a 1D double-channel structure, along the c-axis

Limitations in determining enantiomeric excess of alcohols by 31 P-NMR of the phosphonate derivatives

International Nuclear Information System (INIS)

Laverde Junior, Antonio; Conceicao, Jelson J.A. da; Pilli, Ronaldo A.; Marsaioli, Anita J.; Miranda, Domingos S. de; Schirmer, Heiko; Meijere, Armin de

1999-01-01

The use of diastereomeric alcohol dialkyl-phosphonate derivatives to determine the enantiomeric excesses via 31 P-NMR signal ratios of anisochronous meso and threo isomers was successfully applied to secondary alcohols (Feringa's method). Expansion of the methodology to primary alcohols processing the hydroxyl groups tethered to the stereogenic centers by two or more methylene groups proved the method to be inefficient. The comparison between the coupled and decoupled spectra is important in order to identify the signals corresponding to the dialkyl-phosphonates. Nevertheless the methodology should be applied whenever the amount of the alcohol and its structure are not the limiting factors. (author)

Synthesis, crystal structures, and luminescent properties of two series' of new lanthanide (III) amino-carboxylate-phosphonates.

Science.gov (United States)

Zhou, Tian-Hua; Yi, Fei-Yan; Li, Pei-Xin; Mao, Jiang-Gao

2010-02-01

Hydrothermal reactions of lanthanide(III) chlorides with 4-HOOC-C(6)H(4)-CH(2)NHCH(2)PO(3)H(2) (H(3)L) at different ligand-to-metal (L/M) ratios afforded nine new lanthanide(III) carboxylate-phosphonates with two types of 3D network structures, namely, LnCl(HL)(H(2)O)(2) (Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Er, 6) and [Ln(2)(HL)(H(2)L)(L)(H(2)O)(2)].4H(2)O (Ln = Nd, 7; Sm, 8; Eu, 9). Compounds 1-6 are isostructural and feature a 3D network in which the LnO(7)Cl polyhedra are interconnected by bridging CPO(3) tetrahedra into 2D inorganic layers parallel to the bc plane. These layers are further cross-linked by organic groups of the carboxylate-phosphonate ligands via the coordination of the carboxylate groups into a pillared-layered architecture. Compounds 7-9 are also isostructural and feature a 3D open-framework composed of 1D lanthanide(III) phosphonate inorganic slabs which are further bridged by organic groups of the carboxylate-phosphonate liagnds via the coordination of the carboxylate groups, forming large 1D tunnels along the b-axis which are filled by lattice water molecules. Luminescent measurements indicate that compounds 2, 4, and 5 show strong emission bands in red, green, and yellow light region, respectively. Magnetic properties of 2, 3, 5, and 7 have also been studied.

Covalent modification of calcium hydroxyapatite surface by grafting phenyl phosphonate moieties

International Nuclear Information System (INIS)

Aissa, Abdallah; Debbabi, Mongi; Gruselle, Michel; Thouvenot, Rene; Gredin, Patrick; Traksmaa, Rainer; Tonsuaadu, Kaia

2007-01-01

The reaction between phenyl phosphonic dichloride (C 6 H 5 P(O)Cl 2 ) and synthetic calcium hydroxy- and fluorapatite has been investigated. The presence of mono- or polymeric (C 6 H 5 PO) fragment bound to hydroxyapatite was evidenced by IR, and solid-state 31 P NMR spectroscopy. X-ray powder analysis has shown that the apatitic structure remains unchanged during the reaction. In contrast, no reaction was found using fluorapatite. According to the results found for these two different apatites a mechanism was proposed for the formation of covalent P-O-P bonds as the result of a reaction between the C 6 H 5 P(O)Cl 2 organic reagent and (HPO 4 ) - and/or OH - ions of the hydroxyapatite. - Graphical abstract: Representation of the first step of the reaction between the phenyl phosphonic dichloride and the hydroxyl groups on the surface of the apatite, leading to covalent P-O-P bond with elimination of HCl

Novel alpha-hydroxy phosphonic acids via castor oil

Science.gov (United States)

Hydroxy fatty acids (HFAs) have found a number of uses in today’s market, with uses ranging from materials to pharmaceuticals. Castor oil has served as a versatile HFA; its principle component, ricinoleic acid, can be isolated from castor oil and has been modified extensively for a number of applica...

Use of new phosphonylating and coupling agents in the synthesis of oligodeoxyribonucleotides via the H-phosphonate approach.

OpenAIRE

Sakatsume, O; Yamane, H; Takaku, H; Yamamoto, N

1990-01-01

New phosphonylating and coupling agents for the synthesis of oligodeoxyribonucleotides via H-phosphonate approach have been developed. Tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, prepared by the reaction of lithium salt of 1,1,1,3,3,3-hexafluoro-2-propoxide with PCl3, reacts with deoxyribonucleosides in the presence of a catalytic amount of triethylamine to produce in the high yield the corresponding deoxyribonucleoside 3'-H-phosphonate units. The use of a new coupling reagent, 1,3-dimet...

Proton conducting graft copolymers with tunable length and density of phosphonated side chains for fuel cell membranes

DEFF Research Database (Denmark)

Dimitrov, Ivaylo; Takamuku, Shogo; Jankova Atanasova, Katja

2014-01-01

Polysulfones functionalized with highly phosphonated poly(pentafluorostyrene) side chains of different lengths were synthesized applying controlled polymerization and modification methods. The graft copolymers' thermal properties were evaluated by differential scanning calorimetry and thermal...... gravimetrical analyses. The proton conductivity of membrane prepared from the graft copolymer with the shortest phosphonated side chains was 134 mS cm(-1) at 100 degrees C under fully immersed conditions. The graft copolymer TEM image shows a nanophase separation of ion-rich segments within the polysulfone...

Ionic flotation of uranium contained in industrial phosphoric acid

International Nuclear Information System (INIS)

Jdid; Blazy; Bessiere

1983-01-01

A new process for uranium recovery from industrial phosphoric acid at 30% of P 2 O 5 is applied by the ionic flotation process. Research is carried out on determination of the nature of ionic species of U in H 3 PO 4 5.5 M and the behavior of reagents from CECA Co. in very acid media. Reagents able to form complexes directly with uranium and stable in phosphoric acid selected are: potassium ethylene diamine tetra (methylene phosphonate) (INIPOL AD32) and sodium dialkyldiphosphonate (34S). Uranium IV, obtained by reduction of uranium VI with iron powder, is precipitated by these reagents. Flotation of the precipitate obtained with INIPOL AD 32 is realized by addition of hexylamino bis (methylene phosphonic acid). A recovery of 80 wt% is obtained. Flotation of the coprecipitate 34S-U(IV) is obtained without any other additions because 34S is a surfactant. Metal recovery is better than 90% and the coprecipitate contains more than 10% U. The process is fast precipitation 10 minutes and flotation 5 minutes and is efficient even at 60 0 C [fr

A functionalized phosphonate-rich organosilica layered hybrid material (PSLM) fabricated through a mild process for heavy metal uptake

Energy Technology Data Exchange (ETDEWEB)

Daikopoulos, Chris [Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110 (Greece); Bourlinos, Athanasios B. [Institute of Materials Science, NCSR “Demokritos”, Ag. Paraskevi Attikis, Athens 15310 (Greece); Georgiou, Yiannis [Laboratory of Physical Chemistry, Department of Environmental and Natural Resources Management, University of Patras, Seferi 2, Agrinio 30100 (Greece); Deligiannakis, Yiannis, E-mail: ideligia@cc.uoi.gr [Laboratory of Physical Chemistry, Department of Environmental and Natural Resources Management, University of Patras, Seferi 2, Agrinio 30100 (Greece); Zboril, Radek [Regional Centre of Advanced Technologies and Materials, Faculty of Science, Department of Physical Chemistry and Experimental Physics, Palacky University, Olomouc 77146 (Czech Republic); Karakassides, Michael A. [Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110 (Greece)

2014-04-01

Highlights: • Novel phosphonate-rich organosilica layered hybrid material (PSLM) fabricated through a mild xerogel process. • Surface Complexation Modeling reveals that PSLM bears 2 types of functional groups able to bind heavy metal. • Maximum metal uptake capacities were found 2.72 mmol g{sup −1} for Cu{sup 2+}, 1.67 mmol g{sup −1} for Pb{sup 2+} and 1.00 mmol g{sup −1} for Cd{sup 2+} at pH 7. • EPR spectroscopy reveals local coordination environment for Cu{sup 2+} ions. - Abstract: A phosphonate-rich organosilica layered hybrid material (PSLM) made of 3-(trihydroxysilyl)propyl methylphosphonate, monosodium salt, as the single silica source, has been obtained from its aqueous solution through a xerogel process and mild thermal aging. The method is simple, affording bulk quantities of powdered PSLM in a single-step. The hybrid is stable in water and possesses a high content of phosphonate groups fixed on the solid matrix. In addition, PSLM shows good thermal stability, which exceeds 300 °C in air. The material was characterized using SEM, TEM, XRD, FT-IR and TGA techniques. Potentiometric titrations show that PSLM bears high-surface density of phosphonate groups (3 mmol g{sup −1}). As a result, the material displays high metal uptake capacity for heavy metal ions such as Cu{sup 2+} (2.72 mmol g{sup −1}), Pb{sup 2+} (1.67 mmol g{sup −1}) and Cd{sup 2+} (1.00 mmol g{sup −1}) at neutral pH values e.g. the pH of natural waters. Detailed theoretical modeling using a Surface Complexation Model combined with Electron Paramagnetic Resonance (EPR) spectroscopy shows that the surface distribution of surface bound Cu{sup 2+} ions is rather homogeneous e.g. copper-binding phosphonate sites are arranged in average distances 5–8 Å.

Polysulfone Functionalized With Phosphonated Poly(pentafluorostyrene) Grafts for Potential Fuel Cell Applications

DEFF Research Database (Denmark)

Dimitrov, Ivaylo; Takamuku, Shogo; Jankova Atanasova, Katja

2012-01-01

A multi‐step synthetic strategy to polysulfone (PSU) grafted with phosphonated poly(pentafluorostyrene) (PFS) is developed. It involves controlled radical polymerization resulting in alkyne‐end functional PFS. The next step is the modification of PSU with a number of azide side groups. The grafting...

Hydrothermal syntheses and anion-induced structural transformation of three Cadmium phosphonates

Science.gov (United States)

Hu, Han; Zhai, Fupeng; Liu, Xiaofeng; Ling, Yun; Chen, Zhenxia; Zhou, Yaming

2018-05-01

Three cadmium phosphonate coordinated polymers, namely as [Cd5(ptz)3(SO4)2(5H2O)]·6H2O (Cdptz-1), [Cd3(ptz)2(Cl)2(4H2O)]·2H2O (Cdptz-2) and [Cd4(ptz)2(SO4)(Cl)(OH)H2O]·H2O (Cdptz-3) have been hydrothermally synthesized using 4-(1,2,4-triazol-4-yl)phenylphosphonic acid (H2ptz) as ligand. Single crystal X-ray analyses revealed Cdptz-2 as layered structure and Cdptz-1,3 as pillar-layered structures with Cl- or SO42- as bridging anions. Due to the weak bonding between metal and anions, Cdptz-1 and 2 can reversibly convert into each other by simple immersing in the corresponding solution at room temperature. While the transformations between Cdptz-1,2 and Cdptz-3 can only happen under hydrothermal condition. The causes for the transformation involve the metal-ligand bond breaking/formation, replacement of anions and enhancement/decrement of the network dimensionality.

Lanthanide phosphonates: Synthesis, thermal stability and magnetic characterization

Energy Technology Data Exchange (ETDEWEB)

Amghouz, Z., E-mail: amghouz.uo@uniovi.es [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Garcia, J.R.; Garcia-Granda, S. [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Clearfield, A. [Department of Chemistry, Texas A and M University, College Station, TX 77842-3012 (United States); Rodriguez Fernandez, J.; Pedro, I. de [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

2012-09-25

Highlights: Black-Right-Pointing-Pointer Report of the complete series of lanthanide 1,4-phenylbis(phosphonate). Black-Right-Pointing-Pointer Synthesis under conventional hydrothermal synthesis or microwave-assisted hydrothermal synthesis. Black-Right-Pointing-Pointer Cation size is the key factor for the structural and particles size variations. Black-Right-Pointing-Pointer Thermal behaviour is characterized by unusual very high thermal stability. - Abstract: Series of novel organic-inorganic hybrids materials based on trivalent lanthanides (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and 1,4-phenylbis(phosphonate) obtained under hydrothermal conditions either by oven heat or microwave irradiation. The anhydrous compounds containing La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho, are isostructural. However, the compounds based on Y, Er, Tm, Yb, and Lu are hydrated and their structures have not yet been solved. The series of compounds are characterized by PXRD, TEM, SEM-EDX and thermal analyses (TG-MS and DSC). TEM study show a variable particles size with a minimum mean-particle size of ca. 30 nm. These compounds exhibit unusual very high thermal stability. The size of particles and the thermal stability are depending on lanthanide(III) cation features. All the investigated materials show paramagnetic behaviour. The magnetic susceptibility data follow a Curie-Weiss laws with paramagnetic effective moments in good agreement with those expected for Ln{sup 3+} free ions.

Cu-Catalyzed Asymmetric Allylic Alkylation of Phosphonates and Phosphine Oxides with Grignard Reagents

NARCIS (Netherlands)

Hornillos, Valentin; Perez, Manuel; Fananas-Mastral, Martin; Feringa, Ben L.

An efficient and highly enantioselective copper-catalyzed allylic alkylation of phosphonates and phosphine oxides with Grignard reagents and Taniaphos or phosphoramidites as chiral ligands is reported. Transformation of these products leads to a variety of new phosphorus-containing chiral

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

Science.gov (United States)

Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

2018-05-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

Geminal difunctionalization of α-diazo arylmethylphosphonates: synthesis of fluorinated phosphonates.

Science.gov (United States)

Zhou, Yujing; Zhang, Yan; Wang, Jianbo

2016-11-08

A general approach towards diverse fluorinated phosphonates via geminal difunctionalization reactions of α-diazo arylmethylphosphonates is described. The diazo functionality (RR'C[double bond, length as m-dash]N 2 ) is successfully converted to RR'CF 2 , RR'CHF, RR'CFBr or RR'CFNR'' 2 groups by employing different fluorination reagents. A variety of fluorinated organophosphorus compounds were readily accessed in good to excellent yields from a common type of precursor.

Secretion of antiretroviral chemokines by human cells cultured with acyclic nucleoside phosphonates

Czech Academy of Sciences Publication Activity Database

Zídek, Zdeněk; Kmoníčková, Eva; Holý, Antonín

2007-01-01

Roč. 574, - (2007), s. 77-84 ISSN 0014-2999 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z50390512; CEZ:AV0Z40550506 Keywords : Acyclic nucleoside phosphonate * Chemokine * Cytokine Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.376, year: 2007

Studies on the preparation and stability of samarium-153 propylene diamine tetramethylene phosphonate (PDTMP) complex as a bone seeker

International Nuclear Information System (INIS)

Majali, M.A.; Mathakar, A.R.; Shimpi, H.H.; Banerjee, Sharmila; Samuel, Grace

2000-01-01

Propylene diamine tetra methylene phosphonate (PDTMP) was synthesised by modifying a method reported for the synthesis of EDTMP. Complexation of the synthesised phosphonate ligand with 153 Sm was carried out by varying the experimental parameters and the complex was radiochemically characterized. Biodistribution studies showed that the uptake by bone in rats was 2% per g of bone, which was retained up to 48 h. The uptake by other organs was insignificant, except by the liver which showed a slightly higher absorption

New prodrugs of two pyrimidine acyclic nucleoside phosphonates: Synthesis and antiviral activity

Czech Academy of Sciences Publication Activity Database

Krečmerová, Marcela; Dračínský, Martin; Snoeck, R.; Balzarini, J.; Pomeisl, Karel; Andrei, G.

2017-01-01

Roč. 25, č. 17 (2017), s. 4637-4648 ISSN 0968-0896 R&D Projects: GA ČR(CZ) GA14-00522S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * open-ring * PMEO-DAPy * 5-azacytosine * PME-azaC * HPMP-5-azaC Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.930, year: 2016

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

Energy Technology Data Exchange (ETDEWEB)

Coan, Patrick D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Ellis, Lucas D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Griffin, Michael B. [National Bioenergy Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Schwartz, Daniel K. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Medlin, J. Will [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States

2018-03-01

Cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

Science.gov (United States)

2016-01-01

Summary Multicomponent reactions (MCRs) are one of the most important processes for the preparation of highly functionalized organic compounds in modern synthetic chemistry. As shown in this review, they play an important role in organophosphorus chemistry where phosphorus reagents are used as substrates for the synthesis of a wide range of phosphorylated heterocycles. In this article, an overview about multicomponent reactions used for the synthesis of heterocyclic compounds bearing a phosphonate group on the ring is given. PMID:27559377

A New Multichelating Acid System for High-Temperature Sandstone Reservoirs

Directory of Open Access Journals (Sweden)

Nianyin Li

2015-01-01

Full Text Available Sandstone reservoir acidizing is a complex and heterogeneous acid-rock reaction process. If improper acid treatment is implemented, further damage can be induced instead of removing the initial plug, particularly in high-temperature sandstone reservoirs. An efficient acid system is the key to successful acid treatment. High-temperature sandstone treatment with conventional mud acid system faces problems including high acid-rock reaction rate, short acid effective distance, susceptibility to secondary damage, and serious corrosion to pipelines. In this paper, a new multichelating acid system has been developed to overcome these shortcomings. The acid system is composed of ternary weak acid, organic phosphonic chelating agent, anionic polycarboxylic acid chelating dispersant, fluoride, and other assisted additives. Hydrogen ion slowly released by multistage ionization in ternary weak acid and organic phosphonic within the system decreases the concentration of HF to achieve retardation. Chelating agent and chelating dispersant within the system inhibited anodic and cathodic reaction, respectively, to protect the metal from corrosion, while chelating dispersant has great chelating ability on iron ions, restricting the depolarization reaction of ferric ion and metal. The synergic effect of chelating agent and chelating dispersant removes sulfate scale precipitation and inhibits or decreases potential precipitation such as CaF2, silica gel, and fluosilicate. Mechanisms of retardation, corrosion-inhibition, and scale-removing features have been discussed and evaluated with laboratory tests. Test results indicate that this novel acid system has good overall performance, addressing the technical problems and improving the acidizing effect as well for high-temperature sandstone.

Exploiting the high-affinity phosphonate-hydroxyapatite nanoparticle interaction for delivery of radiation and drugs

International Nuclear Information System (INIS)

Ong, Hooi Tin; Loo, Joachim S. C.; Boey, Freddy Y. C.; Russell, Stephen J.; Ma Jan; Peng, Kah-Whye

2008-01-01

Hydroxyapatite is biocompatible and used in various biomedical applications. Here, we generated hydroxyapatite nanoparticles (HNPs) of various sizes (40-200 nm) and demonstrated that they can be stably loaded with drugs or radioisotopes by exploiting the high-affinity HA-(poly)phosphonate interaction. Clinically available phosphonates, clodronate, and Tc-99m-methylene-diphosphonate (Tc-99m-MDP), were efficiently loaded onto HNPs within 15 min. Biodistribution of radiolabeled HNP-MDP-Tc99m in mice was monitored non-invasively using microSPECT-CT. Imaging and dosimetry studies indicated that the HNPs, regardless of size, were quickly taken up by Kupffer cells in the liver after systemic administration into mice. Clodronate loaded onto HNPs remained biologically active and were able to result in selective depletion of Kupffer cells. This method of drug or isotope loading on HA is fast and easy as it eliminates the need for additional surface modifications of the nanoparticles

Production, biodistribution, and dosimetry of 47Sc-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetramethylene phosphonic acid as a bone-seeking radiopharmaceutical

Directory of Open Access Journals (Sweden)

Fatemeh Fathi

2015-01-01

Full Text Available In this study 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetramethylene phosphonic acid (DOTMP was used as the polyaminophosphonic acid carrier ligand and the therapeutic potential of the bone seeking radiopharmaceutical 47Sc-DOTMP was assessed by measuring its dosage–dependent skeletal uptake and then the absorbed radiation dose of human organs was estimated. Because of limited availability of 47Sc we performed some preliminary studies using 46Sc. 46Sc was produced with a specific activity of 116.58 MBq/mg (3.15 mCi/mg and radionuclide purity of 98%. 46Sc-DOTMP was prepared and an activity of 1.258 MBq (34 μCi at a chelant-to-metal ratio of 60:1 was administered to five groups of mice with each group containing 3 mice that were euthanized at 4, 24, 48, 96 and 192 h post administration. The heart, lungs, liver, spleen, kidneys, intestine, skin, muscle, and a femur were excised, weighed, and counted. The data were analyzed to determine skeletal uptake and source organ residence times and cumulated activities for 47Sc-DOTMP. 46Sc-DOTMP complex was prepared in radiochemical purity about 93%. In vitro stability of complex was evaluated at room temperature for 48 h. Biodistribution studies of complex in mice were studied for 7 days. The data were analyzed to estimate skeletal uptake and absorbed radiation dose of human organs using biodistribution data from mice. By considering the results, 47Sc-DOTMP is a possible therapeutic agent for using in palliation of bone pain due to metastatic skeletal lesions from several types of primary cancers in prostate, breast, etc.

Racemic cobalt phosphonates incorporating flexible bis(imidazole) co-ligands.

Science.gov (United States)

Feng, Jian-Shen; Cai, Zhong-Sheng; Ren, Min; Bao, Song-Song; Zheng, Li-Min

2015-11-07

By incorporating flexible bis(imidazol-1-ylmethyl)benzene (bix) co-ligands, four new racemic cobalt phosphonates with formulae Co3(3-ppap)2(1,4-bix)2(H2O)4·4H2O (1), Co3(3-ppap)2(1,3-bix)2(H2O)4·5H2O (2), Co3(3-ppap)2(1,2-bix)2(H2O)4·4H2O (3) and Co3(ppa)2(1,2-bix)2·4H2O (4) are isolated, where 3-ppapH3 represents 3-phenyl-3-((phosphonomethyl)amino)propanoic acid and ppaH3 is 2-phenyl-2-(phosphonomethylamino)acetic acid. Compounds 1-3 crystallize in the monoclinic space group P21/c and show two-dimensional structures in which the Co3(3-ppap)2 chains are bridged by 1,4-bix, 1,3-bix and 1,2-bix ligands in trans-modes, respectively. Within the chain, a racemic dimer of Co2(3-ppap)2(2-) is found, where the Co atoms are doubly bridged by O-P-O units from the (S)- and (R)-3-ppap(3-) ligands. The dimers are connected by another crystallographically independent Co atom through O-P-O linkages to form an infinite racemic chain. The packing modes of the layers in 1-3 are quite different, however, which are ABAB in the cases of 1 and 3 while ABCDABCD in the case of 2, attributed to the positional isomerism of the bix co-ligands. Compound 4 displays a chain structure in which the 1,2-bix bridges the Co atoms in cis-mode within the chain. Magnetic properties are investigated for all compounds.

N-Branched acyclic nucleoside phosphonates as monomers for the synthesis of modified oligonucleotides

Czech Academy of Sciences Publication Activity Database

Hocková, Dana; Rosenbergová, Šárka; Ménová, Petra; Páv, Ondřej; Pohl, Radek; Novák, Pavel; Rosenberg, Ivan

2015-01-01

Roč. 13, č. 15 (2015), s. 4449-4458 ISSN 1477-0520 R&D Projects: GA ČR GAP207/11/0108; GA ČR GA13-26526S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * oligonucleotides * solid phase synthesis Subject RIV: CC - Organic Chemistry Impact factor: 3.559, year: 2015

Synthesis and characterization of poly(vinylphosphonic acid) for proton exchange membranes in fuel cells

Energy Technology Data Exchange (ETDEWEB)

Bingoel, Bahar

2007-07-01

Vinylphosphonic acid (VPA) was polymerized at 80 C by free radical polymerization to give polymers (PVPA) of different molecular weight depending on the initiator concentration. The highest molecular weight, Mw, achieved was 6.2 x 10{sup 4} g/mol as determined by static light scattering. High resolution nuclear magnetic resonance (NMR) spectroscopy was used to gain microstructure information about the polymer chain. Information based on tetrad probabilities was utilized to deduce an almost atactic configuration. In addition, {sup 13}CNMR gave evidence for the presence of head-head and tail-tail links. Refined analysis of the {sup 1}H NMR spectra allowed for the quantitative determination of the fraction of these links (23.5 percent of all links). Experimental evidence suggested that the polymerization proceeded via cyclopolymerization of the vinylphosphonic acid anhydride as an intermediate. Titration curves indicated that high molecular weight poly(vinylphosphonic acid) PVPA behaved as a monoprotic acid. Proton conductors with phosphonic acid moieties as protogenic groups are promising due to their high charge carrier concentration, thermal stability, and oxidation resistivity. Blends and copolymers of PVPA have already been reported, but PVPA has not been characterized sufficiently with respect to its polymer properties. Therefore, we also studied the proton conductivity behaviour of a well-characterized PVPA. PVPA is a conductor; however, the conductivity depends strongly on the water content of the material. The phosphonic acid functionality in the resulting polymer, PVPA, undergoes condensation leading to the formation of phosphonic anhydride groups at elevated temperature. Anhydride formation was found to be temperature dependent by solid state NMR. Anhydride formation affects the proton conductivity to a large extent because not only the number of charge carriers but also the mobility of the charge carriers seems to change. (orig.)

Preparates for the production of technetium 99m radiodiagnostics

International Nuclear Information System (INIS)

Schmidt-Dunker, M.; Greb, W.

1984-01-01

The preparates serve the production of Tc 99m radiodiagnostics for the scintiscanning of bones or calcareous tumors, muscle tissue or arterial sclerosis. They consist of mixtures of a carboxy phosphonic acid and/or carboxy phosphonate or its water-soluble salts, as well as 1-5 wt.% of a Sn(II), Fe(II) or Cr(II) salt. The mixture has a pH value of 3 to 9. The preparates are in particular of phosphons-ethane-1,2-dicarbonic acid (mixture of di/trisodium slat of 2:1) and SnCl2; 1-phosphons-propane-1,2-dicarbonic acid (di/tri-sodium salt 2:1) and chromium (II) chloride; 2-phosphons-butane-1,2,4-tricarbonic acid (trisodium salt) and iron(II) sulphate; 1-phosphons-propane-1,2-dicarbonic acid (di/tri-sodium salt 2:1) and Sn(II) chloride; 1-phosphons-propane-1,2-dicarbonic acid (di/tri-sodium salt 2:1) and 2-phosphono-butane-1,2,4-tricarbonic acid (trisodium salt) and Fe(II) sulphate; or phosphons-ethane-1,2-dicarbonic acid (di/tri-sodium salt 2:1) and Sn(II) Cl2 and Fe(II) sulphate. They may be produced as solution or dragee. The Sn(II), Fe(II) and Cr(II) salts serve as reducing agent for the eluated pertechnetate 99m. Glucose or NaCl may be used as filler. (orig./PW)

Preparates for the production of technetium 99m radiodiagnostics

International Nuclear Information System (INIS)

Schmidt-Dunker, M.; Greb, W.

1977-01-01

The preparates serve the production of Tc 99m radiodiagnostics for the scintiscanning of bones or calcareous tumors, muscle tissue or arterial sclerosis. They consist of mixtures of a carboxy phosphonic acid and/or carboxy phosphonate or its water-soluble salts, as well as 1-5 wt.% of a Sn(II), Fe(II) or Cr(II) salt. The mixture has a pH valve of 3 to 9. The preparates are in particular of phosphons-ethane-1,2-dicarbonic acid (mixture of di/trisodium slat of 2:1) an SnCl 2 ; 1-phosphons-propane-1,2-dicarbonic acid (di/tri-sodiium salt 2:1) and chromium (II) chloride; 2- phosphons-butane-1,2,4-tricarbonic acid (trisodium salt) and iron(II) sulphate; 1-phosphons-propane-1,2-dicarbonic acid (di/tri-sodium salt 2:1) and Sn(II) chloride; 1-phosphons-propane-1,2-dicarbonic acid (di/tri-sodium salt 2:1) and 2-phosphono-butane-1,2,4-tricarbonic acid (trisodium salt) and F(II) sulphate; or phosphons-ethane-1,2-dicarbonic acid (di/tri-sodium salt 2:1) and Sn(II) Cl 2 and Fe(II) sulphate. They many be produced as solution or dragee. The Sn(II), Fe(II) and Cr(II) salts serve as reducing agent for the eluated pertechnetate 99m. Glucose or NaCl may be used as filler. (DG) 891 HP [de

Phosphonate self-assembled monolayers as organic linkers in solid-state quantum dot sensetized solar cells

KAUST Repository

Ardalan, Pendar

2010-06-01

We have employed X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) spectroscopy, infrared (IR) spectroscopy, water contact angle (WCA) measurements, ellipsometry, and electrical measurements to study the effects of self-assembled monolayers (SAMs) with phosphonic acid headgroups on the bonding and performance of cadmium sulfide (CdS) solid-state quantum dot sensitized solar cells (QDSSCs). ∼2 to ∼6 nm size CdS quantum dots (QDs) were grown on the SAM-passivated TiO2 surfaces by successive ionic layer adsorption and reaction (SILAR). Our results show differences in the bonding of the CdS QDs at the TiO2 surfaces with a SAM linker. Moreover, our data indicate that presence of a SAM increases the CdS uptake on TiO2 as well as the performance of the resulting devices. Importantly, we observe ∼2 times higher power conversion efficiencies in the devices with a SAM compared to those that lack a SAM. © 2010 IEEE.

Surface functionalization of detonation nanodiamonds by phosphonic dichloride derivatives.

Science.gov (United States)

Presti, Charlene; Alauzun, Johan G; Laurencin, Danielle; Mutin, P Hubert

2014-08-05

A new method for the functionalization of detonation nanodiamonds (DNDs) is proposed, on the basis of surface modification with phosphonic dichloride derivatives. DNDs were first modified by phenylphosphonic dichloride, and the grafting modes and hydrolytic stability under neutral conditions were investigated using (1)H, (13)C, and (31)P solid state NMR spectroscopy, Fourier transform infrared spectroscopy, as well as elemental analysis. Then, in order to illustrate the possibilities offered by this method, DNDs functionalized by mesityl imidazolium groups were obtained by postmodification of DNDs modified by 12-bromododecylphosphonic dichloride. The oxidative thermal stability of the functionalized DNDs was investigated using thermogravimetric analysis.

Passive films and corrosion protection due to phosphonic acid inhibitors

Energy Technology Data Exchange (ETDEWEB)

Fang, J.L.; Liu, Q. (Nanjing Univ. (China)); Li, Y.; Wang, Z.W. (Nanjing Inst. of Chemical Tech. (China))

1993-04-01

For protecting mild steel from corrosion, aminotrimethylidenephosphonic acid (ATMP) was more effective than 1-hydroxyethylidene diphosphonic acid (HEDP), N.N-dimethylidenediphosphonic acid (EEDP), and ethylenediaminetetramethylidenephosphonic acid (EDTMP). A 20-min treatment in 1.0 mol/l of ATMP with a pH 0.23 at 45 C formed an anti-corrosive complex film that was composed of 48.4% O, 28.6% P, 7.0% Fe, 4.3% N, and 11.7% C, based on x-ray photoelectron spectroscopy and Auger electron spectroscopy. From differences in binding energies of Fe, N, and O, in the shift of C-N and P-O vibration, in the reflection FTIR spectra, and in the change of P-OH and Fe-N vibration before and after film formation, it was deduced that N and O in ATMP were coordinated with Fe[sub 2+] in the film.

Evaluation of Titanium Dioxide as a Binding Phase for the Passive Sampling of Glyphosate and Aminomethyl Phosphonic Acid in an Aquatic Environment.

Science.gov (United States)

Fauvelle, Vincent; Nhu-Trang, Tran-Thi; Feret, Thibaut; Madarassou, Karine; Randon, Jérôme; Mazzella, Nicolas

2015-06-16

Glyphosate is the most widely used herbicide on a world scale for the last 40 years, for both urban and agricultural uses. Here we describe the first passive sampling method for estimating the concentration of glyphosate and AMPA (aminomethyl phosphonic acid, one of its major degradation products) in surface water. The sampling method is based on a newly developed configuration of the diffusive gradient in thin-film (DGT) technique, which includes a TiO2 binding phase, already in use for a wide range of anions. Glyphosate and AMPA were retained well on a TiO2 binding phase, and elution in a 1 mL of 1 M NaOH led to recoveries greater than 65%. We found no influence of pH or flow velocity on the diffusion coefficients through 0.8 mm polyacrylamide gels, although they did increase with temperature. TiO2 binding gels were able to accumulate up to 1167 ng of P for both glyphosate and AMPA, and linear accumulation was expected over several weeks, depending on environmental conditions. DGT sampling rates were close to 10 mL day(-1) in ultrapure water, while they were less than 1 mL day(-1) in the presence of naturally occurring ions (e.g., copper, iron, calcium, magnesium). These last results highlighted (i) the ability of DGT to measure only the freely dissolved fraction of glyphosate and AMPA in water and (ii) the needs to determine which fraction (total, particulate, dissolved, freely dissolved) is indeed bioactive.

A Pyrene- and Phosphonate-Containing Fluorescent Probe as Guest Molecule in a Host Polymer Matrix

Directory of Open Access Journals (Sweden)

Jacqueline Marchand-Brynaert

2013-02-01

Full Text Available New host-guest materials have been prepared by incorporation of a home-made organic probe displaying a pyrene motif and a phosphonate function into a regular amphiphilic copolymer. Using powder X-Ray diffraction, photoluminescence and FT-IR spectroscopy, we have been able to study the non-covalent interactions between the host matrix and the guest molecule in the solid state. Interestingly, we have shown that the matrix directs the guest spatial localization and alters its properties. Thanks to the comparison of pyrene vs. N-pyrenylmaleimide derivatives, the influence of the chemical nature of the guest molecules on the non-covalent interactions with the host have been studied. In addition, using polyethylene glycol as a reference host, we have been able to evidence a true matrix effect within our new insertion materials. The phosphonated guest molecule appears to be a novel probe targeting the hydrophilic domain of the host copolymer.

Passivation of aluminum with alkyl phosphonic acids for biochip applications

Science.gov (United States)

Attavar, Sachin; Diwekar, Mohit; Linford, Matthew R.; Davis, Mark A.; Blair, Steve

2010-09-01

Self-assembly of decylphosphonic acid (DPA) and octadecylphosphonic acid (ODPA) was studied on aluminum films using XPS, ToF-SIMS and surface wettability. Modified aluminum films were tested for passivation against silanization and subsequent oligonucleotide attachment. Passivation ratios of at least 450:1 compared to unprotected aluminum were obtained, as quantified by attachment of radio-labeled oligos.

Excitatory amino acid receptor antagonists

DEFF Research Database (Denmark)

Johansen, T N; Frydenvang, Karla Andrea; Ebert, B

1997-01-01

We have previously shown that (RS)-2-amino-2-(5-tert-butyl-3-hydroxyisoxazol-4-yl)acetic acid (ATAA) is an antagonist at N-methyl-D-aspartic acid (NMDA) and (RS)-2-amino-3-(3-hydroxy-5-methylisoxazol-4-yl)propionic acid (AMPA) receptors. We have now resolved ATAA via diastereomeric salt formation......)-phenylethylamine salt of N-BOC-(R)-ATAA. Like ATAA, neither (R)- nor (S)-ATAA significantly affected (IC50 > 100 microM) the receptor binding of tritiated AMPA, kainic acid, or (RS)-3-(2-carboxypiperazin-4-yl)propyl-1-phosphonic acid, the latter being a competitive NMDA antagonist. Electrophysiological experiments......, using the rat cortical wedge preparation, showed the NMDA antagonist effect as well as the AMPA antagonist effect of ATAA to reside exclusively in the (R)-enantiomer (Ki = 75 +/- 5 microM and 57 +/- 1 microM, respectively). Neither (R)- nor (S)-ATAA significantly reduced kainic acid-induced excitation...

Structures of metal complexes with anions of di(hydroxymethyl)phosphinic and di(chloromethyl)phosphinic acids

International Nuclear Information System (INIS)

Sergienko, V.S.; Aleksandrov, G.G.

2001-01-01

The structural peculiarities of the different metals [Cu, Ni, rare earths (La, Nd, Er, Lu), Ag, Li, Na, Sr] with anions of di-substituted monophosphonic acids - di(hydroxymethyl) phosphonic acid (HOCH 2 ) 2 PO 2 - (L 1 ) and di(chloromethyl) phosphonic acid (ClCH 2 ) 2 PO 2 - (L 2 ), and the methods of coordinating ligands L 1 and L 2 with these metals were viewed. Coordination number of metal decreases from eight in the case of La, Nd to seven for Er, and further to six for Lu with decreasing size of rare earth element. M-O bond lengths decrease the same way. The LiL 2 · H 2 O structure was determined, Li atom shows tetrahedron coordination by three oxygen atoms of the three ligands L 2 and atom O(ω) of water molecule. The ligand L 1 are acting as a tetradentate chelate μ 3 -bridge function in the structure of the Sr(L 1 ) 2 compound. The interval of Sr-O distances comprises 2.521 - 2.683 A [ru

"Customizable" units in di- and tripeptides: selective conversion into substituted dehydroamino acids.

Science.gov (United States)

Saavedra, Carlos J; Boto, Alicia; Hernández, Rosendo

2012-07-20

The selective conversion of serine or threonine units of di- and tripeptides into substituted dehydroamino acids is reported. Thus, these common α-amino acids undergo a scission-phosphorylation process to give α-amino phosphonate residues. A Horner-Wadsworth-Emmons reaction with aldehydes or ketones follows to afford the final products with excellent Z-stereoselectivity (Z:E > 98:2). In this way, a single peptide precursor can selectively be transformed into a variety of derivatives.

Synthesis of alpha-Branched Acyclic Nucleoside Phosphonates as Potential Inhibitors of Bacterial Adenylate Cyclases

Czech Academy of Sciences Publication Activity Database

Frydrych, Jan; Skácel, Jan; Šmídková, Markéta; Mertlíková-Kaiserová, Helena; Dračínský, Martin; Gnanasekaran, Ramachandran; Lepšík, Martin; Soto-Velasquez, M.; Watts, V. J.; Janeba, Zlatko

2018-01-01

Roč. 13, č. 2 (2018), s. 199-206 ISSN 1860-7179 R&D Projects: GA MV VG20102015046; GA ČR(CZ) GBP208/12/G016; GA MŠk LO1302 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * adenylate cyclase toxin * bisamidates * Bordetella pertussis * prodrugs Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.225, year: 2016

Synergism studies on some radionuclides of nuclear and environmental importance using phosphonate compounds mixed with oxygen and phosphorous containing neutral compounds

International Nuclear Information System (INIS)

EL-Zahhar, A.Abd El Wahed M.

1998-01-01

As solvent extraction is a technique which has been highly developed within various national energy programs because of its suitability as selective separation process for fission products, actinides and other radioactive substances. It is very important to look for to be used as extractants and to study the optimum condition under which these compounds can be used as such. This work aims at studying the use of the carbamoyl phosphonate as an extractant in the extraction of certain elements. Also studying the effect of mixed extraction (possibility of enhancing extraction or synergism) as will as temperature effect on the extraction process and calculating the thermodynamic parameters of the proposed extraction reactions. To compare the extraction behavior of the phosphonate compound with other chelating agents as HTTA and HDEHP , studying the extraction of the same elements with these cheating agents under the same conditions is also one of the objectives of this work. This work also aims at studying the extraction of certain elements in comparable oxidation states. The selected elements; uranium which represents the main pert in the nuclear fuel, cobalt which is produced in the nuclear fission products, europium which is also produced as a fission product and is analog of the trivalent actinides series and chromium which is a corrosion product in the nuclear fuel cycle and is an analogue of transition elements. The work also aims at studying the extraction of the selected elements from different aqueous media of low acidic nature to classify the effect of the aqueous phase on the extraction systems handled

Selective removal of lanthanides from natural waters, acidic streams and dialysate

Energy Technology Data Exchange (ETDEWEB)

Yantasee, Wassana, E-mail: wassana.yantasee@pnl.gov [Pacific Northwest National Laboratory (PNNL), P.O. Box 999, Richland, WA 99352 (United States); Fryxell, Glen E.; Addleman, R. Shane; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya [Pacific Northwest National Laboratory (PNNL), P.O. Box 999, Richland, WA 99352 (United States); Xu Jide; Raymond, Kenneth N. [Chemistry Department, University of California, Berkeley, CA 94720 (United States); LBNL, Berkeley, CA 94720 (United States)

2009-09-15

The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, which increases public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd and Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS{sup TM}), that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (Prop-Phos), and 1-hydroxy-2-pyridinone (1,2-HOPO), from natural waters (river, ground and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate. The affinity, capacity, and kinetics of the lanthanide sorption, as well as regenerability of SAMMS materials were investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. In acid solutions, Prop-Phos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their use in chromatographic lanthanide separation. Over 95% of 100 {mu}g/L of Gd in dialysate was removed by the Prop-Phos-SAMMS after 1 min and 99% over 10 min. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties. Thus, they have a great potential to be used as in large-scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and in sorbent dialyzers for treatment of acute lanthanide poisoning.

Selective removal of lanthanides from natural waters, acidic streams and dialysate

International Nuclear Information System (INIS)

Yantasee, Wassana; Fryxell, Glen E.; Addleman, R. Shane; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya; Xu Jide; Raymond, Kenneth N.

2009-01-01

The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, which increases public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd and Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS TM ), that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (Prop-Phos), and 1-hydroxy-2-pyridinone (1,2-HOPO), from natural waters (river, ground and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate. The affinity, capacity, and kinetics of the lanthanide sorption, as well as regenerability of SAMMS materials were investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. In acid solutions, Prop-Phos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their use in chromatographic lanthanide separation. Over 95% of 100 μg/L of Gd in dialysate was removed by the Prop-Phos-SAMMS after 1 min and 99% over 10 min. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties. Thus, they have a great potential to be used as in large-scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and in sorbent dialyzers for treatment of acute lanthanide poisoning.

Inhibition of hypoxanthine-guanine phosphoribosyltransferase by acyclic nucleoside phosphonates: A new class of antimalarial therapeutics

Czech Academy of Sciences Publication Activity Database

Keough, D. T.; Hocková, Dana; Holý, Antonín; Naesens, L.; Skinner-Adams, T. S.; de Jersey, J.; Guddat, L. W.

2009-01-01

Roč. 52, č. 14 (2009), s. 4391-4399 ISSN 0022-2623 R&D Projects: GA MŠk 1M0508; GA AV ČR 1QS400550501 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * phosphoribosyltransferase * enzyme inhibitors * Plasmodium falciparum Subject RIV: CC - Organic Chemistry Impact factor: 4.802, year: 2009

Inhibition of the Escherichia coli 6-oxopurine phosphoribosyltransferases by nucleoside phosphonates: potential for new antibacterial agents

Czech Academy of Sciences Publication Activity Database

Keough, D. T.; Hocková, Dana; Rejman, Dominik; Špaček, Petr; Vrbková, Silvie; Krečmerová, Marcela; Eng, W. S.; Jans, H.; West, N. P.; Naesens, L. M. J.; de Jersey, J.; Guddat, L. W.

2013-01-01

Roč. 56, č. 17 (2013), s. 6967-6984 ISSN 0022-2623 R&D Projects: GA ČR GAP207/11/0108 Institutional support: RVO:61388963 Keywords : nucleoside phosphonates * antibacterial agents * hypoxanthine-guanine phosphoribosyltransferase * state analog inhibitor * antimalarial chemotherapy Subject RIV: CC - Organic Chemistry Impact factor: 5.480, year: 2013

Enhanced Topical and Transdermal Delivery of Antineoplastic and Antiviral Acyclic Nucleoside Phosphonate cPr-PMEDAP

Czech Academy of Sciences Publication Activity Database

Vávrová, K.; Kovaříková, P.; Školová, B.; Líbalová, M.; Roh, J.; Čáp, R.; Holý, Antonín; Hrabálek, A.

2011-01-01

Roč. 28, č. 12 (2011), s. 3105-3115 ISSN 0724-8741 R&D Projects: GA MŠk 1M0508 Grant - others:GA ČR(CZ) GAP207/11/0365 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * antivirals * antineoplastics * permeation enhancer * topical skin application * transdermal delivery Subject RIV: CC - Organic Chemistry Impact factor: 4.093, year: 2011

Understanding the interactions of phosphonate-based flame-retarding additives with graphitic anode for lithium ion batteries

International Nuclear Information System (INIS)

Feng, Jinkui; Ma, Peng; Yang, Hanxi; Lu, Li

2013-01-01

Highlights: •Diethyl ethylphosphonate (DEEP) and dimethyl methylphosphonate are tested as flame retardants for lithium ion batteries. •The DMMP shows a destructive reaction with graphitic anode while DEEP shows a self-reduction mechanism. •DEEP is reported for the first time as flame-retardant additive for lithium ion batteries and demonstrates a much better compatibility with graphitic anode. -- Abstract: The compatibility with graphitic anode has been one key problem in developing flame-retarding additives for lithium ion batteries. To understand the interactions between flame-retarding additives and graphitic anode, two phosphonate esters (dimethyl methylphosphonate DMMP and diethyl ethylphosphonate DEEP) are selected and characterized as flame retardant addtives. DEEP is reported as a flame-retarding additive for the first time. Their interactions with graphite anode are characterized via current-static charge–discharge, ex-situ XRD, FE-SEM and AC impedance. The results reveal that the two phosphonate esters demonstrate different reaction mechanisms with graphitic anode, which result in different anode compatibility. These findings may be useful for designing better flame-retarding additives for lithium ion batteries

Gas chromatography of alkylphosphonic and dialkylphosphinic acids

International Nuclear Information System (INIS)

Gasco, L.; Barrera, R.; Ramirez, A.; Martin Munoz, N.

1978-01-01

After carrying out an optimization study on the separation conditions for the TMS-derivatives, of the hexyl-, cyclohexyl-, heptyl-, and octyl-phosphonic acids; dihexyl-, dicyclohexyl-, heptyl-, and octyl-phosphinic acids, and dioctylphosphine oxide, their retention indices (I) at two temperatures and on the 0V-1 and 0V-17 stationary phase were determined. Correlations between I and molecular structure were established. Calibration factors of these compounds in the flame ionization detector were studied, and the results analized taking into account the variables afecting the quantitative results. These results were unbiased but they had a lower precission than usually achieveble in gas chromatography. (author)

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.

Gas chromatography of alkylphosphonic and dialkyl phosphinic acids

International Nuclear Information System (INIS)

Gasco Sanchez, L.; Barrera Pinero, R.; Ramirez Caceres, A.; Martin Munoz, M.

1978-01-01

After carrying out an optimization study on the separation conditions for the TMSr- derivatives, of the hexyl-, cyclohexyl-, heptyl-, and octyl-phosphonic acids; dihexyl dicyclohexyl-, heptyl-, and octyl-phosphinic acids, and dioctyl phosphine oxide, their retention indices (I) at two temperatures and on the OV-1 and OV-17 stationary phase were determined. Correlations between I and molecular structure were established. Calibration factors of these compounds in the flame ionization detector were studied, and the results analyzed taking into account the variables affecting the quantitative results, These results were unbiased but they had a lower precision than that usually achievable in gas chromatography. (Author) 24 refs

Synthesis and Evaluation of Novel Acyclic Nucleoside Phosphonates as Inhibitors of Plasmodium falciparum and Human 6-Oxopurine Phosphoribosyltransferases

Czech Academy of Sciences Publication Activity Database

Kaiser, Martin Maxmilian; Hocková, Dana; Wang, T. H.; Dračínský, Martin; Poštová Slavětínská, Lenka; Procházková, Eliška; Edstein, M. D.; Chavchich, M.; Keough, D. T.; Guddat, L. W.; Janeba, Zlatko

2015-01-01

Roč. 10, č. 10 (2015), s. 1707-1723 ISSN 1860-7179 R&D Projects: GA MV VG20102015046; GA ČR GAP207/11/0108 Institutional support: RVO:61388963 Keywords : 6-oxopurine * acyclic nucleoside phosphonates * phosphoribosyltransferases * malaria * phosphoramidates Subject RIV: CC - Organic Chemistry Impact factor: 2.980, year: 2015

Kinetic study of ion exchange in phosphoric acid chelating resin

International Nuclear Information System (INIS)

Brikci-Nigassa, Mounir; Hamouche, Hafida

1995-11-01

Uranium may be recovered as a by product of wet phosphoric acid using a method based on specific ion exchange resins. These resins called chelates contain amino-phosphonic functional groups. The resin studied in this work is a purolite S-940; uranium may be loaded on this resin from 30% P2O5 phosphoric acid in its reduced state. The influence of different parameters on the successive steps of the process have been studied in batch experiments: uranium reduction, loading and oxydation. Uranium may be eluted with ammonium carbonate and the resin regeneration may be done with hydrochloric acid.Ferric ions reduce the effective resin capacity considerably and inert fixation conditions are proposed to enhance uranium loading

Lanthanide(III) complexes of a mono(methylphosphonate) analogue of H4dota: the influence of protonation of the phosphonate moiety on the TSAP/SAP isomer ratio and the water exchange rate.

Science.gov (United States)

Rudovský, Jakub; Cígler, Petr; Kotek, Jan; Hermann, Petr; Vojtísek, Pavel; Lukes, Ivan; Peters, Joop A; Vander Elst, Luce; Muller, Robert N

2005-04-08

A monophosphonate analogue of H4dota, 1,4,7,10-tetraazacyclododecane-4,7,10-tris(carboxymethyl)-1-methylphosphonic acid (H5do3aP), and its complexes with lanthanides were synthesized. Multinuclear NMR studies reveal that, in aqueous solution, lanthanide(III) complexes of the ligand exhibit structures analogous to those of H4dota complexes. Thus, the central ion is nine-coordinate, surrounded by four nitrogen atoms, three acetate and one phosphonate oxygen atoms, and one water molecule in an apical position. For complexes of H5do3aP with Ln(III) ions in the middle of the series, the abundance of the desired twisted square-antiprismatic (TSAP) isomer is higher than for the corresponding H4dota complexes. The TSAP/square-antiprismatic (SAP) isomer ratio is highly sensitive to protonation of the phosphonate group: a higher abundance of the TSAP isomer was found in acidic solutions. The microscopic protonation constants of the TSAP isomers are higher than those of the SAP isomers. The presence of one water molecule in the first coordination sphere of the complexes in the pH region studied (pH 2.5-7.0) is confirmed by 17O NMR spectroscopy. The results of a simultaneous fit of variable-temperature 17O NMR relaxation data and 1H NMRD profiles show that the residence time of water (tauM) in the Gd(III) complex is much smaller than for [Gd(dota)(H2O)]-. The exchange rate appears to be dependent on the pH of the solution. The values of tauM are 37, 40, and 14 ns at pH 2.5, 4.7, and 7.0, respectively. These observations can be explained by an extensive second-sphere hydrogen-bonding network that varies with the state of protonation of the phosphonate moiety. Upon protonation of the complex, the second-sphere hydration probably becomes more ordered, which may result in a decrease in penetrability and an increase in tauM. The relaxivity of the Gd(III) complex is almost independent of the pH and is equal to 4.7 s(-1) mM(-1) (20 MHz, pH 7 and 37 degrees C). The solid

Acyclic Nucleoside Phosphonates Containing 9-Deazahypoxanthine and a Five-Membered Heterocycle as Selective Inhibitors of Plasmodial 6-Oxopurine Phosphoribosyltransferases

Czech Academy of Sciences Publication Activity Database

Kaiser, Martin Maxmilian; Baszczyňski, Ondřej; Hocková, Dana; Poštová Slavětínská, Lenka; Dračínský, Martin; Keough, D. T.; Guddat, L. W.; Janeba, Zlatko

2017-01-01

Roč. 12, č. 14 (2017), s. 1133-1141 ISSN 1860-7179 R&D Projects: GA ČR(CZ) GA16-06049S Institutional support: RVO:61388963 Keywords : inhibitors * nucleosides * malaria * phosphonates * purine salvage Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.225, year: 2016

Enantiopurity analysis of new types of acyclic nucleoside phosphonates by capillary electrophoresis with cyclodextrins as chiral selectors

Czech Academy of Sciences Publication Activity Database

Šolínová, Veronika; Kaiser, Martin Maxmilian; Lukáč, Miloš; Janeba, Zlatko; Kašička, Václav

2014-01-01

Roč. 37, č. 3 (2014), s. 295-303 ISSN 1615-9306 R&D Projects: GA ČR(CZ) GAP206/12/0453; GA ČR(CZ) GA13-17224S; GA MV VG20102015046 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * CE * chiral analysis * cyclodextrins * nucleotide analogs Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.737, year: 2014

Influence of Acyclic Nucleoside Phosphonate Antivirals on Gene Expression of Chemokine Receptors CCR5 and CXCR4

Czech Academy of Sciences Publication Activity Database

Potměšil, P.; Holý, Antonín; Zídek, Zdeněk

2015-01-01

Roč. 61, č. 1 (2015), s. 1-7 ISSN 0015-5500 R&D Projects: GA ČR GA305/03/1470; GA MŠk 1M0508 Institutional support: RVO:61388963 ; RVO:68378041 Keywords : acyclic nucleoside phosphonate * HIV * CCR5 * CXCR4 * cytokine * RT-PCR Subject RIV: CC - Organic Chemistry; FR - Pharmacology ; Medidal Chemistry (UEM-P) Impact factor: 0.833, year: 2015

Surface modification of poly(D,L-lactic acid) scaffolds for orthopedic applications: a biocompatible, nondestructive route via diazonium chemistry.

Science.gov (United States)

Mahjoubi, Hesameddin; Kinsella, Joseph M; Murshed, Monzur; Cerruti, Marta

2014-07-09

Scaffolds made with synthetic polymers such as polyesters are commonly used in bone tissue engineering. However, their hydrophobicity and the lack of specific functionalities make their surface not ideal for cell adhesion and growth. Surface modification of these materials is thus crucial to enhance the scaffold's integration in the body. Different surface modification techniques have been developed to improve scaffold biocompatibility. Here we show that diazonium chemistry can be used to modify the outer and inner surfaces of three-dimensional poly(D,L-lactic acid) (PDLLA) scaffolds with phosphonate groups, using a simple two-step method. By changing reaction time and impregnation procedure, we were able to tune the concentration of phosphonate groups present on the scaffolds, without degrading the PDLLA matrix. To test the effectiveness of this modification, we immersed the scaffolds in simulated body fluid, and characterized them with scanning electron microscopy, X-ray photoelectron spectroscopy, Raman, and infrared spectroscopy. Our results showed that a layer of hydroxyapatite particles was formed on all scaffolds after 2 and 4 weeks of immersion; however, the precipitation was faster and in larger amounts on the phosphonate-modified than on the bare PDLLA scaffolds. Both osteogenic MC3T3-E1 and chondrogenic ATDC5 cell lines showed increased cell viability/metabolic activity when grown on a phosphonated PDLLA surface in comparison to a control PDLLA surface. Also, more calcium-containing minerals were deposited by cultures grown on phosphonated PDLLA, thus showing the pro-mineralization properties of the proposed modification. This work introduces diazonium chemistry as a simple and biocompatible technique to modify scaffold surfaces, allowing to covalently and homogeneously bind a number of functional groups without degrading the scaffold's polymeric matrix.

Reaction of Diazo Compounds with Difluorocarbene: An Efficient Approach towards 1,1-Difluoroolefins.

Science.gov (United States)

Zhang, Zhikun; Yu, Weizhi; Wu, Chenggui; Wang, Chengpeng; Zhang, Yan; Wang, Jianbo

2016-01-04

A transition-metal-free difluoromethylenation of diazo compounds that proceeds under mild conditions has been developed and is based on the use of TMSCF2 Br as the difluoromethylene source and tetrabutylammonium bromide (TBAB) as the promoter. The chemoselective formal carbene dimerization reaction is achieved owing to the electronic properties and the relative stability of the difluorocarbene intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chirality- and pH-Controlled Supramolecular Isomerism in Cobalt Phosphonates and Its Impact on the Magnetic Behavior.

Science.gov (United States)

Feng, Jian-Shen; Bao, Song-Song; Ren, Min; Cai, Zhong-Sheng; Zheng, Li-Min

2015-11-23

Two pairs of enantiomeric compounds with formulas (S)- or (R)-Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅4 H2 O [(S)-1 or (R)-1], (S)- or (R)-Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅3 H2 O [(S)- or (R)-2), and related racemic compound Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅4 H2 O (rac-3; 4,4'-bpy=4,4'-bipyridine, H3 ppap=3-phenyl-2-[(phosphonomethyl)amino]propanoic acid) are reported. Compounds 1 and rac-3 show identical three-dimensional framework structures, whereas compounds 2 have two-dimensional layer structures. Compounds 1 and 2 are catenation isomers, formation of which is controlled solely by the pH of the reaction mixtures, whereas the formation of isomeric compounds 1 and rac-3 is controlled purely by the chirality of the phosphonate ligand. The magnetic properties of fully dehydrated (S)-1, (S)-2, and rac-3 are highly dependent on both structure and chirality. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methyl 4-toluenesulfonyloxymethylphosphonate, a new and versatile reagent for the convenient synthesis of phosphonate-containing compounds

Czech Academy of Sciences Publication Activity Database

Kóšiová, Ivana; Točík, Zdeněk; Buděšínský, Miloš; Šimák, Ondřej; Liboska, Radek; Rejman, Dominik; Pačes, Ondřej; Rosenberg, Ivan

2009-01-01

Roč. 50, č. 49 (2009), s. 6745-6747 ISSN 0040-4039 R&D Projects: GA ČR GA202/09/0193; GA ČR GA203/09/0820; GA MŠk(CZ) LC06061; GA MŠk(CZ) LC06077; GA AV ČR KAN200520801 Institutional research plan: CEZ:AV0Z40550506 Keywords : nucleoside phosphonates * phosphonylation * methyl 4-toluenesulfonyloxymethylphosphonate Subject RIV: CC - Organic Chemistry Impact factor: 2.660, year: 2009

Inhibitors of bacterial N-succinyl-L,L-diaminopimelic acid desuccinylase (DapE) and demonstration of in vitro antimicrobial activity.

Science.gov (United States)

Gillner, Danuta; Armoush, Nicola; Holz, Richard C; Becker, Daniel P

2009-11-15

The dapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase (DapE) is a critical bacterial enzyme for the construction of the bacterial cell wall. A screen biased toward compounds containing zinc-binding groups (ZBG's) including thiols, carboxylic acids, boronic acids, phosphonates and hydroxamates has delivered a number of micromolar inhibitors of DapE from Haemophilus influenzae, including the low micromolar inhibitor L-captopril (IC(50)=3.3 microM, K(i)=1.8 microM). In vitro antimicrobial activity was demonstrated for L-captopril against Escherichia coli.

Hydrogen bonds and van der Waals forces as tools for the construction of a herringbone pattern in the crystal structure of hexane-1,6-diaminium hexane-1,6-diyl bis(hydrogen phosphonate

Directory of Open Access Journals (Sweden)

Guido J. Reiss

2017-01-01

Full Text Available The asymmetric unit of the title salt, [H3N(CH26NH3][(HOO2P(CH26PO2(OH], consists of one half of a hexane-1,6-diaminium dication and one half of a hexane-1,6-diyl bis(hydrogen phosphonate dianion. Both are located around different centres of inversion (Wyckoff sites: 2a and 2d of the space group P21/c. The shape of the hexane-1,6-diaminium cation is best described as a double hook. Both aminium groups as well as the two attached CH2 groups are turned out from the plane of the central four C atoms. In contrast, all six C atoms of the dianion are almost in a plane. The hydrogen phosphonate (–PO3H groups of the anions and the aminium groups of the cations form two-dimensional O—H... and O—H...N hydrogen-bonded networks parallel to the ac plane, built up from ten-membered and twelve-membered ring motifs with graph-set descriptors R33(10 and R54(12, respectively. These networks are linked by the alkylene chains of the anions and cations. The resulting three-dimensional network shows a herringbone pattern, which resembles the parent structures 1,6-diaminohexane and hexane-1,6-diphosphonic acid.

Distinct modulation of telomere length in two T-lymphoblastic leukemia cell lines by cytotoxic nucleoside phosphonates PMEG and PMEDAP

Czech Academy of Sciences Publication Activity Database

Hájek, Miroslav; Cvilink, Viktor; Votruba, Ivan; Holý, Antonín; Mertlíková-Kaiserová, Helena

2010-01-01

Roč. 643, č. 1 (2010), s. 6-12 ISSN 0014-2999 R&D Projects: GA MŠk 1M0508; GA AV ČR 1QS400550501 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * PMEG * PMEDAP * telomere length * telomerase inhibition Subject RIV: CC - Organic Chemistry Impact factor: 2.737, year: 2010

Extraction of Trivalent La, Nd and Eu from Nitric Acid Solution by Ion quest-801 Loaded on Lewatit CA 9221

International Nuclear Information System (INIS)

Nowier, H.G; Metwally, S.S; Abd El-Rehim, S.S; Aly, H.F.

2005-01-01

The extraction of La 3+ , Nd 3+ and Eu 3+ from nitric acid medium by Lewatit CA 9221, Containing 2-ethylhexyl mono -2- ethylhexyl phosphonic acid ester, Ion quest-801, was studied. Batch experiments were carried out to investigate the effect of contact time, V/M ratio, extractant concentration, nitric acid molarity, lanthanide concentration and temperature. The data obtained are discussed in terms of extraction equilibrium and separation factors between the lanthanides as well as certain sorption models. Possible use of column chromatography containing the developed extractant material was assessed

Hybrid inorganic-organic adsorbents Part 1: Synthesis and characterization of mesoporous zirconium titanate frameworks containing coordinating organic functionalities.

Science.gov (United States)

Griffith, Christopher S; De Los Reyes, Massey; Scales, Nicholas; Hanna, John V; Luca, Vittorio

2010-12-01

A series of functional hybrid inorganic-organic adsorbent materials have been prepared through postsynthetic grafting of mesoporous zirconium titanate xerogel powders using a range of synthesized and commercial mono-, bis-, and tris-phosphonic acids, many of which have never before been investigated for the preparation of hybrid phases. The hybrid materials have been characterized using thermogravimetric analysis, diffuse reflectance infrared (DRIFT) and 31P MAS NMR spectroscopic techniques and their adsorption properties studied using a 153Gd radiotracer. The highest level of surface functionalization (molecules/nm2) was observed for methylphosphonic acid (∼3 molecules/nm2). The level of functionalization decreased with an increase in the number of potential surface coordinating groups of the phosphonic acids. Spectral decomposition of the DRIFT and 31P MAS NMR spectra showed that each of the phosphonic acid molecules coordinated strongly to the metal oxide surface but that for the 1,1-bis-phosphonic acids and tris-phosphonic acids the coordination was highly variable resulting in a proportion of free or loosely coordinated phosphonic acid groups. Functionalization of a porous mixed metal oxide framework with the tris-methylenephosphonic acid (ATMP-ZrTi-0.33) resulted in a hybrid with the highest affinity for 153Gd3+ in nitric acid solutions across a wide range of acid concentrations. The ATMP-ZrTi-0.33 hybrid material extracted 153Gd3+ with a Kd value of 1×10(4) in 0.01 M HNO3 far exceeding that of the other hybrid phases. The unfunctionalized mesoporous mixed metal oxide had negligible affinity for Gd3+ (KdATMP-ZrTi-0.33 hybrid phase for Gd3+ has been determined to be about 0.005 mmol/g in 0.01 M HNO3. This behavior and that of the other hybrid phases suggests that the surface-bound ATMP ligand functions as a chelating ligand toward 153Gd3+ under these acidic conditions.

Some studies on the extraction of plutonium from phosphate containing nitric acid solutions using DBDECMP as extractant

International Nuclear Information System (INIS)

Sagar, V.B.; Oak, M.S.; Pawar, S.M.; Sivaramakrishnan, C.K.; Patil, S.K.

1991-01-01

Extraction studies have been carried out to explore the feasibility of separation of Pu(IV) from phosphate containing analytical wastes generated in the laboratory. Distribution data on the extraction of Pu(IV) from DBDECMP (di-butyl,N,N-diethylcarbamoyl methyl phosphonate) in xylene an aqueous nitric acid and its mixture with sulfuric as well as with sulfuric and phosphoric acids were obtained. Based on the data obtained, the conditions for the recovery of plutonium from such water solutions are suggested. (author) 7 refs.; 1 fig.; 3 tabs

Tetramethyl guanidine (TMG catalyzed synthesis of novel a -amino phosphonates by one-pot reaction

Directory of Open Access Journals (Sweden)

S. Annar

2010-07-01

Full Text Available An efficient method has been developed for the synthesis of a -amino phosphonates (4a-j by the three component one-pot reaction of equimolar quantities of 2-amino methyl furan (1, dimethyl / diethyl phosphite (2 and various aldehydes (3a-j in dry toluene at reflux conditions via Kabachnik – Fields reaction in high yields (70-80% in the presence of tetramethyl guanidine (TMG as catalyst. The TMG can be easily recovered from the reaction mixture after completion of the reaction and can be reused. Their antimicrobial activity has also been evaluated.

The synthesis of phosphonic acids derived from homocysteine via transesterification reactions

Czech Academy of Sciences Publication Activity Database

Pícha, Jan; Buděšínský, Miloš; Fiedler, Pavel; Jiráček, Jiří

-, č. 4 (2012), s. 80-99 ISSN 1551-7004 R&D Projects: GA ČR(CZ) GAP207/10/1277; GA ČR GA203/09/1919 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonohomocysteine * aminophosphonic acids Subject RIV: CC - Organic Chemistry Impact factor: 1.057, year: 2012

Flame-retardant copolymers of dialkyl (meth)acryloyloxyalkyl phosphate or dialkyl (meth)acryloyloxyalkyl phosphonate monomers and polymer foams based made therefrom

Energy Technology Data Exchange (ETDEWEB)

Qi, Yudong; Li, Yan; Bunker, Shana P.; Costeux, Stephane; Morgan, Ted A.

2017-12-12

Polymer foam bodies are made from phosphorus-containing thermoplastic random copolymers of a dialkyl (meth)acryloyloxyalkyl phosph(on)ate. Foam bodies made from these copolymers exhibit increased limiting oxygen indices and surprisingly have good properties. In certain embodiments, the phosphorus-containing thermoplastic copolymer is blended with one or more other polymers and formed into nanofoams.

Alternative synthesis of 9-{3-[(diisopropoxyphosphoryl)-methoxy]-2-hydroxypropyl}adenine and its free phosphonates substituted at the C-8 position of purine base

Czech Academy of Sciences Publication Activity Database

Janeba, Zlatko; Masojídková, Milena; Holý, Antonín

2010-01-01

Roč. 75, č. 3 (2010), s. 371-381 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * HPMPA * nucleophilic substitution * intramolecular cyclization Subject RIV: CC - Organic Chemistry Impact factor: 0.853, year: 2010

Estimation of apparent binding constant of complexes of selected acyclic nucleoside phosphonates with beta-cyclodextrin by affinity capillary electrophoresis

Czech Academy of Sciences Publication Activity Database

Šolínová, Veronika; Mikysková, Hana; Kaiser, Martin Maxmilian; Janeba, Zlatko; Holý, Antonín; Kašička, Václav

2016-01-01

Roč. 37, č. 2 (2016), s. 239-247 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA13-17224S; GA ČR(CZ) GA15-01948S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * affinity capillary electrophoresis * binding constant * nucleotide analogs * beta-cyclodextrin Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 2.744, year: 2016

Synthesis and tissue distribution of fluorine-18 labeled trifluorohexadecanoic acids. Considerations in the development of metabolically blocked myocardial imaging agents

International Nuclear Information System (INIS)

Pochapsky, S.S.; Katzenellenbogen, J.A.; VanBrocklin, H.F.; Welch, M.J.

1990-01-01

A versatile method for the synthesis of trifluoro fatty acids, potential metabolically blocked myocardial imaging agents, has been developed. Two trifluorohexadecanoic (palmitic) acids have been prepared [6,6,16-trifluorohexadecanoic acid (I) and 7,7,16-trifluorohexadecanoic acid (II)], each of which bears two of the fluorine atoms as a gem-difluoromethylene unit on the fatty acid chain (at C-6 or C-7) and the third at the ω (C-16) position. The metabolic stability of carbon-fluorine bonds suggests the gem-difluoro group may block the β-oxidation pathway, while the terminal fluorine could be the site for labeling with fluorine-18. The convergent synthetic approach utilizes a 2-lithio-1,3-dithiane derived from 10-undecenal or 9-decenal, which is alkylated with the OBO (oxabicyclooctyl) ester of 5-bromopentanoic acid or 6-bromohexanoic acid, respectively. Hydroboration-oxidation and alcohol protection are followed by halofluorination to convert the 1,3-dithiane system to a gem-difluoro group. The third fluorine is introduced by fluoride ion displacement of a trifluoromethanesulfonate. This synthesis is adapted to the labeling of these trifluoro fatty acids with the short-lived radionuclide fluorine-18 (t 1/2 = 110 min), with the third fluorine introduced as fluoride ion in the penultimate step. The radiochemical syntheses proceed in 3-34% radiochemical yield (decay corrected), with an overall synthesis and purification time of 90 min. Tissue distribution studies in rats were performed with I and II, as well as with 16-[ 18 F]fluoropalmitic acid (III), [ 11 C]palmitic acid, and [ 11 C]octanoic acid. The heart uptake of the fluoropalmitic acids decreases with substitution, the 2-min activity level for 16-fluoropalmitic acid being 65% and that for both 6,6,16-and 7,7,17-trifluoropalmitic acids being 30% that of palmitic acid

Diphosphonic acid complexants for improved separation efficiency of transuranic elements

International Nuclear Information System (INIS)

Nash, K.L.

1994-01-01

A study was made of the thermodynamics of protonation and complexation of Eu(III), Th(IV), and U(VI) by a series of simple diphosphonic acid chelating agents to assess the potential for application in actinide waste processing. It was found that the strongest complexes are formed with ligands having two phosphonate binding groups on the same C atom (1,1-diphosphonates) and that the water-soluble complexes are formed with protonated ligand species. More efficient separation/recovery processes could be designed using these ligands

Spontaneous arylation of activated carbon from aminobenzene organic acids as source of diazonium ions in mild conditions

International Nuclear Information System (INIS)

Lebègue, Estelle; Brousse, Thierry; Gaubicher, Joël; Cougnon, Charles

2013-01-01

Activated carbon products modified with benzoic, benzenesulfonic and benzylphosphonic acid groups were prepared by spontaneous reduction of aryldiazonium ions in situ generated in water from the corresponding aminobenzene organic acids without addition of an external acid. Electrochemistry and NMR studies show that the advancement of the diazotization reaction depends both on the acidity and the electronic effect of the organic acid substituent, giving a mixture of diazonium, amine and triazene functionalities. Carbon products prepared by reaction of activated carbon Norit with 4-aminobenzenecarboxylic acid, 4-aminobenzenesulfonic acid and (4-aminobenzyl)phosphonic acid were analyzed by chemical elemental analysis and X-ray photoelectron spectroscopy experiments. Results show that this strategy is well suited for the chemical functionalization, giving a maximized grafting yield due to a chemical cooperation of amine and diazonium functionalities

186Re-1,4,8,11-tetraaza cyclotetradecyl-1,4,8,11-tetramethylene phosphonic acid: a novel agent for possible use in metastatic bone-pain palliation

International Nuclear Information System (INIS)

Kothari, Kanchan; Samuel, Grace; Banerjee, Sharmila; Unni, P.R.; Sarma, H.D.; Chaudhari, P.R.; Unnikrishnan, T.P.; Pillai, M.R.A.

2001-01-01

In connection with our work on the development of 186 Re-tetra-phosphonates with optimum properties for use in bone pain palliation, a novel cyclic tetraphosphonate derivative, has been synthesized, complexed with 186 Re and evaluated with promising results. The ligand, which consists of a cyclic array of tetra-aminomethylphosphonate groups, was synthesized using orthophosphorus acid, 1,4,8,11-tetraazacyclotetradecane and formaldehyde. The labeling conditions with 186 Re have been standardized under varying reaction conditions to give maximum yield. In a reaction volume of 1 mL, maximum complexation yield of 98% was observed at pH 2 using 0.1 mg Re (37-370 MBq) for a ligand concentration at 9x10 -2 M/L, under heating at 100 deg. C for 30 min with 2 mg of stannous chloride. The complex was found to be stable for 6 days with RC purity remaining ∼97%. The complex was characterized by paper chromatography in saline and acetone, wherein the R f exhibited were 0.9 and 0, respectively. Biodistribution studies of the complex were performed in male Wistar rats. Activity in femur which was observed to be 1.8%/g (equivalent to about 23% of the injected activity in skeleton) at 3 h post injection remained almost constant up to 48 h. Minimum activity was observed in blood and other soft tissues. The complex showed major renal clearance. Scintigraphic images in rabbits after injecting 70-100 MBq of 186 Re-CTMP and using a dual head gamma camera were observed to be superior to 186 Re-HEDP, prepared by a procedure standardized by us. Insignificant activity was observed in other vital organs. The results suggest the suitability of the complex for further evaluation in higher animals for bone pain palliation

SBA-15 mesoporous silica free-standing thin films containing copper ions bounded via propyl phosphonate units - preparation and characterization

Energy Technology Data Exchange (ETDEWEB)

Laskowski, Lukasz, E-mail: lukasz.laskowski@kik.pcz.pl [Czestochowa University of Technology, Institute of Computational Intelligence, Unit of Microelectronics and Nanotechnology, Al. Armii Krajowej 36, 42–201 Czestochowa (Poland); Laskowska, Magdalena, E-mail: magdalena.laskowska@onet.pl [H. Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, 31-342 Krakow, ul. Radzikowskiego 152 (Poland); Jelonkiewicz, Jerzy, E-mail: jerzy.jelonkiewicz@kik.pcz.pl [Czestochowa University of Technology, Institute of Computational Intelligence, Unit of Microelectronics and Nanotechnology, Al. Armii Krajowej 36, 42–201 Czestochowa (Poland); Dulski, Mateusz, E-mail: mateusz.dulski@us.edu.pl [University of Silesia, Faculty of Computer Science and Materials Science, Institute of Materials Science, Silesian Center for Education and Interdisciplinary Research, ul. 75 Pułku Piechoty 1A, 41–500 Chorzów (Poland); Wojtyniak, Marcin, E-mail: marcin.wojtyniak@us.edu.pl [University of Silesia, Institute of Physics, Silesian Center for Education and Interdisciplinary Research, ul. 75 Pułku Piechoty 1A, 41–500 Chorzów (Poland); Fitta, Magdalena, E-mail: magdalena.fitta@ifj.edu.pl [H. Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, 31–342 Krakow, ul. Radzikowskiego 152 (Poland); Balanda, Maria, E-mail: Maria.Balanda@ifj.edu.pl [H. Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, 31–342 Krakow, ul. Radzikowskiego 152 (Poland)

2016-09-15

The SBA-15 silica thin films containing copper ions anchored inside channels via propyl phosphonate groups are investigated. Such materials were prepared in the form of thin films, with hexagonally arranged pores, laying rectilinear to the substrate surface. However, in the case of our thin films, their free standing form allowed for additional research possibilities, that are not obtainable for typical thin films on a substrate. The structural properties of the samples were investigated by X-ray reflectometry, atomic force microscopy (AFM) and transmission electron microscopy (TEM). The molecular structure was examined by Raman spectroscopy supported by numerical simulations. Magnetic measurements (SQUID magnetometry and EPR spectroscopy) showed weak antiferromagnetic interactions between active units inside silica channels. Consequently, the pores arrangement was determined and the process of copper ions anchoring by propyl phosphonate groups was verified in unambiguous way. Moreover, the type of interactions between magnetic atoms was determined. - Highlights: • Functionalized free-standing SBA-15 thin films were synthesized for a first time. • Thin films synthesis procedure was described in details. • Structural properties of the films were thoroughly investigated and presented. • Magnetic properties of the novel material was investigated and presented.

Prevention of refinery plugging by residual oil gellant chemicals in crude-optimization of phosphonate ester oil gellants

Energy Technology Data Exchange (ETDEWEB)

Lemieux, A.; Alick, C.; Stadnyk, S.; Funkhouser, G.; Fyten, G.; Taylor, R.S. [Halliburton Energy Services, Calgary, AB (Canada); Stemler, P. [Petro-Canada Oil and Gas Inc., Calgary, AB (Canada)

2005-07-01

This study examined the use of phosphonate ester oil gellants for refinery plugging. Field tests were performed to test ways to optimize cost and performance and to establish quality control specifications based on performance testing and compositional analysis determined through nuclear magnetic resonance (NMR). Additional field tests were performed to ensure both operational performance and the ability to control volatile phosphorus while continuing to meet the standards of the 2 initial field trials. The study assessed the ability of phosphonate esters to control volatile phosphorus at higher temperatures. Distillations used to evaluate volatile phosphorus to date have had a 250 degree C end point. This temperature was chosen because it represents the approximate temperature experienced at the distillation tower trays where plugging has been observed from components condensing from the gas phase. However, the actual peak temperature in the tower bottom is closer to 350 degrees C. This higher temperature is the actual temperature at which decomposition or volatilization occurs. In order to fully understand the ability to control volatile phosphorus, distillations were conducted with a 350 degree C end point. Volatile and total phosphorus to both 250 degrees C and 350 degrees C end points were reported. The study also addressed the concern regarding organic halide formation under distillation tower conditions, although no organic halides were detected in the field trials. 3 refs., 2 tabs., 7 figs.

Determination of glyphosate residuals and of their metabolite Aminomethyl-Phosphonic acid in waters, by means of liquid chromatography of high efficiency with post-column derivation and fluorescence detection

International Nuclear Information System (INIS)

Rodriguez, Hugo A; Guerrero, Jairo; Castro, Rene

2002-01-01

The glyphosate is a no selective herbicide largely used in the world in order to control annual and perennial weeds. Its principal metabolite in soils and waters is the Aminomethyl-Phosphonic Acid (AMPA) formed by micro organism's action. This herbicide is used in Colombia in high doses to illegal crops eradication of coca and Amapola and like natural accelerator in sugar cane, constituting an environmental and social problem for the country, being necessary the evaluation of glyphosate residues in different matrices. This study describes the validation of the analytical methodology for the simultaneous determination of glyphosate and its metabolite AMPA in waters of some Colombian regions. The experimental procedure pointed out two main steps: the first one was a cleaning, extraction and concentration step by solid phase extraction; the second step is the separation, identification and quantification of the compounds by High Performance Liquid Chromatography (HPLC) with post-column derivation and fluorescence detection. The results of the validation show that the methodology is specific, selective, precise and robust with linear calibration curve in the linear range between 10 and 750 μg/L, with limits of detection of 0.8 μg/L and limits of quantification of 2 μg/L for the two analyses. The recoveries are in the order of 73% for glyphosate and 70% for AMPA. More over analysis results are presented for water samples of some country regions where glyphosate is applied in different doses with different purposes, finding residues of the herbicide and its metabolite in concentrations above the allowed values in drinking waters for pesticides of toxicology category IV, like the glyphosate, according with the Colombian legislation

An efficient microwave-assisted synthesis and biological properties of polysubstituted pyrimidinyl- and 1,3,5-triazinylphosphonic acids

Czech Academy of Sciences Publication Activity Database

Jansa, Petr; Hradil, Ondřej; Baszczyňski, Ondřej; Dračínský, Martin; Klepetářová, Blanka; Holý, Antonín; Balzarini, J.; Janeba, Zlatko

2012-01-01

Roč. 68, č. 3 (2012), s. 865-871 ISSN 0040-4020 R&D Projects: GA AV ČR KJB400550903; GA MŠk 1M0508 Grant - others:K.U. Leuven(BE) GOA 10/014 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonic acids * pyrimidines * 1,3,5-triazines * microwave-assisted synthesis * influenza virus Subject RIV: CC - Organic Chemistry Impact factor: 2.803, year: 2012

High performance of phosphate-functionalized graphene oxide for the selective adsorption of U(VI) from acidic solution

Energy Technology Data Exchange (ETDEWEB)

Liu, Xia [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); University of Science and Technology of China, Hefei, 230026 (China); Li, Jiaxing, E-mail: lijx@ipp.ac.cn [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions (China); School for Radiological and Interdisciplinary Sciences (RAD-X), Soochow University, 215123, Suzhou (China); Wang, Xiangxue; Chen, Changlun [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Wang, Xiangke [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions (China); School for Radiological and Interdisciplinary Sciences (RAD-X), Soochow University, 215123, Suzhou (China); Faculty of Engineering, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

2015-11-15

In this study, phosphate-functionalized graphene oxide (PGO) was prepared by grafting triethyl phosphite onto the surface of GO using Arbuzov reaction. The as-prepared PGO was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy and Zeta potential. The application of the PGO to remove U(VI) from aqueous solution was investigated with a maximum adsorption capacity of 251.7 mg/g at pH = 4.0 ± 0.1 and T = 303 K. The adsorption mechanism was also investigated by X-ray photoelectron spectroscopy analysis, indicating a chemical adsorption of U(VI) on PGO surface. Moreover, experimental results gave a better removal efficiency toward U(VI) on PGO surface than other heavy metal ions at acidic solution, indicating the selective extraction of U(VI) from environmental pollutants. - Highlights: • The successful grafting phosphonate to graphene oxide by the Arbuzov reaction. • Selective adsorption of U(VI) on PGO surface over other heavy metal ions from acidic solution. • Electrostatic interactions of U(VI) with phosphonate and oxygen-containing functional groups on PGO surface. • Higher sorption capacity on PGO surface than GO surface for the U(VI) removal.

Antiviral activities of 2,6-diaminopurine-based acyclic nucleoside phosphonates against herpesviruses: In vitro study results with pseudorabies virus (PrV, SuHV-1)

Czech Academy of Sciences Publication Activity Database

Zouharová, D.; Lipenská, I.; Fojtiková, M.; Kulich, P.; Neca, J.; Slaný, M.; Kovařčík, K.; Turanek-Knotigová, P.; Hubatka, F.; Celechovská, H.; Mašek, J.; Koudelka, Š.; Procházka, L.; Eyer, L.; Plocková, J.; Bartheldyová, E.; Miller, A. D.; Růžek, Daniel; Raška, M.; Janeba, Zlatko; Turánek, J.

2016-01-01

Roč. 184, FEB 29 (2016), s. 84-93 ISSN 0378-1135 Institutional support: RVO:60077344 ; RVO:61388963 Keywords : Pseudorabies * Acyclic nucleoside phosphonates * DNA viruses * Cidofovir * Antiviral drugs * DNA polymerase Subject RIV: EE - Microbiology, Virology; CC - Organic Chemistry (UOCHB-X) Impact factor: 2.628, year: 2016

Research and performance evaluation on an HA integrated acid system for sandstone acidizing

Directory of Open Access Journals (Sweden)

Liqiang Zhao

2018-03-01

Full Text Available When the conventional sandstone acidizing technologies are adopted, many slugs are needed in the injection of prepad fluid, treatment fluid and postpad fluid, and consequently the production and operation suffers inconveniences and difficulties. In view of this, a kind of HA integrated acid system which is mainly composed of organic polybasic acids (HA+HCl + HF and an efficient organic solvent was developed in this paper based on the idea of integrated acid replacing ''multiple steps'' and high efficiency and intensification. Via this HA integrated acid system, the complicated blockage in sandstone reservoirs can be removed effectively. Then, experiments were carried out on this system to evaluate its performance in terms of its retardance, organic blockage dissolution, chelating and precipitation inhibition. It is indicated that this new system can not only realize the acidizing of conventional integrated acid, but also present a good retarding performance by controlling H+ multi-stage ionization step by step and by forming silica acid-aluminum phosphonate film on the surface of clay minerals; that via this new HA integrated acid system, the organic blockage can be removed efficiently; and that it is wider in pH solution range than conventional APCs (aminopolycarboxyliates chelants, stronger in chelating capacity of Ca2+, Mg2+ and Fe3+ than conventional chelants (e.g. EDTA, NTA and DTPA, and better in precipitation inhibition on metal fluoride, fluosilicic acid alkali metal, fluoaluminic acid alkali metal and hydroxide than multi-hydrogen acid, fluoboric acid and mud acid systems. These research results provide a technical support for the plugging removal in high-temperature deep oil and gas reservoirs. Keywords: Organic polybasic acid, Integrated acid, Retardance, Chelating, Precipitation, Acidizing, Sandstone, Reservoir

Supercritical Fluid Extraction (SFE) of uranium and thorium nitrates using carbon dioxide modified with phosphonates

International Nuclear Information System (INIS)

Pitchaiah, K.C.; Sujatha, K.; Brahmananda Rao, C.V.S.; Sivaraman, N.; Vasudeva Rao, P.R.

2014-01-01

Supercritical Fluid Extraction (SFE) has emerged as a powerful technique for the extraction of metal ions.The liquid like densities and gas like physical properties of supercritical fluids make them unique to act as special solvents. SFE based procedures were developed and demonstrated in our laboratory for the recovery of actinides from various matrices. In the present study, we have examined for the first time, the use of dialkylalkylphosphonates in supercritical carbon dioxide (Sc-CO 2 ) medium to study the extraction behavior of uranium and thorium nitrates. A series of phosphonates were synthesised by Michaelis-Becker reaction in our laboratory and employed for the SFE

Labelling of ethylenediaminetetramethylene phosphonic acid (EDTMP) with 175Yb

International Nuclear Information System (INIS)

Azmairit Aziz

2009-01-01

Ytterbium-175 ( 175 Yb) is one of radioisotopes that can be used for therapy due to its β-particle emission (T 1/2 = 4.2 d, E β(max) = 480 keV). Beside that, this radioisotope also emits γ-rays of 113 keV (1.9%), 282 keV (3.1%) and 396 keV (6.5%) which are suitable energy for imaging as long as therapeutic applications. EDTMP could be labeled with radionuclide of 175 Yb as an alternative radiopharmaceutical for bone pain palliation due to bone metastases. Labeling of ethylenediaminetetramethylenephosphonic acid with 175 Yb has been studied. Various influential parameters in labeling conditions i.e. the amount of EDTMP ligand, the pH of labeling, incubation time and the amount of 175 Yb solution were studied in order to obtain high labeling efficiency of 175 Yb-EDTMP. The labeling efficiency was obtained by radiochemical purity that was determined by paper chromatography and paper electrophoresis techniques. The optimum labeling condition was obtained at pH 7, 4 mg of EDTMP ligand, 100 µL (105 µg; 0.6 µmol) of 175 Yb solution and 30 minutes incubation time at room temperature. The complex formed was gave maximum labeling efficiency of 98.81 ± 0.15%. Owing to the results, EDTMP ligand can be labeled with 175 Yb radionuclide with labeling efficiency more than 95%. (author)

On the Reaction of Carbonyl Diphosphonic Acid with Hydroxylamine and O-alkylhydroxylamines: Unexpected Degradation of P-C-P Bridge.

Science.gov (United States)

Khomich, Olga A; Yanvarev, Dmitry V; Novikov, Roman A; Kornev, Alexey B; Puljulla, Elina; Vepsäläinen, Jouko; Khomutov, Alex R; Kochetkov, Sergey N

2017-06-23

Derivatives of methylenediphosphonic acid possess wide spectra of biological activities and are used in enzymology as research tools as well as in practical medicine. Carbonyl diphosphonic acid is a promising starting building block for synthesis of functionally substituted methylenediphosphonates. Investigation of the interaction of carbonyl diphosphonic acid with hydroxylamine clearly demonstrates that it is impossible to isolate oxime within the pH range 2-12, while only cyanophosphonic and phosphoric acids are the products of the fast proceeding Beckmann-like fragmentation. In the case of O -alkylhydroxylamines, corresponding alcohols are found in the reaction mixtures in addition to cyanophosphonic and phosphoric acids. Therefore, two residues of phosphonic acid being attached to a carbonyl group provide new properties to this carbonyl group, making its oximes very unstable. This principally differs carbonyl diphosphonic acid from structurally related phosphonoglyoxalic acid and other α-ketophosphonates.

Multi-organ technetium complexes production and use thereof

International Nuclear Information System (INIS)

Koehler, G.A.; Pestel, G.M.

1976-01-01

Chemical complexes, useful as radiopharmaceuticals, are formed by reacting technetium-99m with substituted or unsubstituted alkyl monophosphonic acids and certain ester derivatives thereof. The complexes are formed by reducing pertechnetate ion chemically or electrolytically in the presence of the phosphonic acid. By chemical modification of the phosphonic acid complexing agent, it is possible to ''tailor'' complexes for kidney, liver or bone imaging. The complexes are normally used in a physiologically acceptable aqueous medium. 20 Claims, No Drawings

Sm-153 EDTMP (ethylene diamine tetramethylene phosphonic acid) radiotherapeutic radiopharmaceutical

International Nuclear Information System (INIS)

Rehir Dahalan; Wan Anuar Wan Awang

1999-01-01

This work has utilized the technology used in the design of the diagnostic radiopharmaceuticals, which enabled optimum delivery of, the gamma emitting radionuclide to the target organs, enhancing the image of organ of interest. Optimal delivery of radiotherapeutic agents, minimizes the dose to the non target organs, whilst delivering destructive beta emitting radionuclide to target cancerous tissues with the hope of slowing down or completely ablating its growth. This work had been in establishing the parameters in the optimal production of Sm-153 using the MINT Research Reactor (MINTRR). This radionuclide, was then labeled to the ethylene diamine tetramethylene phosphoric acid (EDTMP) ligand, a bone-seeking complex. The results of this work have established the most suitable target form, the optimum labeling conditions and the necessary parameters to enhance the biodistribution of the Sm-153 EDTMP complex in the bone of the animal model, thus similarly in human. (author)

A ω-mercaptoundecylphosphonic acid chemically modified gold electrode for uranium determination in waters in presence of organic matter.

Science.gov (United States)

Merli, Daniele; Protti, Stefano; Labò, Matteo; Pesavento, Maria; Profumo, Antonella

2016-05-01

A chemically modified electrode (CME) on a gold surface assembled with a ω-phosphonic acid terminated thiol was investigated for its capability to complex uranyl ions. The electrode, characterized by electrochemical techniques, demonstrated to be effective for the determination of uranyl at sub-μgL(-1) level by differential pulse adsorptive stripping voltammetry (DPAdSV) in environmental waters, also in presence of humic matter and other potential chelating agents. The accuracy of the measurements was investigated employing as model probes ligands of different complexing capability (humic acids and EDTA). Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of diluents on the extraction of actinides and nitric acid by bidentate organophosphorus compounds

International Nuclear Information System (INIS)

Rozen, A.M.

1986-01-01

The effect of dilutents on extraction by bidentate organophosphorus compounds (diphosphine dioxides, carbamoyl phosphonates, and phosphine oxides) was studied. Figures show the effect of dilutents on the extraction of americium by TOPO and by carbamoylmethylene phosphonate, and the effect of dilutents on the extraction of nitric acid and americium by carbamoylphosphine oxide. Also shown is the effect of dilutents on the extraction of americium by diphenyldioctyl methylenediphosphine dioxide, and the effect of dilutents on the extraction of americium by tetraphenylmethylenediphosphine dioxide. It was concluded that when TBP is added the distribution coefficient of Am increases but the effect of TBP may not be represented by the usual power relationship between the distribution coefficient and the TBP concentration, which would be expected if TBP was found to be very strong but for dilution by DCE it was relatively weak. The observed facts can be explained if it is assumed that TBP reacts with the bridging protons in the complex, which are free for dilution by benzene and are partially occupied when dichlorethane is used

Synthesis of a Benzene-containing C1-Phosphonate Analogue of UDP-GlcNAc for the Inhibition of O-GlcNAc Transferase

Energy Technology Data Exchange (ETDEWEB)

Im, Jungkyun [Soonchunhyang Univ., Asan (Korea, Republic of)

2016-01-15

I report here the design, synthesis, and biological evaluation of a new C1-phosphonate analogue of UDP-GlcNAc as a potential inhibitor of OGT, an enzyme responsible for O-GlcNAc modification. The analogue was designed to mimic the transition state of the natural donor involved in the enzymatic reaction. However, the analogue showed somehow low activity as an inhibitor of OGT.

Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability, mechanical properties and surface resistivity.

Science.gov (United States)

Li, Jihui; Li, Yongshen; Song, Yunna; Niu, Shuai; Li, Ning

2017-11-01

In this paper, polyvinyl alcohol/phytic acid polymer (PVA/PA polymer) was synthesized through esterification reaction of PVA and PA in the case of acidity and ultrasound irradiation and characterized, and PVA/PA polymer film was prepared by PVA/PA polymer and characterized, and the influence of dosage of PA on the thermal stability, mechanical properties and surface resistivity of PVA/PA polymer film were researched, and the influence of sonication time on the mechanical properties of PVA/PA polymer film was investigated. Based on those, it was concluded that the hydroxyl group on the chain of PVA and the phosphonic group on PA were connected together in the form of phosphonate bond, and the hydroxyl group on the chain of PVA were connected together in the form of ether bond after the intermolecular dehydration; in the meantime, it was also confirmed that PVA/PA polymer film prepared from 1.20mL of PA not only had the high thermal stability and favorable ductility but also the low surface resistivity in comparison with PVA/PA polymer film with 0.00mL of PA, and the ductility of PVA/PA polymer film was very sensitive to the sonication time. Copyright © 2017. Published by Elsevier B.V.

Hydroxyapatite-phosphonoformic acid hybrid compounds prepared by hydrothermal method

Science.gov (United States)

Turki, Thouraya; Othmani, Masseoud; Bantignies, Jean-Louis; Bouzouita, Khaled

2014-01-01

Hydroxyapatites were prepared in the presence of different amounts of phosphonoformic acid (PFA) via the hydrothermal method. The obtained powders were characterized through chemical analysis, XRD, IR, 31P MAS-NMR, TEM, and TG-TDA. The XRD showed that the PFA did not affect the apatite composition. Indeed, only a reduction of the crystallite size was noted. After grafting of PFA, the IR spectroscopy revealed the appearance of new bands belonging to HPO42- and carboxylate groups of the apatite and organic moiety, respectively. Moreover, the 31P MAS-NMR spectra exhibited a peak with a low intensity assigned to the terminal phosphonate group of the organic moiety in addition to that of the apatite. Based on these results, a reaction mechanism involving the surface hydroxyl groups (tbnd Casbnd OH) of the apatite and the carboxyl group of the acid was proposed.

Gas chromatography of alkylphosphonic and dialkyl phosphinic acids; Cromatografia en fase gaseosa de acidos alquifosfonicos y dialquilfosinicos

Energy Technology Data Exchange (ETDEWEB)

Gasco Sanchez, L; Barrera Peniero, R; Ramirez Caceres, A; Marin Munoz, M

1978-07-01

After carrying out an optimization study on the separation conditions for the TMSr- derivatives, of the hexyl-, cyclohexyl-, heptyl-, and octyl-phosphonic acids; dihexyl dicyclohexyl-, heptyl-, and octyl-phosphinic acids, and dioctyl phosphine oxide, their retention indices (I) at two temperatures and on the OV-1 and OV-17 stationary phase were determined. Correlations between I and molecular structure were established. Calibration factors of these compounds in the flame ionization detector were studied, and the results analyzed taking into account the variables affecting the quantitative results, These results were unbiased but they had a lower precision than that usually achievable in gas chromatography. (Author) 24 refs.

Bidentate organophosphorus extractants: purification, properties and applications to removal of actinides from acidic waste solutions

International Nuclear Information System (INIS)

Schulz, W.W.; McIsaac, L.D.

1977-05-01

At both Hanford and Idaho, DHDECMP (dihexyl-N, N-diethylcarbamylmethylene phosphonate) continuous counter-current solvent extraction processes are being developed for removal of americium, plutonium, and, in some cases, other actinides from acidic wastes generated at these locations. Bench and, eventually, pilot and plant-scale testing and application of these processes have been substantially enhanced by the discovery of suitable chemical and physical methods of removing deleterious impurities from technical-grade DHDECMP. Flowsheet details, as well as various properties of purified DHDECMP extractants, are enumerated

The Synthesis, Structures and Chemical Properties of Macrocyclic Ligands Covalently Bonded into Layered Arrays

International Nuclear Information System (INIS)

Clearfield, Abraham

2003-01-01

OAK-B135 The immobilization of crown ethers tends to limit the leveling effect of solvents making the macrocycles more selective. In addition immobilization has the added advantage of relative ease of recovery of the otherwise soluble crown. We have affixed CH2PO3H2 groups to azacrown ethers. The resultant phosphorylated macrocycles may spontaneously aggregate into crystalline supramolecular linear arrays or contacted with cations produce layered or linear polymers. In the linear polymers the metal and phosphonic acids covalently bond into a central stem with the macrocyclic rings protruding from the stem as leaves on a twig. Two types of layered compounds were obtained with group 4 metals. Monoaza-crown ethers form a bilayer where the M4+ plus phosphonic acid groups build the layer and the rings fill the interlayer space. 1, 10-diazadiphosphonic acids cross-link the metal phosphonate layers forming a three-dimensional array of crown ethers. In order to improve diffusion into these 3-D arrays they are spaced by inclusion of phosphate or phosphate groups. Two series of azamacrocylic crown ethers were prepared containing rings with 20 to 32 atoms. These larger rings can complex two cations per ring. Methylene phosphonic acid groups have been bonded to the aza ring atoms to increase the complexing ability of these ligands. Our approach is to carry out acid-base titrations in the absence and presence of cations to determine the pKa values of the protons, both those bonded to aza groups and those associated with the phosphonic acid groups. From the differences in the titration curves obtained with and without the cations present we obtain the stoichiometry of complex formation and the complex stability constants. Some of the applications we are targeting include phase transfer catalysis, separation of cations and the separation of radioisotopes for diagnostic and cancer therapeutic purposes

Sorption Efficiency of a New Sorbent towards Cadmium(II: Methylphosphonic Acid Grafted Polystyrene Resin

Directory of Open Access Journals (Sweden)

Nacer Ferrah

2013-01-01

Full Text Available A new chelating polymeric sorbent has been developed using polystyrene resin grafted with phosphonic acid. After characterization by FTIR and elementary analysis, the new resin has been investigated in liquid-solid extraction of cadmium(II. The results indicated that phosphonic resin could adsorb Cd(II ion effectively from aqueous solution. The adsorption was strongly dependent on the pH of the medium and the optimum pH value level for better sorption was between 3.2 and 5.2. The influence of other analytical parameters including contact time, amount of resin, metal ion concentration, and the presence of some electrolytes was investigated. The maximum uptake capacity of Cd(II ions was 37,9 mg·g−1 grafted resin at ambient temperature, at an initial pH value of 5.0. The overall adsorption process was best described by pseudo second-order kinetic. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. Furthermore, more than 92% of Cd(II could be eluted by using 1.0 mol·L−1 HCl in one cycle.

Synthesis of highly stable folic acid conjugated magnetite nanoparticles for targeting cancer cells

International Nuclear Information System (INIS)

Mohapatra, S; Mallick, S K; Maiti, T K; Ghosh, S K; Pramanik, P

2007-01-01

A new approach towards the design of folic acid conjugated magnetic nanoparticles for enhancing their site specific intracellular uptake against a folate receptor overexpressing cancer cells is reported. Magnetite nanoparticles were prepared by coprecipitation from an Fe 3+ and Fe 2+ solution followed by surface modification with 2-carboxyethyl phosphonic acid to form carboxyl group terminated nanoparticles. Then folic acid and fluorescein isothiocyanate (FITC) were conjugated with carboxylic acid functionalized magnetite nanoparticles using 2,2'-(ethylenedioxy)-bis-ethylamine. These folate-conjugated nanoparticles were characterized in terms of their size by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Surface functional groups and surface composition were analyzed by Fourier transform infrared (FTIR) spectroscopy and x-ray photoelectron spectroscopy (XPS), respectively. Vibration sample magnetometry (VSM) measurements showed the superparamagnetic nature of the particles at room temperature. Folate-conjugated magnetic nanoparticles are noncytotoxic and receptor mediated internalization by HeLa and B16 melanoma F0 cancer cells was confirmed by flow cytometry and confocal microscopy

Preparation of Phosphonic Acid Functionalized Graphene Oxide-modified Aluminum Powder with Enhanced Anticorrosive Properties

Science.gov (United States)

He, Lihua; Zhao, Yan; Xing, Liying; Liu, Pinggui; Wang, Zhiyong; Zhang, Youwei; Liu, Xiaofang

2017-07-01

To improve the anticorrosive performance of aluminum powder, a common functional filler in polymer coatings, we report a novel method to prepare graphene oxide modified aluminum powder (GO-Al) using 3-aminoproplyphosphoic acid as "link" agent. The GO nanosheets were firstly functionalized with 3-aminoproplyphosphoic acid (APSA) by the reaction of amine groups of APSA and the epoxy groups of GO. Subsequently, a layer of GO nanosheets uniformly and tightly covered the surface of flaky aluminum particle though the strong linking strength between -PO(OH)2 functional groups of the modified GO and aluminum. The hydrogen evolution experiment suggests that the GO attached on the aluminum powder could effectively improve the anticorrosive performance of the pigments.

A mixed-valent uranium phosphonate framework containing U{sup IV}, U{sup V}, and U{sup VI}

Energy Technology Data Exchange (ETDEWEB)

Chen, Lanhua; Zheng, Tao; Wang, Yaxing; Diwu, Juan; Chai, Zhifang; Wang, Shuao [School for Radiological and interdisciplinary Sciences (RAD-X), Soochow University, Suzhou (China); Collaborative Innovation Center of Radiation Medicine, Jiangsu Higher Education Institutions, Suzhou (China); Bao, Songsong; Zheng, Limin [State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University (China); Zhang, Linjuan; Wang, Jianqiang [Shanghai Institute of Applied Physics and, Key Laboratory of Nuclear Radiation and Nuclear Energy Technology, Chinese Academy of Sciences, Shanghai (China); Liu, Hsin-Kuan [Department of Chemistry, National Central University, Jhongli (China); Albrecht-Schmitt, Thomas E. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL (United States)

2016-08-16

It is shown that U{sup V}O{sub 2}{sup +} ions can reside at U{sup VI}O{sub 2}{sup 2+} lattice sites during mild reduction and crystallization process under solvothermal conditions, yielding a complicated and rare mixed-valent uranium phosphonate compound that simultaneously contains U{sup IV}, U{sup V}, and U{sup VI}. The presence of uranium with three oxidation states was confirmed by various characterization techniques, including X-ray crystallography, X-ray photoelectron, electron paramagnetic resonance, FTIR, UV/Vis-NIR absorption, and synchrotron radiation X-ray absorption spectroscopy, and magnetism measurements. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Liquid-liquid extraction of uranium from Egyptian phosphoric acid using a synergistic D2EHPA-DBBP mixture

International Nuclear Information System (INIS)

Abdel-Khalek, A.A.

2011-01-01

Extraction of uranium from Egyptian phosphoric acid with synergistic mixture of di-2-ethylhexylphosphoric acid (D2EHPA) and di-butyl butyl phosphonate (DBBP) is reported in this paper. The influence of various factors such as D2EHPA concentration, DBBP concentration, phosphoric acid concentration, contact time, aqueous: organic phase's ratio (aq:org) and temperature on the degree of extraction has been established. The data on the effect of temperature on the extraction showed that the enthalpy change is -23.12 kJ/mol. Uranium extracted by D2EHPA- DBBP is further subjected to a second cycle of extraction and scrubbing impurities. The uranium is finally converted to a high purity UO 3 product using precipitation with hydrogen peroxide and heat treatment at 375 deg C. (author)

Selective modification of halloysite lumen with octadecylphosphonic acid: new inorganic tubular micelle.

Science.gov (United States)

Yah, Weng On; Takahara, Atsushi; Lvov, Yuri M

2012-01-25

Selective fatty acid hydrophobization of the inner surface of tubule halloysite clay is demonstrated. Aqueous phosphonic acid was found to bind to alumina sites at the tube lumen and did not bind the tube's outer siloxane surface. The bonding was characterized with solid-state nuclear magnetic resonance ((29)Si, (13)C, (31)P NMR), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy. NMR and FTIR spectroscopy of selectively modified tubes proved binding of octadecylphosphonic acid within the halloysite lumen through bidentate and tridentate P-O-Al linkage. Selective modification of the halloysite clay lumen creates an inorganic micelle-like architecture with a hydrophobic aliphatic chain core and a hydrophilic silicate shell. An enhanced capacity for adsorption of the modified halloysite toward hydrophobic derivatives of ferrocene was shown. This demonstrates that the different inner and outer surface chemistry of clay nanotubes can be used for selective modification, enabling different applications from water purification to drug immobilization and controlled release. © 2011 American Chemical Society

Crystal structure of the complex of carboxypeptidase A with a strongly bound phosphonate in a new crystalline form: comparison with structures of other complexes.

Science.gov (United States)

Kim, H; Lipscomb, W N

1990-06-12

O-[[(1R)-[[N-(Phenylmethoxycarbonyl)-L-alanyl]amino]ethyl] hydroxyphosphinyl]-L-3-phenyllacetate [ZAAP(O)F], an analogue of (benzyloxycarbonyl)-Ala-Ala-Phe or (benzyloxycarbonyl)-Ala-Ala-phenyllactate, binds to carboxypeptidase A with great affinity (Ki = 3 pM). Similar phosphonates have been shown to be transition-state analogues of the CPA-catalyzed hydrolysis [Hanson, J. E., Kaplan, A. P., & Bartlett, P. A. (1989) Biochemistry 28, 6294-6305]. In the present study, the structure of the complex of this phosphonate with carboxypeptidase A has been determined by X-ray crystallography to a resolution of 2.0 A. The complex crystallizes in the space group P2(1)2(1)2(1) with cell dimensions a = 61.9 A, b = 67.2 A, and c = 76.2 A. The structure of the complex was solved by molecular replacement. Refinement of the structure against 20,776 unique reflections between 10.0 and 2.0 A yields a crystallographic residual of 0.193, including 140 water molecules. The two phosphinyl oxygens of the inhibitor bind to the active-site zinc at 2.2 A on the electrophilic (Arg-127) side and 3.1 A on the nucleophilic (Glu-270) side. Various features of the binding mode of this phosphonate inhibitor are consistent with the hypothesis that carboxypeptidase A catalyzed hydrolysis proceeds through a general-base mechanism in which the carbonyl carbon of the substrate is attacked by Zn-hydroxyl (or Zn-water). An unexpected feature of the bound inhibitor, the cis carbamoyl ester bond at the benzyloxycarbonyl linkage to alanine, allows the benzyloxycarbonyl phenyl ring of the inhibitor to interact favorably with Tyr-198. This complex structure is compared with previous structures of carboxypeptidase A, including the complexes with the potato inhibitor, a hydrated keto methylene substrate analogue, and a phosphonamidate inhibitor. Comparisons are also made with the complexes of thermolysin with some phosphonamidate inhibitors.

3-pyrazolone analogues of the 3-isoxazolol metabotropic excitatory amino acid receptor agonist homo-AMPA. Synthesis and pharmacological testing

DEFF Research Database (Denmark)

Zimmermann, D.; Janin, Y.L.; Brehm, L.

1999-01-01

the terminal carboxyl group has been replaced by various bioisosteric groups, such as phosphonic acid or 3-isoxazolol groups, have been shown to interact selectively with different subtypes of mGlu receptors. In this paper we report the synthesis of the 3-pyrazolone bioisosteres of a-AA, compounds (RS)-2-amino......-4-(1,2-dihydro-5-methyl-3-oxo-3H-pyrazol-4-yl)butyric acid (1) and (RS)-2-amino-4-(1,2-dihydro-1,5-dimethyl-3-oxo-3H-pyrazol-4-yl)butyric acid (2). At a number of steps in the reaction sequences used, the reactions took unexpected courses and provided products which could not be transformed......We have previously shown that the higher homologue of (S)-glutamic acid [(S)-Glu], (S)-a-aminoadipic acid [(S)-a-AA] is selectively recognized by the mGlu and mGlu subtypes of the family of metabotropic glutamic acid (mGlu) receptors. Furthermore, a number of analogues of (S)-a-AA, in which...

Metal-Free, Site-Selective Peptide Modification by Conversion of "Customizable" Units into β-Substituted Dehydroamino Acids.

Science.gov (United States)

Saavedra, Carlos J; Hernández, Dácil; Boto, Alicia

2018-01-12

Our site-selective modification of serine or threonine units in peptides allows the generation of β-substituted dehydroamino acids, which increase peptide resistance to hydrolysis and may improve their biological properties. Both the terminal and internal positions can be modified, and different customizable units can be activated separately. Remarkably, high Z selectivity is achieved, even at internal positions. The conversion involves a one-pot oxidative radical scission/phosphorylation process by using the low-toxicity (diacetoxyiodo)benzene/iodine system as the scission reagent. The resulting α-amino phosphonates undergo a Horner-Wadsworth-Emmons reaction to produce the dehydroamino acid derivatives (in a Z/E ratio of usually >98:2) under mild and metal-free conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mn{sub 0.95}I{sub 0.02}[PO{sub 3}(OH)] · 2H{sub 2}O phosphate–iodate, an inorganic analogue of phosphonates

Energy Technology Data Exchange (ETDEWEB)

Belokoneva, E. L., E-mail: elbel@geol.msu.ru; Dimitrova, O. V.; Volkov, A. S. [Moscow State University, Faculty of Geology (Russian Federation)

2015-09-15

The new Mn{sub 0.95}I{sub 0.02}[PO{sub 3}(OH)] · 2H{sub 2}O phosphate–iodate (space group Pnam = Pnma, D{sub 2h}{sup 16}) is obtained under hydrothermal conditions. The crystal structure is determined without preliminary knowledge of the chemical formula. The structure consists of layers of MnO{sub 6} octahedra connected with PO{sub 4} tetrahedra. Water molecules are located between the layers. [IO3]{sup –} groups having a typical umbrella-like coordination are statistically implanted in layers of MnO{sub 6} octahedra at a distance of 1.2 Å from Mn atoms. Their content in the crystal is minor. The structures of the phosphate–iodate coincides with the structures of phosphonates with consideration for the replacement of one (OH) vertex of the PO{sub 4} tetrahedron by the organic methyl radical CH{sub 3}. In the structures of phosphonates and earlier studied phosphates, identical layers are distinguished and the cause of the existence of two MDO varieties is established based on the analysis within the OD theory. Possible hybrid structures derived from the prototypes under consideration are predicted.

Flotation performances and adsorption mechanism of α-hydroxyoctyl phosphinic acid to cassiterite

International Nuclear Information System (INIS)

Li, Fangxu; Zhong, Hong; Zhao, Gang; Wang, Shuai; Liu, Guangyi

2015-01-01

Highlights: • Flotation of cassiterite is carried out using a new collector HPA. • Phosphorous and oxygen of HPA forms chelation with Sn. • HPA exhibits good selectivity to cassiterite against magnetite and hematite. • HPA chemisorbs on cassiterite surface by form of Sn–P and Sn–O–P bond. - Abstract: In this paper, the flotation performances and adsorption mechanism of α-hydroxyoctyl phosphinic acid (HPA) to cassiterite were investigated by adsorption experiments, micro-flotation tests, zeta potential measurements, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses. The micro-flotation results indicated that compared with styrene phosphonic acid (SPA), diphosphonic acid (DPA), benzohydroxamic acid (BHA) and salicylhydroxamic acid (SHA), HPA exhibited excellent collecting power to cassiterite and superior selectivity against magnetite or hematite over a wide pH range. The results of adsorption experiments and zeta potential deduced that HPA chemisorb on cassiterite surfaces. The results of FTIR inferred HPA chemisorb onto cassiterite surfaces through its P and O atoms with the P–H and O–H bonds broken. XPS analysis further demonstrated HPA react with Sn species by formation of Sn–O–P and Sn–P bond.

Morphologies of precise polyethylene-based acid copolymers and ionomers

Science.gov (United States)

Buitrago, C. Francisco

Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been

Design and synthesis of new poly-phosphorylated upper-rim modified calix[4]arenes as potential and selective chelating agents of uranyl ion

International Nuclear Information System (INIS)

Migianu-Griffoni, E.; Mbemba, C.; Burgada, R.; Lecouvey, M.; Lecercle, D.; Taran, F.

2009-01-01

New upper-rim poly-phosphorylated calix[4]arenes were designed for decorporation of uranium in case of nuclear contamination. A ligand system containing four pre-organized 1-hydroxymethylene-1, 1-bisphosphonic acid moieties anchored onto a calix[4]arene platform has been developed. Three calix[4]-arene-bis-phosphonates were efficiently prepared in multi-step syntheses with a variable carbon chain length between the bis-phosphonate and the calix[4]arene. Affinity constants towards uranyl ion were determined and compared with those of bis(HEDP) and tris(HEDP) phosphonates, known as efficient ligands for uranyl. (authors)

Evaluation of Novel Acyclic Nucleoside Phosphonates against Human and Animal Gammaherpesviruses Revealed an Altered Metabolism of Cyclic Prodrugs upon Epstein-Barr Virus Reactivation in P3HR-1 Cells

Czech Academy of Sciences Publication Activity Database

Coen, N.; Duraffour, S.; Naesens, L.; Krečmerová, Marcela; Van Den Oord, J.; Snoeck, R.; Andrei, G.

2013-01-01

Roč. 87, č. 22 (2013), s. 12422-12432 ISSN 0022-538X R&D Projects: GA MPO FR-TI4/625 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonate * gammaherpesvirus * Epstein-Barr virus * Kaposi's sarcoma * HPMP-5-azaC * cidofovir Subject RIV: EE - Microbiology, Virology Impact factor: 4.648, year: 2013

Synthetic Analogs of Phospholipid Metabolites as Antimalarials.

Science.gov (United States)

1979-07-01

phosphatidic acid analogs containing ether and phosphonate groups; completely non- hydrolyzable lecithin analogs containing phosphinate and ether groups...substance is a completely non- hydrolyzable analog of lecithin containing ether and phosphonate moieties instead of the normally labile carboxylic and...and also ant-i-phospholipase C (clostridial enzyme) activity. This substance Is a completely non- hydrolyzable analog of lecithin containing ether

Evaluation and improvement of gamma-ray stability of chelating resins containing oxy-acid groups of phosphorus

International Nuclear Information System (INIS)

Jyo, Akinori; Yamabe, Kazunori; Shuto, Taketomi

1998-01-01

Chelating resins containing oxy-acid groups of phosphorus, such as phosphonic and phosphoric acid groups have been studied from the point of view of solvent extraction processes for the separation of nuclear fuel elements as well as of fission product ones. The present work was planned to evaluate the effect of gamma-ray on properties of the resins and to obtain directional information for design of the resins having high stability to gamma-ray. It was clarified that gamma-ray stability of the resins is not high; tolerance limit is ca. 2.3x10 3 C/kg. The present work also clarified that polymers crosslinked with divinylbenzene have much higher gamma-ray stability than ones crosslinked with dimetacrylate esters of oligo (ethylene glycol)s. (J.P.N.)

10-Undecenoic Acid, an Inexpensive Source for the Synthesis of the Pheromones of Cotton Pests, Peach Tree Borer and Cherry Tree Borer

Directory of Open Access Journals (Sweden)

Subrata Chattopadhyay

1997-06-01

Full Text Available The aldehyde 7, derived from 10-undecenoic acid (5 on cis-selective Wittig reaction with pentylidenetriphenylphosphorane, subsequent deprotection and oxidation gave the pheromone (11Z-hexadecenal (1. Wittig-Horner olefination of 1 with the phosphonate 9 furnished the conjugated ester 10 which on base catalyzed isomerization to the (3Z-ester 11 followed by LAH reduction and acetylation gave (3Z,13Z-octadeadien-1-yl acetate (2. Compound 10 on the other hand was chemoselectively reduced and acetylated to furnish the pheromone (2E,13Z-octadeadien-1-yl acetate (4. For the synthesis of (3E,13Z-octadeadien-1-yl acetate (3, 1 was condensed with malonic acid under modified condition to afford the acid 13 which was converted to 3 by standard reaction protocol.

The development of new, low-cost perfluoroalkylether fluids with excellent low and high-temperature properties

Science.gov (United States)

Bierschenk, Thomas R.; Kawa, Hajimu; Juhlke, Timothy J.; Lagow, Richard J.

1988-01-01

A series of perfluoroalkylether (PFAE) fluids were synthesized by direct fluorination. Viscosity-temperature properties, oxidation stabilities, oxidation-corrosion properties, and lubricity were determined. The fluids were tested in the presence of common elastomers to check for compatibility. The bulk modulus of each was measured to determine if any could be used as nonflammable aircraft hydraulic fluid. It was determined that as the carbon to oxygen ratio decreases, the viscometric properties improve, the fluids may become poor lubricants, the bulk modulus increases, the surface tension increases, and the fluid density increases. The presence of difluoromethylene oxide units in the polymer does not seriously lower the oxidation and oxidation-corrosion stabilities as long as the difluoromethylene oxide units are separated by other units.

Zinc oxide modified with benzylphosphonic acids as transparent electrodes in regular and inverted organic solar cell structures

Energy Technology Data Exchange (ETDEWEB)

Lange, Ilja; Reiter, Sina; Kniepert, Juliane; Piersimoni, Fortunato; Brenner, Thomas; Neher, Dieter, E-mail: neher@uni-potsdam.de [Institute of Physics and Astronomy, University of Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam (Germany); Pätzel, Michael; Hildebrandt, Jana; Hecht, Stefan [Department of Chemistry and IRIS Adlershof, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin (Germany)

2015-03-16

An approach is presented to modify the work function of solution-processed sol-gel derived zinc oxide (ZnO) over an exceptionally wide range of more than 2.3 eV. This approach relies on the formation of dense and homogeneous self-assembled monolayers based on phosphonic acids with different dipole moments. This allows us to apply ZnO as charge selective bottom electrodes in either regular or inverted solar cell structures, using poly(3-hexylthiophene):phenyl-C71-butyric acid methyl ester as the active layer. These devices compete with or even surpass the performance of the reference on indium tin oxide/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Our findings highlight the potential of properly modified ZnO as electron or hole extracting electrodes in hybrid optoelectronic devices.

Functionalisation of Ti6Al4V components fabricated using selective laser melting with a bioactive compound.

Science.gov (United States)

Vaithilingam, Jayasheelan; Kilsby, Samuel; Goodridge, Ruth D; Christie, Steven D R; Edmondson, Steve; Hague, Richard J M

2015-01-01

Surface modification of an implant with a biomolecule is used to improve its biocompatibility and to reduce post-implant complications. In this study, a novel approach has been used to functionalise phosphonic acid monolayers with a drug. Ti6Al4V components fabricated using selective laser melting (SLM) were functionalised with Paracetamol (a pharmaceutically relevant biomolecule) using phosphonic acid based self-assembled monolayers (SAMs). The attachment, stability of the monolayers on the SLM fabricated surface and functionalisation of SAMs with Paracetamol were studied using X-ray photoelectron spectroscopy (XPS) and surface wettability measurements. The obtained results confirmed that SAMs were stable on the Ti6Al4V surface for over four weeks and then began to desorb from the surface. The reaction used to functionalise the phosphonic acid monolayers with Paracetamol was noted to be successful. Thus, the proposed method has the potential to immobilise drugs/proteins to SAM coated surfaces and improve their biocompatibility and reduce post-implant complications. Copyright © 2014. Published by Elsevier B.V.

Molecular recognition: Comparative study of a tunable host-guest system by using a fluorescent model system and collision-induced dissociation mass spectrometry on dendrimers

DEFF Research Database (Denmark)

Pittelkow, M.; Nielsen, C.B.; Broeren, A.C.

2005-01-01

Host-guest interactions between the periphery of adamantylurea-functionalized dendrimers (host) and ureido acetic acid derivatives (guest) were shown to be specific, strong and spatially well-defined. The binding becomes stronger when using phosphonic or sulfonic acid derivatives. In the present...... work we have quantified the binding constants for the host-guest interactions between two different host motifs and six different guest molecules. The host molecules, which resemble the periphery of a poly(propylene imine) dendrimer, have been fitted with an anthracene-based fluorescent probe. The two...... host motifs differ in terms of the length of the spacer between a tertiary amine and two ureido functionalities. The guest molecules all contain an acidic moiety (either a carboxylic acid, a phosphonic acid, or a sulfonic acid) and three of them also contain an ureido moiety capable of forming multiple...

Synthesis of new triphosphonic esters for uranium extraction in phosphoric medium

International Nuclear Information System (INIS)

Sturtz, Georges; Pensec, Thierry

1981-01-01

Triphosphonic acids obtained by nucleophilic addition of dialkyl phosphites on ethylenic diphosphonates are partially hydrolysed into incompletely esterified triphosphonic acids. Their extracting properties for uranium-IV in phosphonic medium are tested [fr

ESI mass spectrometry applied to enantiodiscrimination of chiral systems

International Nuclear Information System (INIS)

Lagana, A.; Paladini, A.; Catone, D.; Giardini, A.; Filippi, A.; D'Ettole, A.; Speranze, M.

2002-01-01

Experiments with electrospray ionization coupled with mass spectrometric detection (ESI-MS) together with collisional induced dissociation (CID) were performed in order to study the affinity of chiral alfa-aminophosphonic acids towards first-group metals (Na, Li, K) in gaseous phase and how this can be affected by the ligands configuration. The results are discussed in the light of structure calculation performed by using an empirical force field. The CID fragmentation spectra of diastereomeric clusters containing (1-amino-2-methylpropyl)phosphonic acid enantiomers (P R , P S ), (S)-(+)-(1-aminoethyl)phosphonic acid (E S ) and a sodium ion ( [NaP R (E S ) 2 ] + and [NaP S (E S ) 2 ] + ) is given. (nevyjel)

Distribution of 14 elements from two solutions simulating Hanford HLW Tank 102-SY (acid-dissolved sludge and acidified supernate) on four cation exchange resins and five anion exchange resins having different functional groups

International Nuclear Information System (INIS)

Marsh, S.F.; Svitra, Z.V.; Bowen, S.M.

1995-01-01

As part of the Tank Waste Remediation System program at Los Alamos, we evaluated a series of cation exchange and anion exchange resins for their ability to remove hazardous components from radioactive high-level waste (HLW). The anion exchangers were Reillex TM HPQ, a polyvinyl pyridine resin, and four strong-base polystyrene resins having trimethyl, tri ethyl, tri propyl, and tributyl amine as their respective functional groups. The cation exchange resins included Amberlyst TM 15 and Amberlyst tM XN-1010 with sulfonic acid functionality, Duolite TM C-467 with phosphonic acid functionality, and poly functional Diphonix TM with di phosphonic acid, sulfonic acid, and carboxylic acid functionalities. We measured the distributions of 14 elements on these resins from solutions simulating acid-dissolved sludge (pH 0.6) and acidified supernate (pH 3.5) from underground storage tank 102-SY at the Hanford Reservation near Richland, Washington, USA. To these simulants, we added the appropriate radionuclides and used gamma spectrometry to measure fission products (Ce, Cs, Sr, Tc, and Y), actinides (U, Pu, and Am), and matrix elements (Cr, Co, Fe, Mn, Zn, and Zr). For each of the 252 element/resin/solution combinations, distribution coefficients (Kds) were measured for dynamic contact periods of 30 minutes, 2 hours, and 6 hours to obtain information about sorption kinetics from these complex media. Because we measured the sorption of many different elements, the tabulated results indicate which unwanted elements are most likely to interfere with the sorption of elements of special interest. On the basis of these 756 measured Kd values, we conclude that some of the tested resins appear suitable for partitioning hazardous components from Hanford HLW. (author). 10 refs., 11 tabs

Aqueous corrosion of phosphide minerals from iron meteorites: a highly reactive source of prebiotic phosphorus on the surface of the early Earth.

Science.gov (United States)

Pasek, Matthew A; Lauretta, Dante S

2005-08-01

We present the results of an experimental study of aqueous corrosion of Fe-phosphide under conditions relevant to the early Earth. The results strongly suggest that iron meteorites were an important source of reactive phosphorus (P), a requirement for the formation of P-based life. We further demonstrate that iron meteorites were an abundant source of phosphide minerals early in Earth history. Phosphide corrosion was studied in five different solutions: deionized water, deionized water buffered with sodium bicarbonate, deionized water with dissolved magnesium and calcium chlorides, deionized water containing ethanol and acetic acid, and deionized water containing the chlorides, ethanol, and acetic acid. Experiments were performed in the presence of both air and pure Ar gas to evaluate the effect of atmospheric chemistry. Phosphide corrosion in deionized water results in a metastable mixture of mixed-valence, P-bearing ions including pyrophosphate and triphosphate, key components for metabolism in modern life. In a pH-buffered solution of NaHCO(3), the condensed and reduced species diphosphonate is an abundant corrosion product. Corrosion in ethanol- and acetic acid-containing solutions yields additional P-bearing organic molecules, including acetyl phosphonate and a cyclic triphosphorus molecule. Phosphonate is a major corrosion product of all experiments and is the only P-bearing molecule that persists in solutions with high concentrations of magnesium and calcium chlorides, which suggests that phosphonate may have been a primitive oceanic source of P. The stability and reactivity of phosphonate and hypophosphite in solution were investigated to elucidate reaction mechanisms and the role of mineral catalysts on P-solution chemistry. Phosphonate oxidation is rapid in the presence of Fe metal but negligible in the presence of magnetite and in the control sample. The rate of hypophosphite oxidation is independent of reaction substrate.

A Comparative Performance Evaluation of Some Novel “Green” and Traditional Antiscalants in Calcium Sulfate Scaling

Directory of Open Access Journals (Sweden)

Konstantin Popov

2016-01-01

Full Text Available A relative ability of industrial samples of four phosphorus-free polymers (polyaspartate (PASP; polyepoxysuccinate (PESA; polyacrylic acid sodium salt (PAAS; copolymer of maleic and acrylic acid (MA-AA and of three phosphonates (aminotris(methylenephosphonic acid, ATMP; 1-hydroxyethane-1,1-bis(phosphonic acid, HEDP; phosphonobutane-1,2,4-tricarboxylic acid, PBTC to inhibit calcium sulfate precipitation is studied following the NACE Standard along with dynamic light scattering (DLS, scanning electron microscopy (SEM, and X-ray diffraction (XRD technique. For the 0.5 mg·dm−3 dosage, the following efficiency ranking was found: MA-AA~ATMP>PESA (400–1500 Da>PASP (1000–5000 Da ≫ PAAS (3000–5000 Da~PBTC~HEDP. The isolated crystals are identified as gypsum. SEM images for PESA, PASP, PAAS, and HEDP and for a blank sample indicated the needle-like crystal morphology. Surprisingly, the least effective reagent PBTC revealed quite a different behavior, changing the morphology of gypsum crystals to an irregular shape. The DLS experiments exhibited a formation of 300 to 700 nm diameter particles with negative ζ-potential around −2 mV for all reagents. Although such ζ-potential values are not capable of providing colloidal stability, all three phosphonates demonstrate significant gypsum particles stabilization relative to a blank experiment.

A structural insight into the P1S1 binding mode of diaminoethylphosphonic and phosphinic acids, selective inhibitors of alanine aminopeptidases

Energy Technology Data Exchange (ETDEWEB)

Węglarz-Tomczak, Ewelina; Berlicki, Łukasz; Pawełczak, Małgorzata; Nocek, Bogusław; Joachimiak, Andrzej; Mucha, Artur

2016-07-01

N0 -substituted 1,2-diaminoethylphosphonic acids and 1,2-diaminoethylphosphinic dipeptides were explored to unveil the structural context of the unexpected selectivity of these inhibitors of M1 alanine aminopeptidases (APNs) versus M17 leucine aminopeptidase (LAP). The diaminophosphonic acids were obtained via aziridines in an improved synthetic procedure that was further expanded for the phosphinic pseudodipeptide system. The inhibitory activity, measured for three M1 and one M17 metalloaminopeptidases of different sources (bacterial, human and porcine), revealed several potent compounds (e.g., Ki ¼ 65 nM of 1u for HsAPN). Two structures of an M1 representative (APN from Neisseria meningitidis) in complex with N-benzyl-1,2-diaminoethylphosphonic acid and N-cyclohexyl-1,2- diaminoethylphosphonic acid were determined by the X-ray crystallography. The analysis of these structures and the models of the phosphonic acid complexes of the human ortholog provided an insight into the role of the additional amino group and the hydrophobic substituents of the ligands within the S1 active site region.

Potentiometric and NMR complexation studies of phenylboronic acid PBA and its aminophosphonate analog with selected catecholamines

Science.gov (United States)

Ptak, Tomasz; Młynarz, Piotr; Dobosz, Agnieszka; Rydzewska, Agata; Prokopowicz, Monika

2013-05-01

Boronic acids are a class of intensively explored compounds, which according to their specific properties have been intensively explored in last decades. Among them phenylboronic acids and their derivatives are most frequently examined as receptors for diverse carbohydrates. In turn, there is a large gap in basic research concerning complexation of catecholamines by these compounds. Therefore, we decided to undertake studies on interaction of chosen catecholamines, namely: noradrenaline (norephinephrine), dopamine, L-DOPA, DOPA-P (phosphonic analog of L-DOPA) and catechol, with simple phenyl boronic acid PBA by means of potentiometry and NMR spectroscopy. For comparison, the binding properties of recently synthesized phenylboronic receptor 1 bearing aminophosphonate function in meta-position were investigated and showed promising ability to bind catecholamines. The protonation and stability constants of PBA and receptor 1 complexes were examined by potentiometry. The obtained results demonstrated that PBA binds the catecholamines with the following affinity order: noradrenaline ⩾ dopamine ≈ L-DOPA > catechol > DOPA-P, while its modified analog 1 reveals slightly different preferences: dopamine > noradrenaline > catechol > L-DOPA > DOPA-P.

Infrared Spectroscopic Observations on the Fate of Organophosphorus Compounds Exposed to Atmospheric Moisture. Part 3

Science.gov (United States)

2007-05-01

FATE OF ORGANOPHOSPHORUS COMPOUNDS EXPOSED TO ATMOSPHERIC MOISTURE PART III. PHOSPHINES, PHOSPHITES , PHOSPHONITES, PHOSPHINITES, PHOSPHORIC ACIDS ...The investigation continues with Phosphines, Phosphites , Phosphonites, Phosphinites, Phosphoric Acids , Phosphonic Acids , Phosphinic Acids , Phosphine...infrared spectrum of di-(2-ethylhexyl) phosphoric acid as a liquid film between KBr windows is given in Figure 104. The band assignments are as follows

Studies of the influence of different anions on extraction of neodymium with di(1-methylheptyl)methyl phosphonate

International Nuclear Information System (INIS)

Chun-Hui Huang; Rong-Fang Xi; Hai Guo; Guang-Xian Xu

1988-01-01

A study was made on extraction of Nd(NCS) 3 , Nd(ClO 4 ) 3 , Nd(NO 3 ) 3 by di-(1-methylhexyl)methyl phosphonate (P-350) in hexane. ΔG 0 (kJ/mol), ΔH 0 (kJ/mol) and ΔS 0 (kJ/mol) were calculated. They are equal to: -9.719, -29.92, -67.78 for P-350(hexane)-Nd(NCS) 3 system; 3.752, -74.31, -261.9 for P-350((hexane)-Nd(ClO 4 ) 3 system; 2.265, -22.69, -83.68 for P-350(hexane)-Nd(NO 3 ) 3 system. Structure of extracted complexes in hexane solution and corresponding solid complexes were correlated with triphenylphosphine oxide as P-350 model. Data of IR-spectroscopy show, that absorption bands of complexes in saturated organic solvents or in the solid phase are shifted to the region of lower frequencies as compared to absorption bands of corresponding salts. This testifies to similarity of complex structures in both phases

Utilization of Glyphosate as Phosphate Source: Biochemistry and Genetics of Bacterial Carbon-Phosphorus Lyase

Science.gov (United States)

Zechel, David L.; Jochimsen, Bjarne

2014-01-01

SUMMARY After several decades of use of glyphosate, the active ingredient in weed killers such as Roundup, in fields, forests, and gardens, the biochemical pathway of transformation of glyphosate phosphorus to a useful phosphorus source for microorganisms has been disclosed. Glyphosate is a member of a large group of chemicals, phosphonic acids or phosphonates, which are characterized by a carbon-phosphorus bond. This is in contrast to the general phosphorus compounds utilized and metabolized by microorganisms. Here phosphorus is found as phosphoric acid or phosphate ion, phosphoric acid esters, or phosphoric acid anhydrides. The latter compounds contain phosphorus that is bound only to oxygen. Hydrolytic, oxidative, and radical-based mechanisms for carbon-phosphorus bond cleavage have been described. This review deals with the radical-based mechanism employed by the carbon-phosphorus lyase of the carbon-phosphorus lyase pathway, which involves reactions for activation of phosphonate, carbon-phosphorus bond cleavage, and further chemical transformation before a useful phosphate ion is generated in a series of seven or eight enzyme-catalyzed reactions. The phn genes, encoding the enzymes for this pathway, are widespread among bacterial species. The processes are described with emphasis on glyphosate as a substrate. Additionally, the catabolism of glyphosate is intimately connected with that of aminomethylphosphonate, which is also treated in this review. Results of physiological and genetic analyses are combined with those of bioinformatics analyses. PMID:24600043

On medicative application of complexons in the case of uranium intoxication

International Nuclear Information System (INIS)

Ivannikov, A.T.

1987-01-01

The report deals with the problem of accelerating the uranium elimination from the body in the light of present knowledge. Based on data available in the literature and obtained by the author, effects of sodium bicarbonate, complexons (polyamine-polycarbonic acids) and their phosphonic analogues - polyamine-polyalkyl-phosphonic acids (AMPAs) in the case of uranium intoxication have been analysed. Thus, sodium bicarbonate recommended by the ICRP and IAEA as a remedy for uranium intoxication produces some adverse action reducing its efficiency, while warning against complexons because of risk for kidneys proved to be unjustified. Experimental evidence presented demonstrates conclusively that AMPAs are the most efficient complexing agents for uranium binding and eliminating from the body, essentially superior to complexons due to greater stability constants of AMPA with uranyl ion. AMPAs form stable protonated complexes with uranyl ion which are resistant to acid medium typical of certain kidney parts, so that decomposition of these complexes and deposition of uranium are prevented, thus lowering risk for kidneys. This compares favourably with sodium bicarbonate whose complex with uranyl ion is rather unstable at low pH values. An AMPA compound, Na 6 Ca 2 -diethylene-triamine-pentamethyl- phosphonic acid (the preparation called trimephacin), is adopted in the USSR as an antidote for uranium intoxication and proposed to be included into ICRP Recommendations. (author)

Iron(III) diethylenetriaminepentaacetic acid complex on polyallylamine functionalized multiwalled carbon nanotubes: immobilization, direct electrochemistry and electrocatalysis.

Science.gov (United States)

Liu, Hailing; Cui, Yanyun; Li, Pan; Zhou, Yiming; Zhu, Xiaoshu; Tang, Yawen; Chen, Yu; Lu, Tianhong

2013-05-07

A nonenzymatic iron(III) diethylenetriaminepentaacetic acid (Fe(III)-DETPA) complex based amperometric sensor for the analytical determination of hydrogen peroxide was developed. By combining the electrostatic interaction between the Fe(III)-DETPA complex and polyallylamine (PAH) functionalized multiwalled carbon nanotubes (MWCNTs) as well as the ionotropic crosslinking interaction between PAH and ethylenediamine-tetramethylene phosphonic acid (EDTMP), the electroactive Fe(III)-DETPA complex was successfully incorporated within the MWCNT matrix, and firmly immobilized on the Au substrate electrode. The fabricated electrochemical sensor was characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical methods. The influences of solution pH and ionic strength on the electrochemical sensor were investigated. The prepared electrochemical sensor had a fast response to hydrogen peroxide (<3 s) and an excellent linear range of concentration from 1.25 × 10(-8) to 4.75 × 10(-3) M with a detection limit of 6.3 × 10(-9) M under the optimum conditions.

Structures and Spectroscopy Studies of Two M(II-Phosphonate Coordination Polymers Based on Alkaline Earth Metals (M = Ba, Mg

Directory of Open Access Journals (Sweden)

Kui-Rong Ma

2013-01-01

Full Text Available The two examples of alkaline-earth M(II-phosphonate coordination polymers, [Ba2(L(H2O9]·3H2O (1 and [Mg1.5(H2O9]·(L-H21.5·6H2O (2 (H4L = H2O3PCH2N(C4H8NCH2PO3H2, N,N′-piperazinebis(methylenephosphonic acid, (L-H2 = O3PH2CHN(C4H8NHCH2PO3 have been hydrothermally synthesized and characterized by elemental analysis, FT-IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Compound 1 possesses a 2D inorganic-organic alternate arrangement layer structure built from 1D inorganic chains through the piperazine bridge, in which the ligand L−4 shows two types of coordination modes reported rarely at the same time. In 1, both crystallographic distinct Ba(1 and Ba(2 ions adopt 8-coordination two caps and 9-coordination three caps triangular prism geometry structures, respectively. Compound 2 possesses a zero-dimensional mononuclear structure with two crystallographic distinct Mg(II ions. Free metal cations   [MgO6]n2+ and uncoordinated anions (L-H2n2- are joined together by static electric force. Results of photoluminescent measurement indicate three main emission bands centered at 300 nm, 378.5 nm, and 433 nm for 1 and 302 nm, 378 nm, and 434.5 nm for 2 (λex=235 nm, respectively. The high energy emissions could be derived from the intraligand π∗-n transition stations of H4L (310 nm and 382 nm, λex=235 nm, while the low energy emission (>400 nm of 1-2 may be due to the coordination effect with metal(II ions.

New N-Acetyltransferase Fold in the Structure and Mechanism of the Phosphonate Biosynthetic Enzyme FrbF

Energy Technology Data Exchange (ETDEWEB)

Bae, Brian; Cobb, Ryan E.; DeSieno, Matthew A.; Zhao, Huimin; Nair, Satish K. (UIUC)

2015-10-15

The enzyme FrbF from Streptomyces rubellomurinus has attracted significant attention due to its role in the biosynthesis of the antimalarial phosphonate FR-900098. The enzyme catalyzes acetyl transfer onto the hydroxamate of the FR-900098 precursors cytidine 5'-monophosphate-3-aminopropylphosphonate and cytidine 5'-monophosphate-N-hydroxy-3-aminopropylphosphonate. Despite the established function as a bona fide N-acetyltransferase, FrbF shows no sequence similarity to any member of the GCN5-like N-acetyltransferase (GNAT) superfamily. Here, we present the 2.0 {angstrom} resolution crystal structure of FrbF in complex with acetyl-CoA, which demonstrates a unique architecture that is distinct from those of canonical GNAT-like acetyltransferases. We also utilized the co-crystal structure to guide structure-function studies that identified the roles of putative active site residues in the acetyltransferase mechanism. The combined biochemical and structural analyses of FrbF provide insights into this previously uncharacterized family of N-acetyltransferases and also provide a molecular framework toward the production of novel N-acyl derivatives of FR-900098.

Glyphosate catabolism by Pseudomonas sp

International Nuclear Information System (INIS)

Shinabarger, D.L.

1986-01-01

The pathway for the degradation of glyphosate (N-phosphonomethylglycine) by Pseudomonas sp. PG2982 has been determined using metabolic radiolabeling experiments. Radiorespirometry experiments utilizing [3- 14 C] glyphosate revealed that approximately 50-59% of the C3 carbon was oxidized to CO 2 . Fractionation of stationary phase cells labeled with [3- 14 C]glyphosate revealed that from 45-47% of the assimilated C3 carbon is distributed to proteins and that amino acids methionine and serine are highly labeled. The nucleic acid bases adenine and guanine received 90% of the C3 label that was incorporated into nucleic acids, and the only pyrimidine base labeled was thymine. Pulse labeling of PG2982 cells with [3- 14 C]glyphosate revealed that [3- 14 C]sarcosine is an intermediate in glyphosate degradation. Examination of crude extracts prepared from PG2982 cells revealed the presence of an enzyme that oxidizes sarcosine to glycine and formaldehyde. These results indicate that the first step in glyphosate degradation by PG2982 is cleavage of the carbon-phosphorus bond, resulting in the release of sarcosine and a phosphate group. The phosphate group is utilized as a source of phosphorus, and the sarcosine is degraded to glycine and formaldehyde. Phosphonate utilization by Pseudomonas sp. PG2982 was investigated. Each of the ten phosphonates tested were utilized as a sole source of phosphorus by PG2982. Representative compounds tested included alkylphosphonates, 1-amino-substituted alkylphosphonates, amino-terminal phosphonates, and an arylphosphonate. PG2982 cultures degraded phenylphosphonate to benzene and produced methane from methylphosphonate. The data indicate that PG2982 is capable of cleaving the carbon-phosphorus bond of several structurally different phosphonates

In vitro antitumour activity, safety testing and subcellular distribution of two poly[oxyethylene(aminophosphonate-co-H-phosphonate]s in Ehrlich ascites carcinoma and BALB/c 3T3 cell culture systems

Directory of Open Access Journals (Sweden)

Ani Georgieva

2016-01-01

Full Text Available Two polyphosphoesters containing anthracene-derived aminophosphonate and hydrophilic H-phosphonate repeating units, poly[oxyethylene(aminophosphonate-co-H-phosphonate]s (1 and 2, were tested for the in vitro antitumour activity on cell cultures derived from ascitic form of Ehrlich mammary adenocarcinoma by 3-(4,5-dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT-dye reduction assay. The in vitro safety testing of the copolymers was performed by BALB/c 3T3 neutral red uptake assay. A study on their uptake and subcellular distribution in non-tumourigenic and tumour cells was performed by means of fluorescence microscopy. Both copolymers showed significant antitumour activity towards Ehrlich ascites carcinoma (EAC cells. However, the in vitro safety testing revealed significant toxicity of polymer 2 to BALB/c 3T3 mouse embryo cells. In contrast, polymer 1 showed complete absence of cytotoxicity to BALB/c 3T3 cells. The fluorescent studies showed that the substances were diffusely distributed in the cytoplasm in both cell culture systems. As opposed to BALB/c 3T3 cells, in EAC cells, intense fluorescent signal was observed in the nuclei and in the perinuclear region. The tested polyphosphoesters are expected to act under physiological conditions as prodrugs of aminophosphonates.

Compostos organofosforados pentavalentes: histórico, métodos sintéticos de preparação e aplicações como inseticidas e agentes antitumorais Organophosphorus pentavalent compounds: history, synthetic methods of preparation and application as insecticides and antitumor agents

Directory of Open Access Journals (Sweden)

Viviane Martins Rebello dos Santos

2007-02-01

Full Text Available This paper is a review of the history, synthesis and application of organophosphorus compounds, especially of those of pentavalent phosphorus, such as phosphoramidates, phosphorothioates, phosphonates and phosphonic acids with insecticide and anticancer activities. The organophosphorus compounds with agrochemical applications show great structural variety, They include not only insecticides, but also fungicides, herbicides, and others. The large variety of commercially available organophosphorus pesticides is remarkable. Even more interesting is the high efficiency of some organophosphorus compounds as anticancer agents such as cyclophosphamide and its derivatives.

Organophosphorus pentavalent compounds: history, synthetic methods of preparation and application as insecticides and antitumor agents

International Nuclear Information System (INIS)

Santos, Viviane Martins Rebello dos; Donnici, Claudio Luis; DaCosta, Joao Batista Neves; Caixeiro, Janaina Marques Rodrigues

2007-01-01

This paper is a review of the history, synthesis and application of organophosphorus compounds, especially of those of pentavalent phosphorus, such as phosphoramidates, phosphorothioates, phosphonates and phosphonic acids with insecticide and anticancer activities. The organophosphorus compounds with agrochemical applications show great structural variety, They include not only insecticides, but also fungicides, herbicides, and others. The large variety of commercially available organophosphorus pesticides is remarkable. Even more interesting is the high efficiency of some organophosphorus compounds as anticancer agents such as cyclophosphamide and its derivatives. (author)

Demonstration of spread-on peel-off consumer products for sampling surfaces contaminated with pesticides and chemical warfare agent signatures.

Science.gov (United States)

Behringer, Deborah L; Smith, Deborah L; Katona, Vanessa R; Lewis, Alan T; Hernon-Kenny, Laura A; Crenshaw, Michael D

2014-08-01

A terrorist attack using toxic chemicals is an international concern. The utility of rubber cement and latex body paint as spray-on/spread-on peel-off collection media for signatures attributable to pesticides and chemical warfare agents from interior building and public transportation surfaces two weeks post-deposition is demonstrated. The efficacy of these media to sample escalator handrail, stainless steel, vinyl upholstery fabric, and wood flooring is demonstrated for two pesticides and eight chemicals related to chemical warfare agents. The chemicals tested are nicotine, parathion, atropine, diisopropyl methylphosphonate, dimethyl methylphosphonate, dipinacolyl methylphosphonate, ethyl methylphosphonic acid, isopropyl methylphosphonic acid, methylphosphonic acid, and thiodiglycol. Amounts of each chemical found are generally greatest when latex body paint is used. Analytes with low volatility and containing an alkaline nitrogen or a sulfur atom (e.g., nicotine and parathion) usually are recovered to a greater extent than the neutral phosphonate diesters and acidic phosphonic acids (e.g., dimethyl methylphosphonate and ethyl methylphosphonic acid). Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Investigation on three new metal carboxydiphosphonates: Syntheses, structures, magnetic and luminescent properties

Energy Technology Data Exchange (ETDEWEB)

Tang Sifu; Pan Xiaobo; Lv Xiaoxia [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Zhao Xuebo, E-mail: zhaoxb@qibebt.ac.cn [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China)

2013-01-15

A new multifunctionalized phosphoric acid, (2-(diphosphonomethylamino)nicotinic acid, Py(COOH)(NHCH--(PO{sub 3}H{sub 2}){sub 2}), H{sub 5}L{sup 1}), has been employed as ligand for the construction of new metal phosphonates. By reacting it with different metal chlorides under hydrothermal condition, three new transition metal phosphonates, namely, [Co{sub 2}(HL{sup 1})(H{sub 2}O){sub 5}][H{sub 2}O]{sub 3} (1), Zn(H{sub 3}L{sup 1}) (2) and [Cd(H{sub 3}L{sup 1})(H{sub 2}O){sub 2}][H{sub 2}O] (3) were successfully obtained. The single-crystal structure measurements indicated that the coordination mode of ligand H{sub 5}L{sup 1} is metal-dependant and results in different structures. For compound 1, it features 2D layered structure. Whereas compounds 2 and 3 have 1D chain structures. Under the excitation of 250 nm light, both compounds 2 and 3 show intraligand and ligand to metal charge transfer (LMCT) emission bands at about 415 and 420 nm, respectively. Magnetic study shows that compound 1 displays antiferromagnetic behavior. - Graphical abstract: Three new metal phosphonates were synthesized from a multifunctionalized phosphonate ligand and different metal chlorides. Their structures, thermal stabilities, luminescent and magnetic properties were characterized. Highlights: Black-Right-Pointing-Pointer Three new metal phosphonates were synthesized under hydrothermal conditions. Black-Right-Pointing-Pointer Compound 1 exhibits 2D layered structure. Black-Right-Pointing-Pointer Compounds 2 and 3 have 1D infinite chain structures. Black-Right-Pointing-Pointer Compound 1 displays antiferromagnetic behavior. Black-Right-Pointing-Pointer Compounds 2 and 3 show intraligand and ligand to metal charge transfer emission bands.

Gas chromatography-mass spectrometric studies of O-alkyl O-2-(N,N-dialkylamino) ethyl alkylphosphonites(phosphonates) for chemical weapons convention verification.

Science.gov (United States)

Saeidian, Hamid; Babri, Mehran; Ramezani, Atefeh; Ashrafi, Davood; Sarabadani, Mansour; Naseri, Mohammad Taghi

2013-01-01

The electron ionization (EI) mass spectra of a series of O-alkyl O-2-(N,N-dialkylaminolethyl alkylphosphonites(phosphonates), which are precursors of nerve agents, were studied for Chemical Weapons Convention (CWC) verification. General El fragmentation pathways were constructed and discussed. Proposed fragment structures were confirmed through analyzing fragment ions of deuterated analogs and density functional theory (DFT) calculations. The observed fragment ions are due to different fragmentation pathways such as hydrogen and McLafferty+1 rearrangements, alkene, amine and alkoxy elimination by alpha- or beta-cleavage process. Fragment ions distinctly allow unequivocal identification of the interested compounds including those of isomeric compounds. The presence and abundance of fragment ions were found to depend on the size and structure of the alkyl group attached to nitrogen, phosphorus and oxygen atoms.

The solid-state structures of organic salts formed by calix[4]arene dihydroxyphosphonic acid with nucleic bases cations: adeninium, cytosinium, guaninium and uracilium

KAUST Repository

Shkurenko, Aleksander

2018-02-19

Calix[4]arene dihydroxyphosphonic acid has been demonstrated to possess an interesting range of biological properties, including atypical anti-cancer activity. The robustness of calix[4]arene dihydroxyphosphonic acid and its ubiquitous dimeric motif offers perspectives for pre-defined solid state complexation with small molecules. In the current article we describe co-crystals (organic salts) of calix[4]arene dihydroxyphosphonic acid with four nucleic base cations: adeninium, cytosinium, guaninium and uracilium. A number of characteristic interactions between the components in the four co-crystals are pointed out also using the Hirshfeld surface analysis. All the four co-crystals are based on layers of calix[4]arene dimers, alternating with layers of nucleic acid molecules. Two of the reported crystal structures (cytosinium and guaninium) are 1D channel-type structures, while the two others (adeninium and uracilium) represent 2D channel-type structures. In three out of four reported structures, interactions between the cations of nucleic bases are present generating 1D chains of cations. A constant motif is that the nucleic base is present in a type of cavity formed by one aromatic ring and a phosphonic acid moiety.

Chlorodifluoromethane-triggered formation of difluoromethylated arenes catalysed by palladium

Science.gov (United States)

Feng, Zhang; Min, Qiao-Qiao; Fu, Xia-Ping; An, Lun; Zhang, Xingang

2017-09-01

Difluoromethylated aromatic compounds are of increasing importance in pharmaceuticals, agrochemicals and materials. Chlorodifluoromethane (ClCF2H), an inexpensive, abundant and widely used industrial raw material, represents the ideal and most straightforward difluoromethylating reagent, but introduction of the difluoromethyl group (CF2H) from ClCF2H into aromatics has not been reported. Here, we describe a direct palladium-catalysed difluoromethylation method for coupling ClCF2H with arylboronic acids and esters to generate difluoromethylated arenes with high efficiency. The reaction exhibits a remarkably broad substrate scope, including heteroarylboronic acids, and was used for difluoromethylation of a range of pharmaceuticals and biologically active compounds. Preliminary mechanistic studies revealed that a palladium difluorocarbene intermediate is involved in the reaction. Although numerous metal-difluorocarbene complexes have been prepared, the catalytic synthesis of difluoromethylated or difluoromethylenated compounds involving metal-difluorocarbene complexes has not received much attention. This new reaction therefore also opens the door to understand metal-difluorocarbene complex catalysed reactions.

Synthesis and characterization of 14C polyvinylphosphonic acid

International Nuclear Information System (INIS)

Stringer, O.D.; Charig, A.

1989-01-01

Ten mCi of 14 C ethylene was converted to 1.16 mCi of 14 C PVPA by oxidative phosphonation with phosphorus trichloride and molecular oxygen, dehydrohalogenation with triethylamine in ether, polymerization, and hydrolysis. The polymer had a specific activity of 12 uCi/mg and a radiochemical purity over 99%. (Author)

Analytical insight into degradation processes of aminopolyphosphonates as potential factors that induce cyanobacterial blooms.

Science.gov (United States)

Drzyzga, Damian; Lipok, Jacek

2017-11-01

Aminopolyphosphonates (AAPs) are commonly used industrial complexones of metal ions, which upon the action of biotic and abiotic factors undergo a breakdown and release their substructures. Despite the low toxicity of AAPs towards vertebrates, products of their transformations, especially those that contain phosphorus and nitrogen, can affect algal communities. To verify whether such chemical entities are present in water ecosystems, much effort has been made in developing fast, inexpensive, and reliable methods for analyzing phosphonates. However, unfortunately, the methods described thus far require time-consuming sample pretreatment and offer relatively high values of the limit of detection (LOD). The aim of this study was to develop an analytical approach to study the environmental fate of AAPs. Four phosphonic acids, N,N-bis(phosphonomethyl)glycine (GBMP), aminotris(methylenephosphonic) acid (ATMP), hexamethylenediamine-N,N,N',N'-tetrakis(methylphosphonic) acid (HDTMP), and diethylenetriamine penta(methylenephosphonic) acid (DTPMP) were selected and examined in a water matrix. In addition, the susceptibility of these compounds to biotransformations was tested in colonies of five freshwater cyanobacteria-microorganisms responsible for the so-called blooms in the water. Our efforts to track the AAP decomposition were based on derivatization of N-alkyl moieties with p-toluenesulfonyl chloride (tosylation) followed by chromatographic (HPLC-UV) separation of derivatives. This approach allowed us to determine seven products of the breakdown of popular phosphonate chelators, in nanomolar concentrations and in one step. It should be noted that the LOD of four of those products, aminemethylphosphonic acid (AMPA), N-phosphomethyl glycine (NPMG), N-(methyl)aminemethanephosphonic acid (MAMPA), and N-(methyl) glycine (SAR), was set below the concentration of 50 nM. Among those substances, N-(methylamino)methanephosphonic acid (MAMPA) was identified for the first time as

Impurities that cause difficulty in stripping actinides from commercial tetraalkylcarbamoylmethylphosphonates

International Nuclear Information System (INIS)

Bahner, C.T.; Shoun, R.R.; McDowell, W.J.

1977-09-01

Dihexyl[(diethylcarbamoyl)methyl]phosphonate (DHDECMP) in diethylbenzene extracts actinides well from 6 M nitric acid solution, but commercially available DHDECMP contains impurities which interfere with stripping the actinides from the organic extract. DHDECMP purified by molecular distillation does not contain these impurities, but the pot residue contains increased concentrations of them. Heating the purified DHDECMP causes the formation of products which interfere with stripping in the same way, suggesting that high temperatures employed in the manufacture of DHDECMP may produce the offending impurities. These impurities can be separated from the heat-decomposed material or the pot residues by dilution with a large volume of hexanes (causing part of the impurities to separate as a second liquid phase) followed by equilibration of the hexane solution with dilute alkali. After the treatment with hexane and dilute alkali, the DHDECMP is readily recovered and functions well in the actinide extraction process. Dibutyl[(dibutylcarbamoyl)methyl]-phosphonate (DBDBCMP) and di(2-ethylhexyl)[(diethylcarbamoyl)-methyl]phosphonate (DEHDECMP) are purified less effectively by these methods. Similar separation methods using diethylbenzene or CCl 4 as solvent do not remove impurities as completely as the hexane process. Impurities can also be removed from a benzene solution of the DHDECMP pot residue by passing it through a column packed with silica gel or diethylaminoethyl cellulose. These impurities have been separated into fractions for analytical examination by use of various solvents and by column chromatography. Hexyl hydrogen [(diethylcarbamoyl)methyl]-phosphonate has been identified tentatively as a principal objectionable impurity. Dihexyl phosphoric acid and possibly dihexylphosphonate have been identified in other fractions

Effects of increasing doses of samarium-153-ethylenediaminetetramethylene phosphonate on axial and appendicular skeletal growth in juvenile rabbits

International Nuclear Information System (INIS)

Essman, Stephanie C.; Lewis, Michael R.; Fox, Derek B.

2008-01-01

Introduction: Targeted radiotherapy using samarium-153-ethylenediaminetetramethylene phosphonate ( 153 Sm-EDTMP) is currently under investigation for treatment of osteosarcoma. Osteosarcoma often occurs in children, and previous studies on a juvenile rabbit model demonstrated that clinically significant damage to developing physeal cartilage may occur as a result of systemic 153 Sm-EDTMP therapy. The aim of this study was to evaluate the late effects of 153 Sm-EDTMP on skeletal structures during growth to maturity and to determine if there is a dose response of 153 Sm-EDTMP on growth of long bones. Methods: Female 8-week-old New Zealand white rabbits were divided into three treatment groups plus controls. Each rabbit was intravenously administered a predetermined dose of 153 Sm-EDTMP. Multiple bones of each rabbit were radiographed every 2 months until physeal closure, with subsequent measurements made to assess for abbreviated bone growth. Statistical analyses were performed to determine the differences in bone length between groups, with significance set at P 153 Sm-EDTMP. Further investigation regarding the effects of bone-seeking radiopharmaceuticals on bone growth and physeal cartilage is warranted

Subnanomolar antisense activity of phosphonate-peptide nucleic acid (PNA) conjugates delivered by cationic lipids to HeLa cells

DEFF Research Database (Denmark)

Shiraishi, Takehiko; Hamzavi, Ramin; Nielsen, Peter E

2008-01-01

oligomer. This modification of the PNA does not interfere with the nucleic acid target binding affinity based on thermal stability of the PNA/RNA duplexes. When delivered to cultured HeLa pLuc705 cells by Lipofectamine, the PNAs showed dose-dependent nuclear antisense activity in the nanomolar range...

Synthesis and X-ray structures of dilithium complexes of the phosphonate anions [PhP(E)(N(t)Bu)(2)](2-) (E = O, S, Se, Te) and dimethylaluminum derivatives of [PhP(E)(N(t)Bu)(NH(t)Bu)](-) (E = S, Se).

Science.gov (United States)

Briand, Glen G; Chivers, Tristram; Krahn, Mark; Parvez, Masood

2002-12-16

The dilithium salts of the phosphonate dianions [PhP(E)(N(t)Bu)(2)](2-) (E = O, S, Se) are generated by the lithiation of [PhP(E)(NH(t)Bu)(2)] with n-butyllithium. The formation of the corresponding telluride (E = Te) is achieved by oxidation of [Li(2)[PhP(N(t)Bu)(2)

The Effects of Anchor Groups on (1) TiO2-Catalyzed Photooxidation and (2) Linker-Assisted Assembly on TiO2

Science.gov (United States)

Anderson, Ian Mark

Quantum dot-sensitized solar cells (QDSSCs) are a popular target for research due to their potential for highly efficient, easily tuned absorption. Typically, light is absorbed by quantum dots attached to a semiconductor substrate, such as TiO2, via bifunctional linker molecules. This research aims to create a patterned monolayer of linker molecules on a TiO2 film, which would in turn allow the attachment of a patterned layer of quantum dots. One method for the creation of a patterned monolayer is the functionalization of a TiO2 film with a linker molecule, followed by illumination with a laser at 355 nm. This initiates a TiO 2-catalyzed oxidation reaction, causing loss of surface coverage. A second linker molecule can then be adsorbed onto the TiO2 surface in the illuminated area. Towards that end, the behaviors of carboxylic and phosphonic acids adsorbed on TiO2 have been studied. TiO2 films were functionalized by immersion in solutions a single adsorbate and surface coverage was determined by IR spectroscopy. It is shown that phosphonic acids attain higher surface coverage than carboxylic acids, and will displace them from TiO2 when in a polar solvent. Alkyl chain lengths, which can influence stabilities of monolayers, are shown not to have an effect on this relationship. Equilibrium binding data for the adsorption of n-hexadecanoic acid to TiO2 from a THF solution are presented. It is shown that solvent polarity can affect monolayer stability; carboxylates and phosphonates undergo more desorption into polar solvents than nonpolar. Through illumination, it was possible to remove nearly all adsorbed linkers from TiO2. However, the illuminated areas were found not to be receptive to attachment by a second adsorbate. A possible reason for this behavior is presented. I also report on the synthesis and characterization of a straight-chain, thiol-terminated phosphonic acid. Initial experiments involving monolayer formation and quantum dot attachment are presented

Nafion/silane nanocomposite membranes for high temperature polymer electrolyte membrane fuel cell.

Science.gov (United States)

Ghi, Lee Jin; Park, Na Ri; Kim, Moon Sung; Rhee, Hee Woo

2011-07-01

The polymer electrolyte membrane fuel cell (PEMFC) has been studied actively for both potable and stationary applications because it can offer high power density and be used only hydrogen and oxygen as environment-friendly fuels. Nafion which is widely used has mechanical and chemical stabilities as well as high conductivity. However, there is a drawback that it can be useless at high temperatures (> or = 90 degrees C) because proton conducting mechanism cannot work above 100 degrees C due to dehydration of membrane. Therefore, PEMFC should be operated for long-term at high temperatures continuously. In this study, we developed nanocomposite membrane using stable properties of Nafion and phosphonic acid groups which made proton conducting mechanism without water. 3-Aminopropyl triethoxysilane (APTES) was used to replace sulfonic acid groups of Nafion and then its aminopropyl group was chemically modified to phosphonic acid groups. The nanocomposite membrane showed very high conductivity (approximately 0.02 S/cm at 110 degrees C, <30% RH).

A novel inorganic-organic compound: Synthesis and structural characterization of tin(II) phenylbis(phosphonate), Sn2(PO3C6H4PO3)

International Nuclear Information System (INIS)

Subbiah, Ayyappan; Bhuvanesh, Nattamai; Clearfield, Abraham

2005-01-01

A novel tin(II) phenylbis(phosphonate) compound has been synthesized hydrothermally and its structure has been determined by single crystal X-ray diffraction. The structure is monoclinic, space group P2 1 /c (no. 14), a=4.8094(4), b=16.2871(13), c=6.9107(6)A; β=106.292(6) o , V=519.59(7)A 3 , Z=2. The three-dimensional structure consists of 3-coordinated tin and 4-coordinated phosphorus double layers separated (pillared) by phenyl rings. These phenyl rings are placed 4.8A apart along the a-axis in the structure resulting in lower surface area (∼14m 2 /g). The porosity has been increased by replacing phenyl groups by methyl groups (∼31m 2 /g)

PEG-bis phosphonic acid based ionic supramolecular structures

DEFF Research Database (Denmark)

Gonzalez, Lidia; Skov, Anne Ladegaard; Hvilsted, Søren

2014-01-01

. The resulting ionic assemblies are very comprehensively characterized by ATR-FTIR, proton, and carbon-13 NMR spectroscopy that unequivocally demonstrate the ionic network formation through ammonium phophonates. The resulting salt and ionic networks are additionally analyzed by differential scanning calorimetry...... and thermogravimetric analysis. The conclusion is that mixing the virgin components at room temperature spontaneously form either a salt or ionic supramolecular networks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

Structure-Activity Relationship Study of Ionotropic Glutamate Receptor Antagonist (2S,3R)-3-(3-Carboxyphenyl)pyrrolidine-2-carboxylic Acid

DEFF Research Database (Denmark)

Krogsgaard-Larsen, Niels; Storgaard, Morten; Møller, Charlotte

2015-01-01

Herein we describe the first structure-activity relationship study of the broad-range iGluR antagonist (2S,3R)-3-(3-carboxyphenyl)pyrrolidine-2-carboxylic acid (1) by exploring the pharmacological effect of substituents in the 4, 4', or 5' positions and the bioisosteric substitution of the distal...... carboxylic acid for a phosphonic acid moiety. Of particular interest is a hydroxyl group in the 4' position 2a which induced a preference in binding affinity for homomeric GluK3 over GluK1 (Ki = 0.87 and 4.8 μM, respectively). Two X-ray structures of ligand binding domains were obtained: 2e in GluA2-LBD...... and 2f in GluK1-LBD, both at 1.9 Å resolution. Compound 2e induces a D1-D2 domain opening in GluA2-LBD of 17.3-18.8° and 2f a domain opening in GluK1-LBD of 17.0-17.5° relative to the structures with glutamate. The pyrrolidine-2-carboxylate moiety of 2e and 2f shows a similar binding mode as kainate...

Corrosion Inhibition by Sodium Gluconate-Zn2+-DTPMP System

Directory of Open Access Journals (Sweden)

P. Manjula

2009-01-01

Full Text Available The inhibition efficiency of a phosphonic acid, Diethylene Triamine Pentamethylene Phosphonic acid (DTPMP in controlling corrosion of carbon steel immersed in an aqueous solution containing 60 ppm of Cl- has been evaluated by weight loss method in the absence and presence of Zn2+. The formulation consisting of DTPMP and Zn2+ has excellent inhibition efficiency (IE. A synergistic effect is noticed between Zn2+ and DTPMP. Addition of sodium gluconate (SG enhances the IE of Zn2+ and DTPMP system. The DTPMP-Zn2+-SG system function as a mixed inhibitor as revealed by polarization study. AC impedance spectrum, optical and atomic force micrographs reveal the formation of a protective film on the metal surface. FTIR spectra reveal that the protective film consists of Fe2+-DTPMP complex, Fe2+-SG complex and Zn(OH2.

Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

Energy Technology Data Exchange (ETDEWEB)

Arnold, John [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2014-12-13

Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Our first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.

Surface modification of calcium hydroxyapatite by grafting of etidronic acid

Science.gov (United States)

Othmani, Masseoud; Aissa, Abdallah; Bac, Christophe Goze; Rachdi, Férid; Debbabi, Mongi

2013-06-01

The surface of prepared calcium hydroxyapatite CaHAp has been modified by grafting the etidronic acid (ETD). For that purpose, CaHAp powders have been suspended in an aqueous etidronate solution with different concentrations. The obtained composites CaHAp-(ETD) were characterized by TEM and AFM techniques to determinate morphological properties and were also characterized by XRD, IR, NMR and chemical and thermal analysis to determinate their physico-chemical properties and essentially the nature of the interaction between the inorganic support and the grafted organic ETD. After reaction with ETD, XRD powder analysis shows that the apatitic structure remains unchanged with slight affectation of its crystallinity. The presence of etidronate fragment bounded to hydroxyapatite was confirmed by IR and solid-state NMR spectroscopy. TEM and AFM techniques indicate that the presence of etidronate changes the morphology of the particles. Basing on the obtained results, a reactional mechanism was proposed to explain the formation of covalent Casbnd Osbnd Porg bonds on the hydroxyapatite surface between the superficial hydroxyl groups (tbnd Casbnd OH) of the apatite and phosphonate group (Psbnd OH) of etidronate.

SEPARATION OF EUROPIUM FROM OTHER LANTHANIDE RAE EARTHS BY SOLVENT EXTRACTION

Science.gov (United States)

Peppard, D.F.; Horwitz, E.P.; Mason, G.W.

1963-02-12

This patent deals with a process of separating europium from other lanthanides present in aqueous hydrochloric or sulfuric acid solutions. The europium is selectively reduced to the divalent state with a divalent chromium salt formed in situ from chromium(III) salt plus zinc amalgam. The other trivalent lanthanides are then extracted away from the divalent europium with a nitrogen-flushed phosphoric acid ester or a phosphonic acid ester. (AEC)

Novel alpha-zirconium phosphonates for the reinforcement of ductile thermoplastics

Science.gov (United States)

Furman, Benjamin R.

2007-12-01

Ductile thermoplastics are useful additives for providing fracture toughness to brittle thermosetting polymers; however, this toughening is usually accompanied by a significant decrease in elastic modulus. Therefore, alpha-zirconium phosphonates (ZrP) were developed and investigated as reinforcing nano-scale fillers that increase the yield strength and elastic modulus of a polyester thermoplastic without causing a reduction in its ductility. ZrP materials are synthetic layered compounds that are imbued with targeted organic surface functionalities and whose structural development can be carefully controlled in the laboratory. Ether-terminal alkyl ZrP materials were designed and synthesized, using a conventional ZrF62--mediated preparation, with the intent of developing strong dipole-dipole interactions between the layer surfaces and polyester macromolecules. Additionally, a general method for using lamellar lyotropic liquid crystals (LLC's) as supramolecular templates for alkyl ZrP was evaluated, whose products showed promising similarity to the conventionally prepared materials. The LLC-forming characteristics of several organophosphonate preparations were determined, showing improved mesophase stability with mixed amphiphiles and preparation with R4N + counterions. A mixed-surface octyl/methoxyundecyl ZrP was produced and combined with polycaprolactone (PCL) and polymethylmethacrylate (PMMA) in concentrations up to 50% (w/w). The mechanical properties of the ZrP/PCL nanocomposite were evaluated by tensile, flexural, and dynamic mechanical testing methods. Nanocomposites containing 5% (w/w) ZrP showed significant increases in tensile yield stress and elastic modulus without suffering any loss of ductility versus the unfilled polymer. Layer delamination from the ZrP tactoids was minimal and did not occur through an intercalative mechanism. Higher ZrP loadings resulted in the agglomeration of tactoids, leading to defect structures and loss of strength and ductility

The sources, fate, and toxicity of chemical warfare agent degradation products.

Science.gov (United States)

Munro, N B; Talmage, S S; Griffin, G D; Waters, L C; Watson, A P; King, J F; Hauschild, V

1999-01-01

We include in this review an assessment of the formation, environmental fate, and mammalian and ecotoxicity of CW agent degradation products relevant to environmental and occupational health. These parent CW agents include several vesicants: sulfur mustards [undistilled sulfur mustard (H), sulfur mustard (HD), and an HD/agent T mixture (HT)]; nitrogen mustards [ethylbis(2-chloroethyl)amine (HN1), methylbis(2-chloroethyl)amine (HN2), tris(2-chloroethyl)amine (HN3)], and Lewisite; four nerve agents (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX), tabun (GA), sarin (GB), and soman (GD)); and the blood agent cyanogen chloride. The degradation processes considered here include hydrolysis, microbial degradation, oxidation, and photolysis. We also briefly address decontamination but not combustion processes. Because CW agents are generally not considered very persistent, certain degradation products of significant persistence, even those that are not particularly toxic, may indicate previous CW agent presence or that degradation has occurred. Of those products for which there are data on both environmental fate and toxicity, only a few are both environmentally persistent and highly toxic. Major degradation products estimated to be of significant persistence (weeks to years) include thiodiglycol for HD; Lewisite oxide for Lewisite; and ethyl methyl phosphonic acid, methyl phosphonic acid, and possibly S-(2-diisopropylaminoethyl) methylphosphonothioic acid (EA 2192) for VX. Methyl phosphonic acid is also the ultimate hydrolysis product of both GB and GD. The GB product, isopropyl methylphosphonic acid, and a closely related contaminant of GB, diisopropyl methylphosphonate, are also persistent. Of all of these compounds, only Lewisite oxide and EA 2192 possess high mammalian toxicity. Unlike other CW agents, sulfur mustard agents (e.g., HD) are somewhat persistent; therefore, sites or conditions involving potential HD contamination should include an

Biodiesel production from esterification of free fatty acid over PA/NaY solid catalyst

International Nuclear Information System (INIS)

Liu, Wei; Yin, Ping; Zhang, Jiang; Tang, Qinghua; Qu, Rongjun

2014-01-01

Highlights: • Biodiesel production from esterification of oleic acid was catalyzed by PA/NaY. • The influences of the process operating parameters were studied. • RSM was employed to optimize the experimental conditions. • The kinetic equation of the esterification reaction was investigated. - Abstract: Because of the incitements from increasing petroleum prices, diminishing petroleum reserves and the environmental consequences of exhaust gases from petroleum fueled engines, biodiesel has been used as a substitute of the regular diesel in recent years. In this paper, biodiesel production from the esterification of the free fatty oil oleic acid with ethanol catalyzed by PA/NaY (PA = organic phosphonic acid) was investigated, and the effect of reaction conditions such as PA loading, catalyst amount, molar ratio of alcohol to acid, reaction temperature and reaction time on the esterification reaction was examined. The process optimization using response surface methodology (RSM) was performed and the interactions between the operational variables were elucidated. The optimum values for maximum conversion ratio of oleic acid could be obtained by using a Box–Behnken center-united design with a minimum of experimental work. The oleic acid conversion reached 79.51 ± 0.68% with the molar ratio of alcohol to oleic acid being 7:1 and 1.7 g PA/NaY catalyst (20 ml of PA loading) at 105 °C for 7 h. Moreover, a kinetic model for the esterification catalyzed by PA/NaY catalyst was established. By fitting the kinetic model with the experimental results, the reaction order n = 2, activation energy of the positive reaction Ea + = 43.41 kJ/mol and that of the reverse reaction Ea − = 59.74 kJ/mol were obtained

Tribology and stability of organic monolayers on CrN: a comparison among silane, phosphonate, alkene, and alkyne chemistries.

Science.gov (United States)

Pujari, Sidharam P; Li, Yan; Regeling, Remco; Zuilhof, Han

2013-08-20

The fabrication of chemically and mechanically stable monolayers on the surfaces of various inorganic hard materials is crucial to the development of biomedical/electronic devices. In this Article, monolayers based on the reactivity of silane, phosphonate, 1-alkene, and 1-alkyne moieties were obtained on the hydroxyl-terminated chromium nitride surface. Their chemical stability and tribology were systematically investigated. The chemical stability of the modified CrN surfaces was tested in aqueous media at 60 °C at pH 3, 7, and 11 and monitored by static water contact angle measurements, X-ray photoelectron spectroscopy (XPS), ellipsometry, and Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). The tribological properties of the resulting organic monolayers with different end groups (fluorinated or nonfluorinated) were studied using atomic force microscopy (AFM). It was found that the fluorinated monolayers exhibit a dramatic reduction of adhesion and friction force as well as excellent wear resistance compared to those of nonfluorinated coatings and bare CrN substrates. The combination of remarkable chemical stability and superior tribological properties makes these fluorinated monolayers promising candidates for the development of robust high-performance devices.

Nafion/ZrSPP composite membrane for high temperature operation of PEMFCs

International Nuclear Information System (INIS)

Kim, Young-Taek; Song, Min-Kyu; Kim, Ki-Hyun; Park, Seung-Bae; Min, Sung-Kyu; Rhee, Hee-Woo

2004-01-01

Nafion/zirconium sulphophenyl phosphate (ZrSPP) composite membranes were prepared to maintain proton conductivity at elevated temperatures. ZrSPP was precipitated by the reaction of Zr 4+ ion and m-sulphophenyl phosphonic (SPP) acid with a stoichiometric ratio P/Zr = 2. The synthesis of ZrSPP was confirmed by phosphonate (P-O) stretching band, assigned at 900-1300 cm -1 in FTIR spectra. The sharp diffraction pattern at 2θ = 5 deg. indicated crystalline α-layered structure of ZrSPP. The proton conductivity of Nafion/ZrSPP (12.5 wt.%) composite membrane reached ca. 0.07 S/cm at 140 deg. C without extra humidification

Organophosphonic acid as precursor to prepare LiFePO4/carbon nanocomposites for high-power lithium ion batteries

International Nuclear Information System (INIS)

Chen, Ming; Shao, Leng-Leng; Yang, Hua-Bin; Zhao, Qian-Yong; Yuan, Zhong-Yong

2015-01-01

Graphical abstract: LiFePO4/C nanocomposites were prepared by a quasi-sol–gel method with the use of organophosphonic acid, exhibiting improved electrochemical performance with excellent cycle stability. Display Omitted -- Highlights: •Amino tris(methylene phosphonic acid) is served as a novel precursor for LiFePO 4 /C. •Nano-sized and high-purity LiFePO 4 /C composites are obtained by a quasi-sol–gel route. •Core-shell structured LiFePO 4 /C nanocomposites are fabricated by further introducing sucrose. •Superior electrochemical performance is observed in the organophosphorus-synthesized LiFePO 4 /C. -- Abstract: Amino tris(methylene phosphonic acid) (ATMP) is selected as phosphorus and carbon co-source for the synthesis of uniformly nano-sized LiFePO 4 /C by a quasi-sol–gel method. This strategy using ATMP instead of conventional NH 4 H 2 PO 4 supplies two advantages: firstly, ATMP in situ chelates Li + onto its framework and subsequently binds with FeC 2 O 4 in aqueous solution, forming a molecule-scale homogeneous precursor which can obviously improve the purity of LiFePO 4 . Secondly, the organic carbon contained in ATMP can form uniformly distributed conductive carbon networks among LiFePO 4 particles after calcination, which improves the electrical conductivity. The resultant LiFePO 4 /C with 1.1 wt.% carbon achieves a higher discharge capacity than those of LiFePO 4 and LiFePO 4 /C prepared with inorganic NH 4 H 2 PO 4 . Moreover, core-shell structured LiFePO 4 /C nanocomposites are also fabricated by further introducing sucrose into the synthesis system. The high-quality carbon shell effectively hinders the LiFePO 4 particle growth and aggregation under high-temperature treatment, which further enhances the electrical conductivity and lithium-ion diffusion, resulting in the improved electrochemical performance with excellent cycle stability (the optimum discharge capacity of 158.6 mAh g −1 at 0.1 C and 138.4 mAh g −1 at 2 C). The high

Calixarene methylene bisphosphonic acids as promising effectors of biochemical processes

Directory of Open Access Journals (Sweden)

S. V. Komisarenko

2013-12-01

rim have been studied with respect to their effects on fibrin polymerization. The most potent inhibitor proved to be calix[4]arene tetrakis-methylene-bis-phosphonic acid (C-192, in which case the maximum rate of fibrin polymerization in the fibrinogen + thrombin reaction decreased by 50% at concentrations of 0.52·10-6 M (IC50. At this concentration, the molar ratio of the compound to fibrinogen was 1.7 : 1. For the case of desAB fibrin polymerization, the IC50 was 1.26·10-6 M at a molar ratio of C-192 to fibrin monomer of 4 : 1. Dipropoxycalix[4]-arene bis-methylene-bis-phosphonic acid (C-98 inhibited fibrin desAB polymerization with an IC50 = 1.31·10-4 M. We hypothesized that C-192 blocks fibrin formation by combining with polymerization site ‘A’ (Aa17–19, which ordinarily initiates protofibril formation in a ‘knob-hole’ manner. This suggestion was confirmed by an HPLC assay, which showed a host–guest inclusion complex of C-192 with the synthetic peptide Gly-Pro-Arg-Pro, an analogue of site ‘A’. Further confirmation that the inhibitor was acting at the initial step of the reaction was obtained by electron microscopy, with no evidence of protofibril formation being evident. Calixarene C-192 also doubled both the prothrombin time and the activated partial thromboplastin time in normal human blood plasma at concentrations of 7.13·10-5 and 1.10·10-5 M, respectively. These experiments demonstrate that C-192 is a specific inhibitor of fibrin polymerization and blood coagulation and can be used for the design of a new class of antithrombotic agents.

Photometric estimation of plutonium in product solutions and acid waste solutions using flow injection analysis technique

International Nuclear Information System (INIS)

Dhas, A.J.A.; Dharmapurikar, G.R.; Kumaraguru, K.; Vijayan, K.; Kapoor, S.C.; Ramanujam, A.

1995-01-01

Flow injection analysis technique is employed for the measurement of plutonium concentrations in product nitrate solutions by measuring the absorbance of Pu(III) at 565 nm and of Pu(IV) at 470 nm, using a Metrohm 662 photometer, with a pyrex glass tube of 2 nm (ID) inserted in the light path of the detector serving as a flow cell. The photometer detector never comes in contact with radioactive solution. In the case of acid waste solutions Pu is first purified by extraction chromatography with 2-ethyl hexyl hydrogen 2 ethyl hexyl phosphonate (KSM 17)- chromosorb and the Pu in the eluate in complexed with Arsenazo III followed by the measured of absorbance at 665 nm. Absorbance of reference solutions in the desired concentration ranges are measured to calibrate the system. The results obtained agree with the reference values within ±2.0%. (author). 3 refs., 1 tab

Preparations and properties of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials.

Science.gov (United States)

Watanabe, Shoji

2008-01-01

This short review describes various types of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials. It is concerned with synthetic additives classified according to their functional groups; silicone compounds, carboxylic acids and dibasic acids, esters, Diels-Alder adducts, various polymers, nitrogen compounds, phosphoric esters, phosphonic acids, and others. Testing methods for water-soluble metal working fluids for aluminum alloy materials are described for a practical application in a laboratory.

Zn(3)(4-OOCC(6)H(4)PO(3))(2): A polar metal phosphonate with pillared layered structure showing SHG-activity and large dielectric anisotropy.

Science.gov (United States)

Li, Jin-Tang; Cao, Deng-Ke; Akutagawa, Tomoyuki; Zheng, Li-Min

2010-10-07

A new metal phosphonate Zn(3)(4-OOCC(6)H(4)PO(3))(2) (1) is reported which crystallizes in orthorhombic space group Pca2(1). It shows a pillared layered structure in which the {ZnO(4)}, {ZnO(5)} and {PO(3)C} polyhedra are connected through corner- or edge-sharing to form an inorganic layer in the ab plane which contains 4- and 5-member rings. These layers are pillared by the uni-oriented 4-carboxylatephenylphosphonate ligands, thus leading to a polar 3D architecture. The dielectric anisotropy measurements of a single crystal of 1 reveal that dielectric constant along the inter-layer is larger than that along the intra-layer with a ratio of about 2.3. Second harmonic generation (SHG) activity is observed.

Bis(2-ethylhexyl)-N,N-diethylcarbamoylmethyl phosphonate as a synergist in the extraction of trivalent lanthanides by 1-phenyl-3-methyl-4-trifluoroacetyl-pyrazolone-5

International Nuclear Information System (INIS)

Luxmi Varma, R.; Sujatha, S.; Reddy, M.L.P.; Prasada Rao, T.; Iyer, C.S.P.; Damodaran, A.D.

1996-01-01

Synergism in the extraction of trivalent lanthanides such as Nd. Eu and Lu has been investigated using mixtures of 1-phenyl-3-methyl-4-trifluoroacetyl-pyrazolone-5 (HPMTFP) and bis(2-ethylhexyl)-N,N-diethylcarbamoylmethyl phosphonate (CMP) in chloroform. Lanthanides are found to be extracted from 0.01 mol/dm 3 chloroacetate medium with HPMTFP as Ln(PMTFP) 3 or Ln(PMTFP) 3 . CMP in the absence or presence of CMP, respectively. The equilibrium constants of these synergistic species do not increase monotonically with atomic number but have a maximum at Eu. The addition of a synergist, CMP to the metal chelate system not only enhances the extraction efficiency but also improves the selectivities among these trivalent lanthanides. The IR results indicate that CMP acts as a bidentate ligand in these mixed-ligand systems. (orig.)

Functionalisation of Ti6Al4V components fabricated using selective laser melting with a bioactive compound

Energy Technology Data Exchange (ETDEWEB)

Vaithilingam, Jayasheelan [Additive Manufacturing and 3D Printing Research Group, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Kilsby, Samuel [Department of Chemistry, Loughborough University, Loughborough LE11 3TU (United Kingdom); Goodridge, Ruth D., E-mail: Ruth.Goodridge@nottingham.ac.uk [Additive Manufacturing and 3D Printing Research Group, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Christie, Steven D.R. [Department of Chemistry, Loughborough University, Loughborough LE11 3TU (United Kingdom); Edmondson, Steve [School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Hague, Richard J.M. [Additive Manufacturing and 3D Printing Research Group, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom)

2015-01-01

Surface modification of an implant with a biomolecule is used to improve its biocompatibility and to reduce post-implant complications. In this study, a novel approach has been used to functionalise phosphonic acid monolayers with a drug. Ti6Al4V components fabricated using selective laser melting (SLM) were functionalised with Paracetamol (a pharmaceutically relevant biomolecule) using phosphonic acid based self-assembled monolayers (SAMs). The attachment, stability of the monolayers on the SLM fabricated surface and functionalisation of SAMs with Paracetamol were studied using X-ray photoelectron spectroscopy (XPS) and surface wettability measurements. The obtained results confirmed that SAMs were stable on the Ti6Al4V surface for over four weeks and then began to desorb from the surface. The reaction used to functionalise the phosphonic acid monolayers with Paracetamol was noted to be successful. Thus, the proposed method has the potential to immobilise drugs/proteins to SAM coated surfaces and improve their biocompatibility and reduce post-implant complications. - Graphical abstract: A significant change in the contact angle confirming the immobilisation of Paracetamol. (a) Before self-assembled monolayer (SAM) attachment, (b) after SAM attachment and (c) after the immobilisation of Paracetamol to the SAMs. - Highlights: • Ti6Al4V parts were fabricated using selective laser melting (SLM). • Monolayers used to modify the SLM surface were stable for over 28 days (in-vitro). • Surface roughness did not have a significant impact on the monolayer stability. • Paracetamol was successfully immobilised to the adsorbed monolayers. • Caution required before selecting Paracetamol as a model drug.

Functionalisation of Ti6Al4V components fabricated using selective laser melting with a bioactive compound

International Nuclear Information System (INIS)

Vaithilingam, Jayasheelan; Kilsby, Samuel; Goodridge, Ruth D.; Christie, Steven D.R.; Edmondson, Steve; Hague, Richard J.M.

2015-01-01

Surface modification of an implant with a biomolecule is used to improve its biocompatibility and to reduce post-implant complications. In this study, a novel approach has been used to functionalise phosphonic acid monolayers with a drug. Ti6Al4V components fabricated using selective laser melting (SLM) were functionalised with Paracetamol (a pharmaceutically relevant biomolecule) using phosphonic acid based self-assembled monolayers (SAMs). The attachment, stability of the monolayers on the SLM fabricated surface and functionalisation of SAMs with Paracetamol were studied using X-ray photoelectron spectroscopy (XPS) and surface wettability measurements. The obtained results confirmed that SAMs were stable on the Ti6Al4V surface for over four weeks and then began to desorb from the surface. The reaction used to functionalise the phosphonic acid monolayers with Paracetamol was noted to be successful. Thus, the proposed method has the potential to immobilise drugs/proteins to SAM coated surfaces and improve their biocompatibility and reduce post-implant complications. - Graphical abstract: A significant change in the contact angle confirming the immobilisation of Paracetamol. (a) Before self-assembled monolayer (SAM) attachment, (b) after SAM attachment and (c) after the immobilisation of Paracetamol to the SAMs. - Highlights: • Ti6Al4V parts were fabricated using selective laser melting (SLM). • Monolayers used to modify the SLM surface were stable for over 28 days (in-vitro). • Surface roughness did not have a significant impact on the monolayer stability. • Paracetamol was successfully immobilised to the adsorbed monolayers. • Caution required before selecting Paracetamol as a model drug

Metal chelates of phosphonate-containing ligands-III Analytical applications of N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid.

Science.gov (United States)

Zaki, M T; Rizkalla, E N

1980-05-01

N,N*,N',N'-Ethylenediaminetetra(methylenephosphonic) acid is used as a titrant for the direct determination of Cu, Co and Ni, with murexide as indicator. Indirect titrimetric procedures are suggested for the determination of silver, mercury, zinc and cyanide and both direct and indirect methods are applied for the analysis of binary mixtures of silver (or mercury) and copper (cobalt or nickel). The stoichiometry of the reaction, interferences of some metal ions and the pH effects on the complexation reactions are discussed. The values of the equilibrium constants of the protonated CuH(n)L (n = 1, 2, 3 and 4) as well as the unprotonated CuL chelates have been measured.

Inhibitors of the alpha-ketoglutarate dehydrogenase complex alter [1-13C]glucose and [U-13C]glutamate metabolism in cerebellar granule neurons.

Science.gov (United States)

Santos, Sónia Sá; Gibson, Gary E; Cooper, Arthur J L; Denton, Travis T; Thompson, Charles M; Bunik, Victoria I; Alves, Paula M; Sonnewald, Ursula

2006-02-15

Diminished activity of the alpha-ketoglutarate dehydrogenase complex (KGDHC), an important component of the tricarboxylic acid (TCA) cycle, occurs in several neurological diseases. The effect of specific KGDHC inhibitors [phosphonoethyl ester of succinyl phosphonate (PESP) and the carboxy ethyl ester of succinyl phosphonate (CESP)] on [1-13C]glucose and [U-13C]glutamate metabolism in intact cerebellar granule neurons was investigated. Both inhibitors decreased formation of [4-13C]glutamate from [1-13C]glucose, a reduction in label in glutamate derived from [1-13C]glucose/[U-13C]glutamate through a second turn of the TCA cycle and a decline in the amounts of gamma-aminobutyric acid (GABA), aspartate, and alanine. PESP decreased formation of [U-13C]aspartate and total glutathione, whereas CESP decreased concentrations of valine and leucine. The findings are consistent with decreased KGDHC activity; increased alpha-ketoglutarate formation; increased transamination of alpha-ketoglutarate with valine, leucine, and GABA; and new equilibrium position of the aspartate aminotransferase reaction. Overall, the findings also suggest that some carbon derived from alpha-ketoglutarate may bypass the block in the TCA cycle at KGDHC by means of the GABA shunt and/or conversion of valine to succinate. The results suggest the potential of succinyl phosphonate esters for modeling the biochemical and pathophysiological consequences of reduced KGDHC activity in brain diseases.

The Hydrolytic Stability and Degradation Mechanism of a Hierarchically Porous Metal Alkylphosphonate Framework

Directory of Open Access Journals (Sweden)

Kai Lv

2018-03-01

Full Text Available To aid the design of a hierarchically porous unconventional metal-phosphonate framework (HP-UMPF for practical radioanalytical separation, a systematic investigation of the hydrolytic stability of bulk phase against acidic corrosion has been carried out for an archetypical HP-UMPF. Bulk dissolution results suggest that aqueous acidity has a more paramount effect on incongruent leaching than the temperature, and the kinetic stability reaches equilibrium by way of an accumulation of a partial leached species on the corrosion conduits. A variation of particle morphology, hierarchical porosity and backbone composition upon corrosion reveals that they are hydrolytically resilient without suffering any great degradation of porous texture, although large aggregates crack into sporadic fractures while the nucleophilic attack of inorganic layers cause the leaching of tin and phosphorus. The remaining selectivity of these HP-UMPFs is dictated by a balance between the elimination of free phosphonate and the exposure of confined phosphonates, thus allowing a real-time tailor of radionuclide sequestration. Moreover, a plausible degradation mechanism has been proposed for the triple progressive dissolution of three-level hierarchical porous structures to elucidate resultant reactivity. These HP-UMPFs are compared with benchmark metal-organic frameworks (MOFs to obtain a rough grading of hydrolytic stability and two feasible approaches are suggested for enhancing their hydrolytic stability that are intended for real-life separation protocols.

Pain therapy with Samario 153-EDTM in prostate cancer. Pilot experience in Paraguay

International Nuclear Information System (INIS)

Jara Yorg, Jorge

2001-07-01

To relieve the skeletal pain in metastasis disseminated in bones, numerous radiotracers have been used without achieving important clinical acceptance. The SAMARIUM 153 EDT (Etilendiaminetrametilen acid phosphonic) is a radiopharmaceutic that is chemically and biologically stable and preferably concentrates on the skeletal metastasis [es

N-Type self-assembled monolayer field-effect transistors for flexible organic electronics

NARCIS (Netherlands)

Ringk, A.; Roelofs, Christian; Smits, E.C.P.; van der Marel, C.; Salzmann, I.; Neuhold, A.; Gelinck, G.H.; Resel, R.; de Leeuw, D.M.; Strohriegl, P.

Within this work we present n-type self-assembled monolayer field-effect transistors (SAMFETs) based on a novel perylene bisimide. The molecule spontaneously forms a covalently fixed monolayer on top of an aluminium oxide dielectric via a phosphonic acid anchor group. Detailed studies revealed an

Designer HF-Based Fluorination Reagent: Highly Regioselective Synthesis of Fluoroalkenes and gem-Difluoromethylene Compounds from Alkynes

Science.gov (United States)

2015-01-01

Hydrogen fluoride (HF) and selected nonbasic and weakly coordinating (toward cationic metal) hydrogen-bond acceptors (e.g., DMPU) can form stable complexes through hydrogen bonding. The DMPU/HF complex is a new nucleophilic fluorination reagent that has high acidity and is compatible with cationic metal catalysts. The gold-catalyzed mono- and dihydrofluorination of alkynes using the DMPU/HF complex yields synthetically important fluoroalkenes and gem-difluoromethlylene compounds regioselectively. PMID:25260170

Pyrrolidine nucleotide analogs with a tunable conformation

Czech Academy of Sciences Publication Activity Database

Poštová Slavětínská, Lenka; Rejman, Dominik; Pohl, Radek

2014-01-01

Roč. 10, Aug 22 (2014), s. 1967-1980 ISSN 1860-5397 R&D Projects: GA ČR GA13-24880S Institutional support: RVO:61388963 Keywords : conformation * NMR * nucleic acids * nucleotide analog * phosphonic acid * pseudorotation * pyrrolidine Subject RIV: CC - Organic Chemistry Impact factor: 2.762, year: 2014 http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-10-205

Improving the Performances of Poly(vinylphosphonic acid) by Compositing or Copolymerization with Poly(4-(α-methyl)vinyl-1H-1,2,3-triazole)

International Nuclear Information System (INIS)

Han, Shuaiyuan; Yue, Baohua; Yan, Liuming

2014-01-01

Graphical abstract: - Highlights: • Poly(4-(α-methyl)vinyl-1H-1,2,3-triazole) is synthesized • PVPA/PMVTri polymeric composite proton conducting membranes are prepared • The proton conductivity of PVPA is improved by compositing with PMVTri • The water resistance of PVPA is improved by compositing with PMVTri • The oxidative stability is greatly improved - Abstract: The poly(vinylphosphonic acid) (PVPA), poly(4-(α-methyl)vinyl-1H-1,2,3-triazole) (PMVTri), and poly(VPA-co-MVTri) were synthesized, and proton exchange membranes were prepared based on the acid-base polymeric composite of PVPA and PMVTri, and acid-base amphoteric copolymer of poly(VPA-co-MVTri). The overall performances of PVPA, proton conductivity, thermal and oxidative stability, and water resistance, are greatly improved by compositing of PMVTri or copolymerization with 4-(α-methyl)vinyl-1H-1,2,3-triazole (MVTri). About four or eight folds improvement in maximum proton conductivity was observed in the polymeric composite of PVPA/PMVTri or acid-base amphoteric copolymer poly(VPA-co-MVTri) because of the redistribution of ions in the heterostructures of PVPA and PMVTri, respectively, compared with the pristine PVPA. At the same time, the oxidative stability and the water resistance of PVPA were also greatly improved attributing to the absent of α-H in the main chain of PMVTri and the acid-base interaction between the phosphonic acid groups and the triazolyl groups, respectively

BaTiO{sub 3}–P(VDF-HFP) nanocomposite dielectrics—Influence of surface modification and dispersion additives

Energy Technology Data Exchange (ETDEWEB)

Ehrhardt, Claudia; Fettkenhauer, Christian [Institute of Chemistry, Martin-Luther-University Halle-Wittenberg, Kurt-Mothes-Straße 2, D-06120 Halle/Saale (Germany); Glenneberg, Jens [Interdisciplinary Centre of Materials Science, Martin-Luther-University Halle-Wittenberg, Heinrich-Damerow-Straße 4, D-06120 Halle/Saale (Germany); Münchgesang, Wolfram; Pientschke, Christoph [Institute of Physics, Martin-Luther-University Halle-Wittenberg, Von-Danckelmann-Platz 3, D-06120 Halle/Saale (Germany); Großmann, Thomas; Zenkner, Mandy [Institute of Chemistry, Martin-Luther-University Halle-Wittenberg, Kurt-Mothes-Straße 2, D-06120 Halle/Saale (Germany); Wagner, Gerald; Leipner, Hartmut S.; Buchsteiner, Alexandra [Interdisciplinary Centre of Materials Science, Martin-Luther-University Halle-Wittenberg, Heinrich-Damerow-Straße 4, D-06120 Halle/Saale (Germany); Diestelhorst, Martin; Lemm, Sebastian; Beige, Horst [Institute of Physics, Martin-Luther-University Halle-Wittenberg, Von-Danckelmann-Platz 3, D-06120 Halle/Saale (Germany); Ebbinghaus, Stefan G., E-mail: stefan.ebbinghaus@chemie.uni-halle.de [Institute of Chemistry, Martin-Luther-University Halle-Wittenberg, Kurt-Mothes-Straße 2, D-06120 Halle/Saale (Germany)

2013-08-01

Highlights: • Polymer composites were prepared using a sol–gel synthesized BaTiO{sub 3}. • BaTiO{sub 3} surface hydroxyle groups act as linkers for surfactant molecules. • The effect of chemical adjustment between surfactant and polymer host is studied. • A positive effect of an additional dispersant was found. • Dielectric properties of the resulting composite films are presented. -- Abstract: We report on BaTiO{sub 3}–polymer composites as dielectrics for film capacitors. BaTiO{sub 3} was synthesized by a sol–gel soft-chemistry method leading to spherical nanoparticles with a high degree of surface hydroxyl groups which turned out to be important for the bonding of surfactant molecules. As surfactants, n-octylphosphonic acid and 2,3,4,5,6-pentafluorobenzyl phosphonic acid were used to inhibit particle agglomeration and to improve the wetting behaviour with the polymer. The phosphonic acid-coated BaTiO{sub 3} nanoparticles were dispersed in solutions of poly(vinylidefluoride-co-hexafluoropropylene). Composite films were prepared by the spin-coating technique. A systematic study was performed on the influence of varying oxide fractions, different surfactants and the effect of additional dispersion aids such as sodium dodecyl sulphate or BYK-W 9010 on the quality and dielectric properties of the films obtained. The chemical adjustment of the 2,3,4,5,6-pentaflourobenzyl phosphonic acid within the fluorinated organic host form a more uniform particle distribution and increase relative permittivity of the resulting composite material compared to the unflourinated surfactant. Additionally, an enhancement of the relative permittivity can be realized by adding of dispersants. These two components can increase the relative permittivity by factor 5 compared to the pure polymer material.

BaTiO3–P(VDF-HFP) nanocomposite dielectrics—Influence of surface modification and dispersion additives

International Nuclear Information System (INIS)

Ehrhardt, Claudia; Fettkenhauer, Christian; Glenneberg, Jens; Münchgesang, Wolfram; Pientschke, Christoph; Großmann, Thomas; Zenkner, Mandy; Wagner, Gerald; Leipner, Hartmut S.; Buchsteiner, Alexandra; Diestelhorst, Martin; Lemm, Sebastian; Beige, Horst; Ebbinghaus, Stefan G.

2013-01-01

Highlights: • Polymer composites were prepared using a sol–gel synthesized BaTiO 3 . • BaTiO 3 surface hydroxyle groups act as linkers for surfactant molecules. • The effect of chemical adjustment between surfactant and polymer host is studied. • A positive effect of an additional dispersant was found. • Dielectric properties of the resulting composite films are presented. -- Abstract: We report on BaTiO 3 –polymer composites as dielectrics for film capacitors. BaTiO 3 was synthesized by a sol–gel soft-chemistry method leading to spherical nanoparticles with a high degree of surface hydroxyl groups which turned out to be important for the bonding of surfactant molecules. As surfactants, n-octylphosphonic acid and 2,3,4,5,6-pentafluorobenzyl phosphonic acid were used to inhibit particle agglomeration and to improve the wetting behaviour with the polymer. The phosphonic acid-coated BaTiO 3 nanoparticles were dispersed in solutions of poly(vinylidefluoride-co-hexafluoropropylene). Composite films were prepared by the spin-coating technique. A systematic study was performed on the influence of varying oxide fractions, different surfactants and the effect of additional dispersion aids such as sodium dodecyl sulphate or BYK-W 9010 on the quality and dielectric properties of the films obtained. The chemical adjustment of the 2,3,4,5,6-pentaflourobenzyl phosphonic acid within the fluorinated organic host form a more uniform particle distribution and increase relative permittivity of the resulting composite material compared to the unflourinated surfactant. Additionally, an enhancement of the relative permittivity can be realized by adding of dispersants. These two components can increase the relative permittivity by factor 5 compared to the pure polymer material

Polymeric Materials For Scale Inhibition In Cooling Water Systems

Directory of Open Access Journals (Sweden)

Najwa S.Majeed

2013-04-01

Full Text Available Calcium carbonate deposition is generally predominant in cooling water-circulating system. For the control of calcium carbonate scale formation two types of polymeric scale inhibitors were used Polyamino polyether methylene phosphonate  (PAPEMPand polyacrylaminde(PAA.Model of cooling tower system have been built up in laboratory scale. Experiments were carried out using different inhibitor concentrations(0.5,1,1.5,2,3ppm ,at water temperature of  40oC and flow rate of 150 l/hr. It was found that Polyamino polyether methylene phosphonate    more effective than polyacryle amide'  as scale inhibitor in all used concentrations and the best inhibition efficiency (95% was at (2.5ppm of Polyamino polyether methylene phosphonate  and (85% with poly acryle amide at concentrations of (3 ppm. The performance of the polymeric scale inhibitors was compared with a method used to control heavy calcium carbonate scale forming by the deposition of sufficiently thin protective calcium carbonate scale using sulfuric acid and depending on Ryznar stability index controlling method. 

Suppression of Powdery Mildew Using the Water Extract of Xylogone ganodermophthora and Aqueous Potassium Phosphonate Solution on Watermelon under Greenhouse Conditions

Directory of Open Access Journals (Sweden)

Hyo-Jung Kang

2015-12-01

Full Text Available Xylogone ganodermophthora (Xg is an ascomycetous fungus that causes yellow rot on cultivated Ganoderma lucidum. Previously, we reported in vitro antifungal activities of a Xg culture extract against several watermelon pathogens. In 2014, we conducted greenhouse experiments to evaluate the control efficacy of a water extract of cultured Xg on watermelon powdery mildew (WPM. The test material (stock solution, ca. 4,000 µg/ml was prepared by an autoclaved Xg culture in water at a ratio of 800 g of culture per 6 liter of water, and then filtering it through filter paper. Six foliar applications of the solutions (diluted 100- and 1,000-fold significantly suppressed the formation of conidiophores and conidia. The inhibitory effect of aqueous potassium phosphonate solution on the disease and its phytotoxicity was tested. Phytotoxicity on watermelon plants was observed at concentrations of 1,000 and 2,000 µg/ml as irregular brownish spots. The control efficacies against WPM were 91.9% at 2,000 µg/ml, 64.9% at 1,000 µg/ml, and 62.2% at 500 µg/ml.

Synthesis and biological properties of prodrugs of (S)-3-(adenin-9-yl)-2-(phosphonomethoxy)propanoic acid

Czech Academy of Sciences Publication Activity Database

Kaiser, Martin Maxmilian; Poštová Slavětínská, Lenka; Dračínský, Martin; Lee, Y. J.; Tian, Y.; Janeba, Zlatko

2016-01-01

Roč. 108, Jan 27 (2016), s. 374-380 ISSN 0223-5234 R&D Projects: GA MV VG20102015046 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * (S)-CPMEA * antiviral * HCV * prodrugs Subject RIV: CC - Organic Chemistry Impact factor: 4.519, year: 2016

Characteristic of lipids and fatty acid compositions of the neon flying squid, Ommastrephes bartramii.

Science.gov (United States)

Saito, Hiroaki; Ishikawa, Satoru

2012-01-01

The lipids and fatty acids of the neon flying squid (Ommastrephes bartramii) were an-alyzed to clarify its lipid physiology and health benefit as marine food. Triacylglycerols were the only major component in the digestive gland (liver). In all other organs (mantle, arm, integument, and ovary), sterols and phospholipids were the major components with noticeable levels of ceramide aminoethyl phosphonate and sphingomyelin. The significant levels of sphingolipids suggest the O. bartramii lipids is a useful source for cosmetics. Although the lipid content between the liver and all other tissues markedly differed from each other, the same nine dominant fatty acids in the triacylglycerols were found in all organs; 14:0, 16:0, 18:0, 18:1n-9, 20:1n-9, 20:1n-11, 22:1n-11, 20:5n-3 (icosapentaenoic acid, EPA), and 22:6n-3 (docosahexaenoic acid, DHA). Unusually high 20:1n-11 levels in the O. bartramii triacylglycerols were probably characteristic for western Pacific animal depot lipids, compared with non-detectable levels of 20:1n-11 reported in other marine animals. O. bartramii concurrently has high levels of DHA in their triacylglycerols. The major fatty acids in the phospholipids were 16:0, 18:0, 20:1n-9, EPA, and DHA without 20:1n-11. Markedly high levels of both EPA and DHA were observed in phosphatidylethanolamine, while only DHA was found as the major one in phosphatidylcholine. In particular, high levels of DHA were found both in its depot triacylglycerols and tissue phospholipids in all organs of O. bartramii, similar to that in highly migratory fishes. The high DHA levels in all its organs suggest that O. bartramii lipids is a healthy marine source for DHA supplements.

The development of a new class of inhibitors for betaine-homocysteine S-methyltransferase

Czech Academy of Sciences Publication Activity Database

Pícha, Jan; Vaněk, Václav; Buděšínský, Miloš; Mládková, Jana; Garrow, T. A.; Jiráček, Jiří

2013-01-01

Roč. 65, July (2013), s. 256-275 ISSN 0223-5234 R&D Projects: GA ČR(CZ) GAP207/10/1277 Institutional support: RVO:61388963 Keywords : BHMT * inhibitor * homocysteine * phosphonate * phosphinate * amino acid derivative * bioisostere * S-alkylated homocysteine Subject RIV: CE - Biochemistry Impact factor: 3.432, year: 2013

Calcium phenylphosphonate as a host for 4-aminobenzoic acid-Synthesis, characterization, and cation adsorption from ethanol solution

International Nuclear Information System (INIS)

Lazarin, Angelica M.; Ganzerli, Thiago A.; Sernaglia, Rosana L.; Andreotti, Elza I.S.; Airoldi, Claudio

2009-01-01

Crystalline lamellar calcium phenylphosphonate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1160-695 cm -1 interval confirmed the presence of the phosphonate groups attached to the inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 1532 and 1751 pm for the original and the intercalated compounds, respectively. The thermogravimetric curves of both layered compounds showed the release of water molecules and the organic moiety in distinct stages, to yield a final Ca(PO 3 ) 2 residue. Solid-state 31 P nuclear magnetic resonance spectra presented only one peak for the phenylphosphonate groups attached to the main inorganic polymeric structure near 12.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 1.68 and 0.50 mmol g -1 for copper and cobalt, respectively, whose average stability constants followed Co > Cu; the number of ligands was determined as four for both cations.

Use of bis phosphonates in prostate cancer

International Nuclear Information System (INIS)

Della Valle, A.

2004-01-01

Prostate cancer is the second leading cause of cancer death in men in the world, meaning a real public health problem. The prevalence of Bone metastases may reach 100% of those who die from this disease printing a serious decline in the quality of life especially in the occurrence of skeletal-related events. Since three decades we try to find an inhibitor bone resorption which might prevent or treat bone metastases develop bisphosphonates (BF). These can not only inhibit the recruitment and differentiation osteoclast but decrease its half-life leading to early apoptosis. All BF have similar physicochemical properties and pharmacokinetics, but they differ in their anti-resorptive potency, ibandronate and zoledronic acid are BF generation that have been successful in the treatment of pain and decreased bone events in several works, however only one study randomized was conducted to show significant therapeutic advantages bone metastasis of prostate cancer. Although most authors indicate a therapeutic benefit, the evidence is weak and higher costs. Urges the implementation of new studies assessing both ibandronate and zoledronic acid in order to assert its virtues

Effect of pKa on the extraction behavior of Am(III) in organo phosphorus acid and diglycolamide solvent system

International Nuclear Information System (INIS)

Swami, K. Rama; Antony, M.P.; Homi Bhabha National Institute, Mumbai; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.

2018-01-01

A combination of neutral and acidic extractant has been proposed for the single-cycle separation of trivalent actinides from high-level liquid waste (HLLW). The nature of acidic extractant in the combined solvent formulation plays a profound role in deciding the extraction and stripping of trivalent actinides. Therefore, the extraction behavior of Am(III) in a solution of tetra-bis(2-ethylhexyl)-diglycolamide (TEHDGA) and acidic extractant (HA) was studied from nitric acid medium. The acidic extractants chosen were bis(2-ethylhexyl)phosphoric acid (HDEHP), bis(2-ethylhexyl)phosphonic acid (PC88A) and bis(2,4,4-trimethylpentyl)phosphinic acid (CYANEX-272) whose pKa values were 3.24, 4.51 and 6.37, respectively. The distribution ratio of Am(III) was measured as a function of various parameters such as concentration of nitric acid, TEHDGA, HA etc. The data were compared with those obtained in individual solvent systems namely 0.1 M TEHDGA/n-DD and HA/n-DD. Slope analysis of the extraction data indicated the synergic participation of both TEHDGA and HDEHP in the extraction of Am(III) at all acidities. However, antagonistic effect was observed at lower acidity when TEHDGA was mixed to PC88A or CYANEX-272 present in n-DD. Accordingly, a suitable mechanism has been proposed for the extraction of Am(III) at all acidities using these combined solvent formulation. Studies with fast reactor simulated high level liquid waste indicated that extraction of Am(III) was accompanied by co-extraction of lanthanides and unwanted metal ions such as Zr(IV), Mo(VI), Y(III) and Pd(II). However, addition of trans-1,2-diaminocyclohexane-N,N,N,N ' -tetraaceticacid (CyDTA) reduced the extraction of unwanted metal ions. Batch extraction and stripping studies indicated the possibility of using 0.1 M TEHDGA+0.25 M HDEHP in n-dodecane for the single cycle separation of Am(III) from FR-SHLLW.

Photocatalytic degradation of paraoxon-ethyl in aqueous solution using titania nanoparticulate film

International Nuclear Information System (INIS)

Prasad, G.K.; Ramacharyulu, P.V.R.K.; Kumar, J. Praveen; Srivastava, A.R.; Singh, Beer

2012-01-01

Photocatalytic degradation of paraoxon-ethyl (o,o-diethyl o-(4-nitrophenyl) phosphate), a well known surrogate of chemical warfare agents, in aqueous solution was studied by using titania nanoparticulate film. Reaction followed pseudo first order behaviour. Photolytic degradation reaction of paraoxon-ethyl demonstrated relatively low rate with a value of rate constant of 2.5 × 10 −3 min −1 . Whereas, degradation reaction in the presence of titania nanoparticulate film and UV light displayed enhanced rate with a value of rate constant of 6.9 × 10 −3 min −1 due to photocatalysis. Gas chromatography–mass spectrometry analysis showed the formation of p-nitrophenol, o,o-diethyl phosphonic acid, o-ethyl, diphosphonic acid, phosphoric acid, dimerized product of o,o-diethyl phosphonic acid, acetaldehyde, and carbon dioxide due to photocatalytic degradation of paraoxon-ethyl. It indicates that, photocatalytic degradation reaction begins with destruction of P–O–C bonds. Subsequently, P, C atoms were found to be oxidized gradually, and contributed to its photocatalytic degradation. - Highlights: ► Synthesis of titania nanoparticles by sol–gel method. ► Fabrication of titania nanoparticulate film by dip coating. ► Paraoxon ethyl degradation reactions followed pseudo first order behaviour. ► Paraoxon-ethyl degraded to non toxic compounds like CO 2 , acetaldehyde, and nitrophenol.

Self-assembled monolayer exchange reactions as a tool for channel interface engineering in low-voltage organic thin-film transistors.

Science.gov (United States)

Lenz, Thomas; Schmaltz, Thomas; Novak, Michael; Halik, Marcus

2012-10-02

In this work, we compared the kinetics of monolayer self-assembly long-chained carboxylic acids and phosphonic acids on thin aluminum oxide surfaces and investigated their dielectric properties in capacitors and low-voltage organic thin-film transistors. Phosphonic acid anchor groups tend to substitute carboxylic acid molecules on aluminum oxide surfaces and thus allow the formation of mixed or fully exchanged monolayers. With different alkyl chain substituents (n-alkyl or fluorinated alkyl chains), the exchange reaction can be monitored as a function of time by static contact angle measurements. The threshold voltage in α,α'-dihexyl-sexithiophene thin-film transistors composed of such mixed layer dielectrics correlates with the exchange progress and can be tuned from negative to positive values or vice versa depending on the dipole moment of the alkyl chain substituents. The change in the dipole moment with increasing exchange time also shifts the capacitance of these devices. The rate constants for exchange reactions determined by the time-dependent shift of static contact angle, threshold voltage, and capacitance exhibit virtually the same value thus proving the exchange kinetics to be highly controllable. In general, the exchange approach is a powerful tool in interface engineering, displaying a great potential for tailoring of device characteristics.

Global recovery process of thorium and rare earths in a nitrate medium

International Nuclear Information System (INIS)

Cailly, F.; Mottot, Y.

1993-01-01

The aqueous solution of thorium and rare earth nitrates, obtained by leaching the ore with nitric acid, is extracted by an organic phosphorous compound (phosphate, phosphonate, phosphinate or phosphine oxide) and a cationic extractant chosen among phosphoric acid di-esters. Extraction of thorium and rare earths is possible even in presence of phosphate ions in the aqueous solution. Thorium and rare earths are separated by liquid-liquid extraction of the organic phase

Multifunctional organophosphorus extractants: a status report on development and applications

International Nuclear Information System (INIS)

Schulz, W.W.; Horwitz, E.P.

1988-01-01

Up-to-date state of the development of science and technology of multifunctional organophosphorus extractants is considered. The detailed classification of these extractants is presented. They attracted pasticular interest because of affinity of some bifunctional phosphonates, phosphine oxides, carbamoylalkylphosphonates to trivalent Am, tetravalent and hexavalent actinides, trivalent lanthanides in strong mineral acids, and because of ability of some alkylpyrophosphoric acids to extract effectively U(4) from concentrated solutions of phosphoric acid. Application of these extractants for analytic purposes and in the field of nuclear technology is considered

Novel route to 5-position vinyl derivatives of thiolactomycin: Olefination vs. deformylation

Science.gov (United States)

Kim, Pilho; Barry, Clifton E.; Dowd*, Cynthia S.

2006-01-01

Vinyl and diene derivatives of thiolactomycin have been prepared via Horner-Wadsworth-Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of desired product to deformylated product. PMID:16699591

Lysophosphatidic acid-functionalised titanium as a superior surface for supporting human osteoblast (MG63 maturation

Directory of Open Access Journals (Sweden)

JP Mansell

2012-05-01

Full Text Available Covalent modifications of titanium with small molecules known to promote human osteoblast maturation are especially attractive in developing superior biomaterials. An important step in securing competent bone formation at implant sites is promoting the formation of mature osteoblasts, either from committed pre-osteoblasts or from their mesenchymal progenitors. To this end our research has focussed on identifying molecules that enhance human osteoblast formation and maturation and to develop ways of covalently attaching these molecules to implant surfaces so that they are more likely to withstand the rigors of the implantation process whilst still retaining their bioactivity. Herein we report the novel production of lipid-functionalised titanium using lysophosphatidic acid or a related compound, (3S 1-fluoro-3-hydroxy-4-butyl-1-phosphonate. Both lipids were especially effective at co-operating with calcitriol to promote human osteoblast maturation at these modified Ti surfaces in vitro. The novel findings presented offer enticing new developments towards the fabrication of next-generation implant devices with the potential to significantly enhance the osseointegration process and with it improvements in future prosthesis performance and longevity.

Determination of glyphosate residuals and of their metabolite Aminomethyl-Phosphonic acid in waters, by means of liquid chromatography of high efficiency with post-column derivation and fluorescence detection; Determinacion de residuos de glifosato y de su metabolito acido aminometilfosfonico en aguas, mediante cromatografia liquida de alta eficiencia con derivacion poscolumna y deteccion por fluorescencia

Energy Technology Data Exchange (ETDEWEB)

Rodriguez, Hugo A; Guerrero, Jairo; Castro, Rene

2002-07-01

The glyphosate is a no selective herbicide largely used in the world in order to control annual and perennial weeds. Its principal metabolite in soils and waters is the Aminomethyl-Phosphonic Acid (AMPA) formed by micro organism's action. This herbicide is used in Colombia in high doses to illegal crops eradication of coca and Amapola and like natural accelerator in sugar cane, constituting an environmental and social problem for the country, being necessary the evaluation of glyphosate residues in different matrices. This study describes the validation of the analytical methodology for the simultaneous determination of glyphosate and its metabolite AMPA in waters of some Colombian regions. The experimental procedure pointed out two main steps: the first one was a cleaning, extraction and concentration step by solid phase extraction; the second step is the separation, identification and quantification of the compounds by High Performance Liquid Chromatography (HPLC) with post-column derivation and fluorescence detection. The results of the validation show that the methodology is specific, selective, precise and robust with linear calibration curve in the linear range between 10 and 750 {mu}g/L, with limits of detection of 0.8 {mu}g/L and limits of quantification of 2 {mu}g/L for the two analyses. The recoveries are in the order of 73% for glyphosate and 70% for AMPA. More over analysis results are presented for water samples of some country regions where glyphosate is applied in different doses with different purposes, finding residues of the herbicide and its metabolite in concentrations above the allowed values in drinking waters for pesticides of toxicology category IV, like the glyphosate, according with the Colombian legislation.

Untitled

African Journals Online (AJOL)

ASSTRACT. The chelating properties of N-aminoalkylaminonethane-phosphonic acids, NAMPA of general formula, ... nickel(II) and cobalt(II) ions form complexes with the ligands in the ratios 11, 12 and 13. Some of the ... been used in peptide synthesis for the preparation of ..... Flse is Asrat iron ref nr 0.2 * picket acett outer.

Browse Title Index

African Journals Online (AJOL)

Items 601 - 650 of 1007 ... Vol 28, No 1 (2014), High yield synthesis of some phosphonic acid derivatives as surface tethers for energy harvesting technologies, Abstract PDF. A. Mungalimane. Vol 1, No 1 (1987), Highfieid 1H and 13C NMR of 5-oxygenated of cholestane-6-oxime derivatives, Abstract PDF. Helmut Duddeck ...

Electrochemical modification of carbon electrode with benzylphosphonic groups

International Nuclear Information System (INIS)

Benjamin, Ossonon Diby; Weissmann, Martin; Bélanger, Daniel

2014-01-01

Electrochemical modification of carbon electrodes by aryl groups bearing a phosphonate terminal functionality was carried out by both electrochemical reduction of diazonium ions (diazobenzylphosphonic acid) and electrochemical oxidation of an amine (aminobenzylphosphonic acid). The grafting by electrochemical reduction of aryl diazonium ions was found to be more efficient. The surface concentration of phosphonate groups, estimated by electrochemical reduction of electrostatically bound Pb(II) ions, was found to be about 25% higher for the layer formed by electrochemical reduction of diazonium ions than for the layer formed by oxidation of the amine. The acid–base properties of the grafted films were slightly influenced by the grafting procedure and the difference in the apparent pK a was most likely related to the presence of the substrate –NH-aryl linkage for the film generated by amine oxidation. X-ray photoelectron spectroscopy was used to get some insight on the chemical species present at the carbon electrode surface. For both procedures, the films consist in mixture of at least two different covalently grafted species

Neutron diffraction by monocrystals of inorganic and elementary organic compounds

International Nuclear Information System (INIS)

Becker, G.; Hauser, H.D.

1992-01-01

The phase of preparation and X-ray structural analysis of the compounds has been completed following the synthetical preparation of compounds sensitive to oxidation and pyrolysis, in this case: phosphonic acid, potassium silanide, lithium dihydrogenphosphide * DME, bis[lithium-tri(tert.butyl)alanate], dibromophenylbismuthate, potassium tetrahydride aluminate, and phosphinic acid. The work was started is neutron diffraction experiments for detecting the positions of the hydrogen and carbon atoms, in order to analyse space group problems. (BBR) [de

Photocatalytic degradation of paraoxon-ethyl in aqueous solution using titania nanoparticulate film

Energy Technology Data Exchange (ETDEWEB)

Prasad, G.K., E-mail: gkprasad2001@yahoo.com; Ramacharyulu, P.V.R.K.; Kumar, J. Praveen; Srivastava, A.R.; Singh, Beer

2012-06-30

Photocatalytic degradation of paraoxon-ethyl (o,o-diethyl o-(4-nitrophenyl) phosphate), a well known surrogate of chemical warfare agents, in aqueous solution was studied by using titania nanoparticulate film. Reaction followed pseudo first order behaviour. Photolytic degradation reaction of paraoxon-ethyl demonstrated relatively low rate with a value of rate constant of 2.5 Multiplication-Sign 10{sup -3} min{sup -1}. Whereas, degradation reaction in the presence of titania nanoparticulate film and UV light displayed enhanced rate with a value of rate constant of 6.9 Multiplication-Sign 10{sup -3} min{sup -1} due to photocatalysis. Gas chromatography-mass spectrometry analysis showed the formation of p-nitrophenol, o,o-diethyl phosphonic acid, o-ethyl, diphosphonic acid, phosphoric acid, dimerized product of o,o-diethyl phosphonic acid, acetaldehyde, and carbon dioxide due to photocatalytic degradation of paraoxon-ethyl. It indicates that, photocatalytic degradation reaction begins with destruction of P-O-C bonds. Subsequently, P, C atoms were found to be oxidized gradually, and contributed to its photocatalytic degradation. - Highlights: Black-Right-Pointing-Pointer Synthesis of titania nanoparticles by sol-gel method. Black-Right-Pointing-Pointer Fabrication of titania nanoparticulate film by dip coating. Black-Right-Pointing-Pointer Paraoxon ethyl degradation reactions followed pseudo first order behaviour. Black-Right-Pointing-Pointer Paraoxon-ethyl degraded to non toxic compounds like CO{sub 2}, acetaldehyde, and nitrophenol.

pKa value and buffering capacity of acidic monomers commonly used in self-etching primers.

Science.gov (United States)

Salz, Ulrich; Mücke, Angela; Zimmermann, Jörg; Tay, Franklin R; Pashley, David H

2006-06-01

The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4-(dihydroxyphosphoryl)-2-ox-abutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/l NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated bythe corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. For all the investigated acidic monomers, pKal values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKal values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0

Process for reducing halogen impurities in oil products

Energy Technology Data Exchange (ETDEWEB)

Basler, F.

1990-08-14

Oil products, in particular waste oils, may be efficiently reprocessed according to an economic and technically simple method for removing impurities, notably halogens. In this method, the oil product is treated at temperatures up to about 150{degree}C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof. The oil product obtained in this step is treated at increased temperatures with at least one halogen binding agent. The water and/or solids from the product so treated are separated out. The process of the invention can be carried out in a conventional stripping apparatus. The strong acid used in the first step is preferably selected from sulfurous acid, phosphoric acid, phosphorous acid, and phosphonic acid. The salt of the weak base and strong acid is preferably ammonium sulfate, ammonium bisulfate, ammonium sulfite, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite, and ammonium phosphonic acid. The second step of the method is preferably a coagulation step in which organic halogen compounds break down into hydrogen halides which are neutralized by the added halogen binding agents. The preferred halogen binding agents are ammonia and/or an organic base. The coagulation is preferably carried out in heat exchangers so that the oil is heated in 3 stages and the oil from each stage is passed through a cascade tower. In the third step, additives may be used to enhance separation of the oil. Experiments are described to illustrate the method of the invention. 1 tab.

Evaluation of synthetic water-soluble metal-binding polymers with ultrafiltration for selective concentration of americium and plutonium

International Nuclear Information System (INIS)

Smith, B.F.; Gibson, R.R.; Jarvinen, G.D.; Jones, M.M.; Lu, M.T.; Robison, T.W.; Schroeder, N.C.; Stalnaker, N.

1997-01-01

Routine counting methods and ICP-MS are unable to directly measure the new US Department of Energy (DOE) regulatory level for discharge waters containing alpha-emitting radionuclides of 30 pCi/L total alpha or the 0.05 pCi/L regulatory level for Pu or Am activity required for surface waters at the Rocky Flats site by the State of Colorado. This inability indicates the need to develop rapid, reliable, and robust analytical techniques for measuring actinide metal ions, particularly americium and plutonium. Selective separation or preconcentration techniques would aid in this effort. Water-soluble metal-binding polymers in combination with ultrafiltration are shown to be an effective method for selectively removing dilute actinide ions from acidic solutions of high ionic strength. The actinide-binding properties of commercially available water-soluble polymers and several polymers which have been reported in the literature were evaluated. The functional groups incorporated in the polymers were pyrrolidone, amine, oxime, and carboxylic, phosphonic, or sulfonic acid. The polymer containing phosphonic acid groups gave the best results with high distribution coefficients and concentration factors for 241 Am(III) and 238 Pu(III)/(IV) at pH 4 to 6 and ionic strengths of 0.1 to 4

Design and synthesis of polyphosphazenes: Hard tissue scaffolding biomaterials and physically crosslinked elastomers

Science.gov (United States)

Modzelewski, Tomasz

The work in this thesis is divided into two main parts. The first part examines the synthesis and characterization of polyphosphazenes as potential scaffolding materials usable for hard tissue repair. The goal of this work was to design polymers containing acidic functional groups in an attempt to encourage the deposition of calcium hydroxyapatite when the polymer is exposed to simulated body fluids. The second part examines the development of a new polymeric architecture which generates elastomeric properties without the use of traditional covalent or physical crosslinks. The goal was to examine the effects of this new architecture on the physical and mechanical properties of the final polymers. Chapter 1 provides a general background for the two main focus areas mentioned above. More specifically: a brief explanation is provided of the necessary physical and chemical properties of a suitable hard tissue engineering scaffolding substrate, and the basis of those requirements; together with an examination of the traditional ways in which elastomeric properties are introduced into a polymeric sample. Chapter 2 details the design and synthesis of polyphosphazenes bearing phosphonic acid and phosphoester side groups using two different routes. The first route utilized a linker unit which was functionalized with phosphoesters prior to its attachment to the polyphosphazene backbone, while the second route involved attachment of the same linking group to the polyphosphazene backbone before the introduction of the phosphoester moieties. In both cases, the samples were treated with iodotrimethylsilane to cleave the ester bonds and afford the parent phosphonic acid. Both routes proved successful. However, varying difficulties were encountered for each route. In Chapter 3 we examine the ability of the phosphonic acid functionalized polyphosphazenes described in Chapter 2 to mineralize calcium hydroxyapatite when exposed to simulated body fluid, which has the same ion

Characterization of Macrophage Endogenous S-Nitrosoproteome Using a Cysteine-Specific Phosphonate Adaptable Tag in Combination with TiO2 Chromatography.

Science.gov (United States)

Ibáñez-Vea, María; Huang, Honggang; Martínez de Morentin, Xabier; Pérez, Estela; Gato, Maria; Zuazo, Miren; Arasanz, Hugo; Fernández-Irigoyen, Joaquin; Santamaría, Enrique; Fernandez-Hinojal, Gonzalo; Larsen, Martin R; Escors, David; Kochan, Grazyna

2018-03-02

Protein S-nitrosylation is a cysteine post-translational modification mediated by nitric oxide. An increasing number of studies highlight S-nitrosylation as an important regulator of signaling involved in numerous cellular processes. Despite the significant progress in the development of redox proteomic methods, identification and quantification of endogeneous S-nitrosylation using high-throughput mass-spectrometry-based methods is a technical challenge because this modification is highly labile. To overcome this drawback, most methods induce S-nitrosylation chemically in proteins using nitrosylating compounds before analysis, with the risk of introducing nonphysiological S-nitrosylation. Here we present a novel method to efficiently identify endogenous S-nitrosopeptides in the macrophage total proteome. Our approach is based on the labeling of S-nitrosopeptides reduced by ascorbate with a cysteine specific phosphonate adaptable tag (CysPAT), followed by titanium dioxide (TiO 2 ) chromatography enrichment prior to nLC-MS/MS analysis. To test our procedure, we performed a large-scale analysis of this low-abundant modification in a murine macrophage cell line. We identified 569 endogeneous S-nitrosylated proteins compared with 795 following exogenous chemically induced S-nitrosylation. Importantly, we discovered 579 novel S-nitrosylation sites. The large number of identified endogenous S-nitrosylated peptides allowed the definition of two S-nitrosylation consensus sites, highlighting protein translation and redox processes as key S-nitrosylation targets in macrophages.

Ab initio design of drug carriers for zoledronate guest molecule using phosphonated and sulfonated calix[4]arene and calix[4]resorcinarene host molecules

Science.gov (United States)

Jang, Yong-Man; Yu, Chol-Jun; Kim, Jin-Song; Kim, Song-Un

2018-04-01

Monomolecular drug carriers based on calix[n]-arenes and -resorcinarenes containing the interior cavity can enhance the affinity and specificity of the osteoporosis inhibitor drug zoledronate (ZOD). In this work we investigate the suitability of nine different calix[4]-arenes and -resorcinarenes based macrocycles as hosts for the ZOD guest molecule by conducting {\\it ab initio} density functional theory calculations for structures and energetics of eighteen different host-guest complexes. For the optimized molecular structures of the free, phosphonated, sulfonated calix[4]-arenes and -resorcinarenes, the geometric sizes of their interior cavities are measured and compared with those of the host-guest complexes in order to check the appropriateness for host-guest complex formation. Our calculations of binding energies indicate that in gaseous states some of the complexes might be unstable but in aqueous states almost all of the complexes can be formed spontaneously. Of the two different docking ways, the insertion of ZOD with the \\ce{P-C-P} branch into the cavity of host is easier than that with the nitrogen containing heterocycle of ZOD. The work will open a way for developing effective drug delivering systems for the ZOD drug and promote experimentalists to synthesize them.

Chemical approaches to zero blowdown operation (TP93-05)

International Nuclear Information System (INIS)

Geiger, G.E.; Ogg, J.; Hatch, M.R.

1993-03-01

Zero blowdown operation was evaluated at a cooling tower at the Stanford Linear Accelerator Center in an attempt to eliminate cooling water discharge. Testing was performed with and without acid feed for pH control using a state-of-the-art treatment which contained polymer, phosphonate, and azole. Supplemental additional of a proprietary calcium carbonate scale inhibitor was also evaluated

Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

International Nuclear Information System (INIS)

Maroun, E.B.; Hagege, A.; Asfari, Z.; Basset, CH.; Quemeneur, E.; Vidaud, C.

2009-01-01

With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

Energy Technology Data Exchange (ETDEWEB)

Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)

2009-07-01

With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

Quantitative determination of acidic hydrolysis products of Chemical Weapons Convention related chemicals from aqueous and soil samples using ion-pair solid-phase extraction and in situ butylation.

Science.gov (United States)

Pal Anagoni, Suresh; Kauser, Asma; Maity, Gopal; Upadhyayula, Vijayasarathi V R

2018-02-01

Chemical warfare agents such as organophosphorus nerve agents, mustard agents, and psychotomimetic agent like 3-quinuclidinylbenzilate degrade in the environment and form acidic degradation products, the analysis of which is difficult under normal analytical conditions. In the present work, a simultaneous extraction and derivatization method in which the analytes are butylated followed by gas chromatography and mass spectrometric identification of the analytes from aqueous and soil samples was carried out. The extraction was carried out using ion-pair solid-phase extraction with tetrabutylammonium hydroxide followed by gas chromatography with mass spectrometry in the electron ionization mode. Various parameters such as optimum concentration of the ion-pair reagent, pH of the sample, extraction solvent, and type of ion-pair reagent were optimized. The method was validated for various parameters such as linearity, accuracy, precision, and limit of detection and quantification. The method was observed to be linear from 1 to 1000 ng/mL range in selected ion monitoring mode. The extraction recoveries were in the range of 85-110% from the matrixes with the limit of quantification for alkyl phosphonic acids at 1 ng/mL, thiodiglycolic acid at 20 ng/mL, and benzilic acid at 50 ng/mL with intra- and interday precisions below 15%. The developed method was applied for the samples prepared in the scenario of challenging inspection. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultra-fast photo-patterning of hydroxamic acid layers adsorbed on TiAlN: The challenge of modeling thermally induced desorption

Energy Technology Data Exchange (ETDEWEB)

Hemgesberg, Maximilian [Fachbereich Chemie, Technische Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse 54, 67663 Kaiserslautern (Germany); Schuetz, Simon [Fachbereich Physik und Forschungszentrum OPTIMAS, Technische Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse 45, 67663 Kaiserslautern (Germany); Heidelberger Druckmaschinen AG, Kurfuerstenanlage 54-60, 66120 Heidelberg (Germany); Mueller, Christine [Fachbereich Physik und Forschungszentrum OPTIMAS, Technische Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse 45, 67663 Kaiserslautern (Germany); Schloerholz, Matthias; Latzel, Harald [Heidelberger Druckmaschinen AG, Kurfuerstenanlage 54-60, 66120 Heidelberg (Germany); Sun, Yu [Fachbereich Chemie, Technische Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse 54, 67663 Kaiserslautern (Germany); Ziegler, Christiane [Fachbereich Physik und Forschungszentrum OPTIMAS, Technische Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse 45, 67663 Kaiserslautern (Germany); Thiel, Werner R., E-mail: thiel@chemie.uni-kl.de [Fachbereich Chemie, Technische Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse 54, 67663 Kaiserslautern (Germany)

2012-10-15

Highlights: Black-Right-Pointing-Pointer Different hydroxamic acids are suitable for the hydrophobization of TiAlN surfaces used in photo-patterning applications. Black-Right-Pointing-Pointer The binding strength of the surfactant on the surface is dependent on the hydrogen and {pi}-bonding interactions within the organic layer. Black-Right-Pointing-Pointer Thermal desorption of selected HA species results in a 20% energy reduction compared to alkyl phosphates. - Abstract: Long-chain n-alkyl terminated hydroxamic acids (HA) are used for the modification of titanium aluminum nitride (TiAlN) surfaces. HA coatings improve the hydrophobicity of this wear resistant and industrially relevant ceramic. Therefore, HAs with different structural properties are evaluated with respect to their wear resistance and their thermal desorption properties. In order to find new coatings for rewritable offset printing plates, the changes in the surface polarity, composition, and morphology are analyzed by contact angle measurements, X-ray photoemission spectroscopy (XPS), and scanning force microscopy (SFM), respectively. The results are referenced to the strongly bonding molecule n-dodecyl phosphonate (PO11M), which has been used for surface hydrophobization before but proved difficult to remove due to the high laser outputs required for thermal desorption. It is found that for certain HAs, an equally good hydrophobization compared to PO11M can be achieved. Contact angles obtained for different hydroxamic acid coatings can be correlated to their modes of adsorption. Only for selected HA species, resistance to mechanical wear is sufficient for further investigations. Photo-patterning of these hydroxamic acid layers is achieved using a high energy IR laser beam at different energy inputs. Fitting of the obtained data and further evaluation using finite element analysis (FEM) calculations reveal significantly reduced energy consumption of about 20% for the removal of a specific hydroxamic

Studying on process for labeling of EDTMP with 90Y using for bone pain palliation

International Nuclear Information System (INIS)

Pham Ngoc Dien; Duong Van Dong; Dang Ho Hong Quang; Nguyen Thanh Binh; Bui Van Cuong; Nguyen Dang Khoa; Nguyen Thi Thu; Mai Phuoc Tho; Vo Cam Hoa

2013-01-01

This Study describes the method for preparation of labelling compound Ethylene diamine tetramethylene phosphonic acid (EDTMP) with 90 Y. Malignant cancer is one of the most important resulting in human death. Bone metastases in nearly 25% of all cancer patients; so it is useful to develop radiopharmaceuticals for the treatment of bone cancer. Yttrium-90 is high energy (2.3 MeV) beta emitter required with a physical haft life of 2.7 days which has limited bone-seeking properties. Its physical properties make it ideal for therapeutic application, the most energetic beta emission being able to penetrate to 1 cm from the site of deposition in soft tissue with an average range of approximately 4 mm. Theoretically, therefore, it can penetrate all marrow spaces in normal trabecular bone and conceivably even to the centre of large tumours where bone destruction may be extensive. Specific deposition of 90 Y into the skeleton demands its delivery in a chemical form with affinity for bone mineral alone. Compounds with these properties are the phosphonate analogues of polyaminocarboxylic acids, and one in particular EDTMP (ethylen diamine tetra methylene phosphonate) has already been used to target 153 Sm to bone mineral with success. Because of chemical similarities between 90 Y and the rare earths, EDTMP should form stable complexes with 90 Y and carry it specifically to the bone with comparable efficiency. Skeletal uptake of β - emitting radionuclides may be used for bone pain palliation or myeloablation. The physical characteristics of the β - particles required for the two conditions are, however, different, that is, higher energies are favorable for destruction of bone marrow. (author)

New bisphosphonate labeled with Iodine-131 for the palliative therapy for bone metastases pain

International Nuclear Information System (INIS)

Prats Capote, Anaís; Perera Pintado, Alejandro; León, Mariela; Hernández González, Ignacio; Leyva Montaña, René; Mocelo Castell, Raúl; O'Reilly, Beatriz; Calderón, Osmar; Griffith Pérez, Yoel; García Batle, Marisé; Rodríguez Tanty, Chryslaine

2016-01-01

The aim of this work was to obtain new bisphosphonate marked with 131I suitable for palliative treatment of bone metastases pain characteristics. Materials and Methods: It started with aromatic amino acids and the synthesis consisted of three stages: 1) Protection of amino groups by acetylation; 2) phosphonation protected amino acids with a mixture of phosphorous acid and phosphorus pentachloride; 3) Lack of protection of the amino groups by basic hydrolysis. The compounds obtained were characterized by IR, 1H NMR, RMN13-C mass. Los spectrometry bisphosphonic acids obtained were labeled with 131I using chloramine T and iodogen as oxidants. Stability of labeled compounds in aqueous solution was studied serum. 3 mg of 2-amino-3- (4-hydroxyphenyl) -1-hydroxypropyl-1,1-bisphosphonic acid labeled of 131I were administered to male wistar rats (170-190 g) through a lateral tail vein. The scintigraphic study was conducted at 2, 6 and 12 hours. Results: The yield of the reactions of the amino group protection four compounds ranged from 75 to 80%, while the phosphonation was between 50 and 60%. The radiochemical purity of 2-amino-3- (4-hydroxyphenyl) -1-hydroxypropyl-1,1- bisphosphonic acid labeled with 131I was (91.5 ± 1.4)% and its stability was satisfactory for 72h. Scintigraphic images suggest excretion by the kidneys of the compound and from 12 h post-administration begin to visualize bone structures of the animal, suggesting that the compound exhibits affinity for these tissues. Conclusions: A novel synthesis method with modifications that yielded the sodium salts of bisphosphonic acids starting from the respective aromatic amino acids was developed. 2-amino-3- (4-hydroxyphenyl) -1-hydroxypropyl-1,1-bisphosphonic acid 131I labeled was stable up to 72h and showed affinity for bone tissue. (author)

Degradation of the Phosphonate Herbicide Glyphosate by Arthrobacter atrocyaneus ATCC 13752

OpenAIRE

Pipke, Rüdiger; Amrhein, Nikolaus

1988-01-01

Of nine authentic Arthrobacter strains tested, only A. atrocyaneus ATCC 13752 was capable of using the herbicide glyphosate [N-(phosphonomethyl)glycine] as its sole source of phosphorus. Contrary to the previously isolated Arthrobacter sp. strain GLP-1, which degrades glyphosate via sarcosine, A. atrocyaneus metabolized glyphosate to aminomethylphosphonic acid. The carbon of aminomethylphosphonic acid was entirely converted to CO2. This is the first report on glyphosate degradation by a bacte...

An investigation of the electrochemical action of the epoxy zinc-rich coatings containing surface modified aluminum nanoparticle

Energy Technology Data Exchange (ETDEWEB)

Jalili, M. [Nanomaterials and Nanocoatings Department, Institute for Color Science and Technology (ICST), PO 16765-654, Tehran (Iran, Islamic Republic of); Surface Coatings and Corrosion Department, Institute for Color Science and Technology (ICST), PO 16765-654, Tehran (Iran, Islamic Republic of); Rostami, M. [Nanomaterials and Nanocoatings Department, Institute for Color Science and Technology (ICST), PO 16765-654, Tehran (Iran, Islamic Republic of); Ramezanzadeh, B., E-mail: ramezanzadeh-bh@icrc.ac.ir [Surface Coatings and Corrosion Department, Institute for Color Science and Technology (ICST), PO 16765-654, Tehran (Iran, Islamic Republic of)

2015-02-15

Highlights: • Aluminum nanoparticle was modified with amino trimethylene phosphonic acid. • 2 wt% of zinc dust in zinc-rich paint was substituted by aluminum nanoparticles. • Surface modified aluminum nanoparticle improved the cathodic period of protection. • Aluminum nanoparticles enhanced the corrosion protection of the zinc-rich coating. - Abstract: Aluminum nanoparticle was modified with amino trimethylene phosphonic acid (ATMP). The surface characterization of the nanoparticles was done by X-ray photo electron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and thermal gravimetric analysis. The influence of the replacement of 2 wt% of zinc dust in the standard zinc-rich epoxy coating by nanoparticles on the electrochemical action of the coating was studied by electrochemical impedance spectroscopy (EIS) and salt spray tests. The morphology and phase composition of the zinc rich paints were evaluated by X-ray diffraction (XRD) and filed-emission scanning electron microscopy (FE-SEM). Results showed that the ATMP molecules successfully adsorbed on the surface of Al nanoparticles. Results obtained from salt spray and electrochemical measurements revealed that the addition of surface modified nanoparticles to the zinc rich coating enhanced its galvanic action and corrosion protection properties.

An investigation of the electrochemical action of the epoxy zinc-rich coatings containing surface modified aluminum nanoparticle

International Nuclear Information System (INIS)

Jalili, M.; Rostami, M.; Ramezanzadeh, B.

2015-01-01

Highlights: • Aluminum nanoparticle was modified with amino trimethylene phosphonic acid. • 2 wt% of zinc dust in zinc-rich paint was substituted by aluminum nanoparticles. • Surface modified aluminum nanoparticle improved the cathodic period of protection. • Aluminum nanoparticles enhanced the corrosion protection of the zinc-rich coating. - Abstract: Aluminum nanoparticle was modified with amino trimethylene phosphonic acid (ATMP). The surface characterization of the nanoparticles was done by X-ray photo electron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and thermal gravimetric analysis. The influence of the replacement of 2 wt% of zinc dust in the standard zinc-rich epoxy coating by nanoparticles on the electrochemical action of the coating was studied by electrochemical impedance spectroscopy (EIS) and salt spray tests. The morphology and phase composition of the zinc rich paints were evaluated by X-ray diffraction (XRD) and filed-emission scanning electron microscopy (FE-SEM). Results showed that the ATMP molecules successfully adsorbed on the surface of Al nanoparticles. Results obtained from salt spray and electrochemical measurements revealed that the addition of surface modified nanoparticles to the zinc rich coating enhanced its galvanic action and corrosion protection properties

Degradation of the Herbicide Glyphosate by Members of the Family Rhizobiaceae

OpenAIRE

Liu, C.-M.; McLean, P. A.; Sookdeo, C. C.; Cannon, F. C.

1991-01-01

Several strains of the family Rhizobiaceae were tested for their ability to degrade the phosphonate herbicide glyphosate (isopropylamine salt of N-phosphonomethylglycine). All organisms tested (seven Rhizobium meliloti strains, Rhizobium leguminosarum, Rhizobium galega, Rhizobium trifolii, Agrobacterium rhizogenes, and Agrobacterium tumefaciens) were able to grow on glyphosate as the sole source of phosphorus in the presence of the aromatic amino acids, although growth on glyphosate was not a...

Stabilized radiographic scanning agents

International Nuclear Information System (INIS)

Fawzi, M.B.

1982-01-01

Stable compositions useful as technetium 99m-based scintigraphic agents comprise gentisic acid or a pharmaceutically-acceptable salt or ester thereof in combination with a pertechnetate reducing agent or dissolved in pertechnetate-99m (sup(99m)TcOsub(4)sup(-)) solution. The compositions are especially useful in combination with a phosphate or phosphonate material that carries the radionuclide to bone, thus providing a skeletal imaging agent

Low-voltage self-assembled monolayer field-effect transistors on flexible substrates.

Science.gov (United States)

Schmaltz, Thomas; Amin, Atefeh Y; Khassanov, Artoem; Meyer-Friedrichsen, Timo; Steinrück, Hans-Georg; Magerl, Andreas; Segura, Juan José; Voitchovsky, Kislon; Stellacci, Francesco; Halik, Marcus

2013-08-27

Self-assembled monolayer field-effect transistors (SAMFETs) of BTBT functionalized phosphonic acids are fabricated. The molecular design enables device operation with charge carrier mobilities up to 10(-2) cm(2) V(-1) s(-1) and for the first time SAMFETs which operate on rough, flexible PEN substrates even under mechanical substrate bending. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structure and magnetic properties of a new iron phosphonate-oxalate with 3D framework: [Fe(O3PCH3)(C2O4)0.5(H2O)

International Nuclear Information System (INIS)

Zhang Yangyang; Qi Yue; Zhang Ying; Liu Ziyu; Zhao Yinfeng; Liu Zhongmin

2007-01-01

A new iron phosphonate-oxalate [Fe(O 3 PCH 3 )(C 2 O 4 ) 0.5 (H 2 O)] (1), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction studies reveal that 1 consists of layers of vertex-linked FeO 6 octahedra and O 3 PC tetrahedra, which are further connected by bis-chelate oxalate bridges, giving to a 3D structure with 10-membered channels. Crystal data: monoclinic, P2 1 /n (no. 14), a=4.851(2)A, b=16.803(7)A, c=7.941(4)A, β=107.516(6) o , V=617.2(5)A 3 , Z=4, R 1 =0.0337 and wR 2 =0.0874 for 1251 reflections [I>2σ(I)]. Mossbauer spectroscopy measurement confirms the existence of high-spin Fe(III) in 1. Magnetic studies show that 1 exhibits weak ferromagnetism with T N =30K due to a weak spin canting

f-Element Ion Chelation in Highly Basic Media - Final Report

International Nuclear Information System (INIS)

Paine, R.T.

2000-01-01

A large body of data has been collected over the last fifty years on the chemical behavior of f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueous solutions that produce poorly understood oxide-hydroxide species; therefore, most of the fundamental f-element solution chemistry has allowed synthetic and separations chemists to rationally design advanced organic chelating ligands useful for highly selective partitioning and separation of f-element ions from complex acidic solution matrices. These ligands and new examples under development allow for the safe use and treatment of solutions containing highly radioactive species. This DOE/EMSP project was undertaken to address the following fundamental objectives: (1) study the chemical speciation of Sr and lanthanide (Ln) ions in basic aqueous media containing classical counter anions found in waste matrices; (2) prepare pyridine N-oxide phosphonates and phosphonic acids that might act as selective chelator s for Ln ions in model basic pH waste streams; (3) study the binding of the new chelators toward Ln ions and (4) examine the utility of the chelators as decontamination and dissolution agents under basic solution conditions. The project has been successful in attacking selected aspects of the very difficult problems associated with basic pH solution f-element waste chemistry. In particular, the project has (1) shed additional light on the initial stages of Ln ion sol-gel-precipitate formulation under basic solution conditions; (2) generated new families of pyridine phosphonic acid chelators; (3) characterized the function of the chelators and (4) examined their utility as oxide-hydroxide dissolution agents. These findings have contributed significantly to an improved understanding of the behavior of Ln ions in basic media containing anions found in typical waste sludges as well as to the development of sludge dissolution agents. The new chelating reagents are easily made and could be

f-Element Ion Chelation in Highly Basic Media

International Nuclear Information System (INIS)

Paine, R.T.

2000-01-01

A large body of data has been collected over the last fifty years on the chemical behavior of f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueous solutions that produce poorly understood oxide-hydroxide species; therefore, most of the fundamental f-element solution chemistry has allowed synthetic and separations chemists to rationally design advanced organic chelating ligands useful for highly selective partitioning and separation of f-element ions from complex acidic solution matrices. These ligands and new examples under development allow for the safe use and treatment of solutions containing highly radioactive species. This DOE/EMSP project was undertaken to address the following fundamental objectives: (1) study the chemical speciation of Sr and lanthanide (Ln) ions in basic aqueous media containing classical counter anions found in waste matrices; (2) prepare pyridine N-oxide phosphonates and phosphonic acids that might act as selective chelators for Ln ions in model basic pH waste streams; (3) study the binding of the new chelators toward Ln ions and (4) examine the utility of the chelators as decontamination and dissolution agents under basic solution conditions. The project has been successful in attacking selected aspects of the very difficult problems associated with basic pH solution f-element waste chemistry. In particular, the project has (1) shed additional light on the initial stages of Ln ion sol-gel-precipitate formulation under basic solution conditions; (2) generated new families of pyridine phosphonic acid chelators; (3) characterized the function of the chelators and (4) examined their utility as oxide-hydroxide dissolution agents. These findings have contributed significantly to an improved understanding of the behavior of Ln ions in basic media containing anions found in typical waste sludges as well as to the development of sludge dissolution agents. The new chelating reagents are easily made and could be

Effects of increasing doses of samarium-153-ethylenediaminetetramethylene phosphonate on axial and appendicular skeletal growth in juvenile rabbits

Energy Technology Data Exchange (ETDEWEB)

Essman, Stephanie C. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States)], E-mail: essmans@missouri.edu; Lewis, Michael R. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States); Department of Radiology, University of Missouri-Columbia, Columbia, MO 65211 (United States); Nuclear Science and Engineering Institute, University of Missouri-Columbia, Columbia, MO 65211 (United States); Research Service, Harry S. Truman Memorial Veterans' Hospital, Columbia, MO 65201 (United States); Fox, Derek B. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States)

2008-02-15

Introduction: Targeted radiotherapy using samarium-153-ethylenediaminetetramethylene phosphonate ({sup 153}Sm-EDTMP) is currently under investigation for treatment of osteosarcoma. Osteosarcoma often occurs in children, and previous studies on a juvenile rabbit model demonstrated that clinically significant damage to developing physeal cartilage may occur as a result of systemic {sup 153}Sm-EDTMP therapy. The aim of this study was to evaluate the late effects of {sup 153}Sm-EDTMP on skeletal structures during growth to maturity and to determine if there is a dose response of {sup 153}Sm-EDTMP on growth of long bones. Methods: Female 8-week-old New Zealand white rabbits were divided into three treatment groups plus controls. Each rabbit was intravenously administered a predetermined dose of {sup 153}Sm-EDTMP. Multiple bones of each rabbit were radiographed every 2 months until physeal closure, with subsequent measurements made to assess for abbreviated bone growth. Statistical analyses were performed to determine the differences in bone length between groups, with significance set at P<.05. Results: Significant differences in lengths of multiple bones were detected between the high-dose group and other treatment groups and controls at each time interval. A significant difference in lengths of the tibias was also noted in the medium-treatment group, compared to controls. Mean reduction of bone length was first detected at 4 months and did not increase significantly over time. Conclusions: These data suggest that clinically significant bone shortening may occur as a result of high-dosage administration of {sup 153}Sm-EDTMP. Further investigation regarding the effects of bone-seeking radiopharmaceuticals on bone growth and physeal cartilage is warranted.

The linear rule of metal extraction

International Nuclear Information System (INIS)

Han Li; Yushuang Wang; Zhichun Chen; Shulan Meng

1988-01-01

On the basis of experimental results a linear rule for the solvent extraction of rare earths and yttrium over a definite range of acidity and metal ion concentration is found. Relations between the coefficients of the linear rule and initial acidity are presented for the extraction systems: HEH(EHP)-kerosene-HNO 3 -R(NO 3 ) 3 , HEH(EHP)-kerosene-HCl-RCl 3 , D2EHPA-n-heptane-HCl-RCl 3 , HEH(EHP)-n-heptane-HCl-RCl 3 , where R=La-Nd, Sm-Lu, Y; HEH(EHP)=momo(2-ethyl-hexyl)2-ethyl-hexyl phosphonate; D2EHPA=di(2-ethyl-hexyl) phosphoric acid. 3 refs.; 1 tab

Synthesis, characterization and fuel cell performance tests of boric acid and boron phosphate doped, sulphonated and phosphonated poly(vinyl alcohol) based composite membranes

Science.gov (United States)

Şahin, Alpay; Ar, İrfan

2015-08-01

The aim of this study is to synthesize a composite membrane having high proton conductivity, ion exchange capacity and chemical stability. In order to achieve this aim, poly(vinyl alcohol) (PVA) based composite membranes are synthesized by using classic sol-gel method. Boric acid (H3BO3) and boron phosphate (BPO4) are added to the membrane matrix in different ratios in order to enhance the membrane properties. Characterization tests, i.e; FT-IR analysis, mechanical strength tests, water hold-up capacities, swelling properties, ion exchange capacities, proton conductivities and fuel cell performance tests of synthesized membranes are carried out. As a result of performance experiments highest performance values are obtained for the membrane containing 15% boron phosphate at 0.6 V and 750 mA/cm2. Water hold-up capacity, swelling ratio, ion exchange capacity and proton conductivity of this membrane are found as 56%, 8%, 1.36 meq/g and 0.37 S/cm, respectively. These values are close to the values obtained ones for perfluorosulphonic acid membranes. Therefore this membrane can be regarded as a promising candidate for usage in fuel cells.

PNA-PEG modified silicon platforms as functional bio-interfaces for applications in DNA microarrays and biosensors.

Science.gov (United States)

Cattani-Scholz, Anna; Pedone, Daniel; Blobner, Florian; Abstreiter, Gerhard; Schwartz, Jeffrey; Tornow, Marc; Andruzzi, Luisa

2009-03-09

The synthesis and characterization of two types of silicon-based biofunctional interfaces are reported; each interface bonds a dense layer of poly(ethylene glycol) (PEG(n)) and peptide nucleic acid (PNA) probes. Phosphonate self-assembled monolayers were derivatized with PNA using a maleimido-terminated PEG(45). Similarly, siloxane monolayers were functionalized with PNA using a maleimido-terminated PEG(45) spacer and were subsequently modified with a shorter methoxy-terminated PEG(12) ("back-filling"). The long PEG(45) spacer was used to distance the PNA probe from the surface and to minimize undesirable nonspecific adsorption of DNA analyte. The short PEG(12) "back-filler" was used to provide additional passivation of the surface against nonspecific DNA adsorption. X-ray photoelectron spectroscopic (XPS) analysis near the C 1s and N 1s ionization edges was done to characterize chemical groups formed in the near-surface region, which confirmed binding of PEG and PNA to the phosphonate and silane films. XPS also indicated that additional PEG chains were tethered to the surface during the back-filling process. Fluorescence hybridization experiments were carried out with complementary and noncDNA strands; both phosphonate and siloxane biofunctional surfaces were effective for hybridization of cDNA strands and significantly reduced nonspecific adsorption of the analyte. Spatial patterns were prepared by polydimethylsiloxane (PDMS) micromolding on the PNA-functionalized surfaces; selective hybridization of fluorescently labeled DNA was shown at the PNA functionalized regions, and physisorption at the probe-less PEG-functionalized regions was dramatically reduced. These results show that PNA-PEG derivatized phosphonate monolayers hold promise for the smooth integration of device surface chemistry with semiconductor technology for the fabrication of DNA biosensors. In addition, our results confirm that PNA-PEG derivatized self-assembled carboxyalkylsiloxane films are

Ionic Copolymer-Magnetite Complexes for Magnetic Resonance Imaging and Drug Delivery

OpenAIRE

Zhang, Rui

2015-01-01

This thesis is focused on the design, synthesis and characterization of magnetite-ionic copolymer complexes as nanocarriers for drug delivery and magnetic resonance imaging. The polymers included phosphonate and carboxylate-containing graft and block copolymers. Oleic-acid coated magnetite nanoparticles (8-nm and 16-nm diameters) were investigated. Cisplatin and carboplatin were used as sample drugs. The potentials of the magnetite-ionomer complexes as dual drug delivery carriers and magneti...

Synthesis of novel deoxynucleoside S-methylphosphonic acids using S-(diisopropylphosphonomethyl)isothiouronium tosylate, a new equivalent of mercaptomethylphosphonate

Czech Academy of Sciences Publication Activity Database

Kóšiová, Ivana; Buděšínský, Miloš; Panova, Natalya; Rosenberg, Ivan

2011-01-01

Roč. 9, č. 8 (2011), s. 2856-2860 ISSN 1477-0520 R&D Projects: GA AV ČR KAN200520801; GA ČR GA202/09/0193; GA ČR GA203/09/0820; GA MŠk(CZ) LC06061 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonate internucleotide linkage * organosulfur compounds * NTP analogues * nucleosides * nucleotides Subject RIV: CC - Organic Chemistry Impact factor: 3.696, year: 2011

Acute effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate, on cardiovascular parameters in anaesthetized, artificially ventilated rats

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Yoshimasa [Department of Pharmacology, Graduate School of Medical Sciences, Nagoya City University, Nagoya (Japan); Itoh, Takeo, E-mail: titoh@med.nagoya-cu.ac.jp [Department of Pharmacology, Graduate School of Medical Sciences, Nagoya City University, Nagoya (Japan); Shiraishi, Hiroaki [Department of Forensic Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan); Maeno, Yoshitaka [Department of Forensic Medical Science, Graduate School of Medical Sciences, Nagoya City University, Nagoya (Japan); Arima, Yosuke; Torikoshi, Aiko; Namera, Akira [Department of Forensic Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan); Makita, Ryosuke [Department of Nursing, Faculty of Health Sciences, Hiroshima Cosmopolitan University, Hiroshima (Japan); Yoshizumi, Masao [Department of Cardiovascular Physiology and Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan); Nagao, Masataka [Department of Forensic Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan)

2013-10-01

The organophosphorus compound sarin irreversibly inhibits acetylcholinesterase. We examined the acute cardiovascular effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate (BIMP), in anaesthetized, artificially ventilated rats. Intravenous administration of BIMP (0.8 mg/kg; the LD50 value) induced a long-lasting increase in blood pressure and tended to increase heart rate. In rats pretreated with the non-selective muscarinic-receptor antagonist atropine, BIMP significantly increased both heart rate and blood pressure. In atropine-treated rats, hexamethonium (antagonist of ganglionic nicotinic receptors) greatly attenuated the BIMP-induced increase in blood pressure without changing the BIMP-induced increase in heart rate. In rats treated with atropine plus hexamethonium, intravenous phentolamine (non-selective α-adrenergic receptor antagonist) plus propranolol (non-selective β-adrenergic receptor antagonist) completely blocked the BIMP-induced increases in blood pressure and heart rate. In atropine-treated rats, the reversible acetylcholinesterase inhibitor neostigmine (1 mg/kg) induced a transient increase in blood pressure, but had no effect on heart rate. These results suggest that in anaesthetized rats, BIMP induces powerful stimulation of sympathetic as well as parasympathetic nerves and thereby modulates heart rate and blood pressure. They may also indicate that an action independent of acetylcholinesterase inhibition contributes to the acute cardiovascular responses induced by BIMP. - Highlights: • A sarin-like agent BIMP markedly increased blood pressure in anaesthetized rats. • Muscarinic receptor blockade enhanced the BIMP-induced increase in blood pressure. • Ganglionic nicotinic receptor blockade attenuated the BIMP-induced response. • Blockade of α- as well as β-receptors attenuated the BIMP-induced response.

Acute effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate, on cardiovascular parameters in anaesthetized, artificially ventilated rats

International Nuclear Information System (INIS)

Watanabe, Yoshimasa; Itoh, Takeo; Shiraishi, Hiroaki; Maeno, Yoshitaka; Arima, Yosuke; Torikoshi, Aiko; Namera, Akira; Makita, Ryosuke; Yoshizumi, Masao; Nagao, Masataka

2013-01-01

The organophosphorus compound sarin irreversibly inhibits acetylcholinesterase. We examined the acute cardiovascular effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate (BIMP), in anaesthetized, artificially ventilated rats. Intravenous administration of BIMP (0.8 mg/kg; the LD50 value) induced a long-lasting increase in blood pressure and tended to increase heart rate. In rats pretreated with the non-selective muscarinic-receptor antagonist atropine, BIMP significantly increased both heart rate and blood pressure. In atropine-treated rats, hexamethonium (antagonist of ganglionic nicotinic receptors) greatly attenuated the BIMP-induced increase in blood pressure without changing the BIMP-induced increase in heart rate. In rats treated with atropine plus hexamethonium, intravenous phentolamine (non-selective α-adrenergic receptor antagonist) plus propranolol (non-selective β-adrenergic receptor antagonist) completely blocked the BIMP-induced increases in blood pressure and heart rate. In atropine-treated rats, the reversible acetylcholinesterase inhibitor neostigmine (1 mg/kg) induced a transient increase in blood pressure, but had no effect on heart rate. These results suggest that in anaesthetized rats, BIMP induces powerful stimulation of sympathetic as well as parasympathetic nerves and thereby modulates heart rate and blood pressure. They may also indicate that an action independent of acetylcholinesterase inhibition contributes to the acute cardiovascular responses induced by BIMP. - Highlights: • A sarin-like agent BIMP markedly increased blood pressure in anaesthetized rats. • Muscarinic receptor blockade enhanced the BIMP-induced increase in blood pressure. • Ganglionic nicotinic receptor blockade attenuated the BIMP-induced response. • Blockade of α- as well as β-receptors attenuated the BIMP-induced response

Improving the Performance of Semiconductor Sensor Devices Using Surface Functionalization

Science.gov (United States)

Rohrbaugh, Nathaniel W.

As production and understanding of III-nitride growth has progressed, this class of material has been used for its semiconducting properties in the fields of computer processing, microelectronics, and LEDs. As understanding of materials properties has advanced, devices were fabricated to be sensitive to environmental surroundings such as pH, gas, or ionic concentration. Simultaneously the world of pharmaceuticals and environmental science has come to the age where the use of wearable devices and active environmental sensing can not only help us learn more about our surroundings, but help save lives. At the crossroads of these two fields work has been done in marrying the high stability and electrical properties of the III-nitrides with the needs of a growing sensor field for various environments and stimuli. Device architecture can only get one so far, and thus the need for well understood surface functionalization techniques has arisen in the field of III-nitride environmental sensing. Many existing schemes for functionalization involve chemistries that may be unfriendly to a biological environment, unstable in solution, or expensive to produce. One possible solution to these issues is the work presented here, which highlights a surface modification scheme utilizing phosphonic acid based chemistry and biomolecular attachment. This dissertation presents a set of studies and experiments quantifying and analyzing the response behaviors of AlGaN/GaN field effect transistor (FET) devices via their interfacial electronic properties. Additional investigation was done on the modification of these surfaces, effects of stressful environmental conditions, and the utility of the phosphonic acid surface treatments. Signals of AlGaN/GaN FETs were measured as IDrain values and in the earliest study an average signal increase of 96.43% was observed when surfaces were incubated in a solution of a known recognition peptide sequence (SVSVGMKPSPRP). This work showed that even without

Transition state analogue imprinted polymers as artificial amidases for amino acid p-nitroanilides: morphological effects of polymer network on catalytic efficiency.

Science.gov (United States)

Mathew, Divya; Thomas, Benny; Devaky, K S

2017-11-13

The morphology of the polymer network - porous/less porous - plays predominant role in the amidase activities of the polymer catalysts in the hydrolytic reactions of amino acid p-nitroanilides. Polymers with the imprints of stable phosphonate analogue of the intermediate of hydrolytic reactions were synthesized as enzyme mimics. Molecular imprinting was carried out in thermodynamically stable porogen dimethyl sulphoxide and unstable porogen chloroform, to investigate the morphological effects of polymers on catalytic amidolysis. It was found that the medium of polymerization has vital influence in the amidase activities of the enzyme mimics. The morphological studies of the polymer catalysts were carried out by scanning electron microscopy and Bruner-Emmett-Teller analysis. The morphology of the polymer catalysts and their amidase activities are found to be dependent on the composition of reaction medium. The polymer catalyst prepared in dimethyl sulphoxide is observed to be efficient in 1:9 acetonitrile (ACN)-Tris HCl buffer and that prepared in chloroform is noticed to be stereo specifically and shape-selectively effective in 9:1 ACN-Tris HCl buffer. The solvent memory effect in catalytic amidolysis was investigated using the polymer prepared in acetonitrile.

Investigation of the acid-base and electromigration properties of 5-azacytosine derivatives using capillary electrophoresis and density functional theory calculations.

Science.gov (United States)

Geffertová, Denisa; Ali, Syed Tahir; Šolínová, Veronika; Krečmerová, Marcela; Holý, Antonín; Havlas, Zdeněk; Kašička, Václav

2017-01-06

Capillary electrophoresis (CE) and quantum mechanical density functional theory (DFT) were applied to the investigation of the acid-base and electromigration properties of important compounds: newly synthesized derivatives of 5-azacytosine - analogs of efficient antiviral drug cidofovir. These compounds exhibit a strong antiviral activity and they are considered as potential new antiviral agents. For their characterization and application, it is necessary to know their acid-base properties, particularly the acidity constants (pK a ) of their ionogenic groups (the basic N 3 atom of the triazine ring and the acidic phosphonic acid group in the alkyl chain). First, the mixed acidity constants (pK a mix ) of these ionogenic groups and the ionic mobilities of these compounds were determined by nonlinear regression analysis of the pH dependence of their effective electrophoretic mobilities. Effective mobilities were measured by CE in a series of background electrolytes in a wide pH range (2.0-10.5), at constant ionic strength (25mM) and constant temperature (25°C). Subsequently, the pK a mix values were recalculated to thermodynamic pK a values using the Debye-Hückel theory. The thermodynamic pK a value of the NH + moiety at the N 3 atom of the triazine ring was found to be in the range 2.82-3.30, whereas the pK a of the hydrogenphosphonate group reached values from 7.19 to 7.47, depending on the structure of the analyzed compounds. These experimentally determined pK a values were in good agreement with those calculated by quantum mechanical DFT. In addition, DFT calculations revealed that from the four nitrogen atoms in the 5-azacytosine moiety, the N 3 atom of the triazine ring is preferentially protonated. Effective charges of analyzed compounds ranged from zero or close-to-zero values at pH 2 to -2 elementary charges at pH≥9. Ionic mobilities were in the range (-16.7 to -19.1)×10 -9 m 2 V -1 s -1 for univalent anions and in the interval (-26.9 to -30.3)×10 -9 m

Study of recovery and stability of derivatized gliphosate and AMPA in soil using national resins

OpenAIRE

Souza, Tomaz Alves de; Matta, Marcia Helena de Rizzo da; Montagner, Émerson; Abreu, Adley Bergson Gonçalves de

2006-01-01

In the present paper we studied the recoveries of glyphosate, N-(phosphonomethyl)glycine (GLY) and its major metabolite, (aminomethyl)phosphonic acid (AMPA) in soil using national (Brazilian) ion-exchange resins, derivatization by a mixture of trifluoroacetic anhydride and trifluoroethanol and analyses by GC-MS. The quantification limits were 12 ng.g-1 for both compounds and the methodology showed a range of recuperation from 85 to 94% with coefficients of variation (CV) ranging from 4.07 to ...

Corrosion inhibitors for carbon steel surfaces in contact with fresh water

International Nuclear Information System (INIS)

Abubacker, K.M.; Mehta, C.T.; Pillai, B.P.

1985-01-01

Technical evaluation of indigenously available proprietary formulations as well as some non-proprietary chemicals such as phosphates, silicates, borax, benzoic acid, amines, amino-methylene phosphonates etc. have been carried out, with a view, to find the best combination for use in cooling water systems of the Heavy Water Projects of the Department of Atomic Energy. Material compatibility experiments were carried out through laboratory experiments as well as small 10 litre capacity test assembly simulating plant conditions. (author)

A functional assay to measure postsynaptic gamma-aminobutyric acidB responses in cultured spinal cord neurons: Heterologous regulation of the same K+ channel

Energy Technology Data Exchange (ETDEWEB)

Kamatchi, G.L.; Ticku, M.K. (Univ. of Texas Health Science Center, San Antonio (USA))

1991-02-01

The stimulation of postsynaptic gamma-aminobutyric acid (GABA)B receptors leads to slow inhibitory postsynaptic potentials due to the influx of K(+)-ions. This was studied biochemically, in vitro in mammalian cultured spinal cord neurons by using 86Rb as a substitute for K+. (-)-Baclofen, a GABAB receptor agonist, produced a concentration-dependent increase in the 86Rb-influx. This effect was stereospecific and blocked by GABAB receptor antagonists like CGP 35 348 (3-aminopropyl-diethoxymethyl-phosphonic acid) and phaclofen. Apart from the GABAB receptors, both adenosine via adenosine1 receptors and 5-hydroxytryptamine (5-HT) via 5-HT1 alpha agonists also increased the 86Rb-influx. These agonists failed to show any additivity between them when they were combined in their maximal concentration. In addition, their effect was antagonized specifically by their respective antagonists without influencing the others. These findings suggest the presence of GABAB, adenosine1 and 5-HT1 alpha receptors in the cultured spinal cord neurons, which exhibit a heterologous regulation of the same K(+)-channel. The effect of these agonists were antagonized by phorbol 12,13-didecanoate, an activator of protein kinase C, and pretreatment with pertussis toxin. This suggests that these agonists by acting on their own receptors converge on the same K(+)-channel through the Gi/Go proteins. In summary, we have developed a biochemical functional assay for studying and characterizing GABAB synaptic pharmacology in vitro, using spinal cord neurons.

Sequence Classification: 488452 [

Lifescience Database Archive (English)

Full Text Available TMB Non-TMH TMB TMB TMB TMB >gi|28869747|ref|NP_792366.1| phosphonates ABC transpor...ter, periplasmic phosphonates-binding protein || http://www.ncbi.nlm.nih.gov/protein/28869747 ...

Sequence Classification: 206174 [

Lifescience Database Archive (English)

Full Text Available TMB Non-TMH TMB TMB TMB TMB >gi|16124617|ref|NP_419181.1| phosphonates ABC transpor...ter, periplasmic phosphonates-binding protein || http://www.ncbi.nlm.nih.gov/protein/16124617 ...

Recovery of phosphonate surface contaminants from glass using a simple vacuum extractor with a solid-phase microextraction fiber

International Nuclear Information System (INIS)

Groenewold, Gary S.; Scott, Jill R.; Rae, Catherine

2011-01-01

operational equilibrium is being approached. Fractional recovery decreased with increasing time between exposure and sampling; however, recordable quantities of the phosphonates could be collected three weeks after exposure.

(1 H, 13 C and 31 P) NMR of phosphonic acid derivatives

International Nuclear Information System (INIS)

Campos, Valdevino; Costa, Valentim E. Uberti

1991-01-01

In the last years the development of phosphates analogues in the medical and agricultural pesticides has being very expressive. 1 H, 13 C and mainly 31 P NMR are used for stereochemical and conformational analysis, and reactivity studies on the compounds resulting from those chemical processes

40 CFR 704.95 - Phosphonic acid, [1,2-ethanediyl-bis[nitrilobis-(methylene)

Science.gov (United States)

2010-07-01

... of the substance for which the report is submitted. (ii) Company name and headquarters address. (iii... transaction; the import site may in some cases be the organization's headquarters office in the United States... Abstracts Service Registry Number of the substance for which the report is submitted. (ii) Company name and...

Two-stage supported liquid membrane method for the separation of carrier-free {sup 90}Y from {sup 90}Sr using KSM-17 and CMPO as carriers

Energy Technology Data Exchange (ETDEWEB)

Dhami, P S; Naik, P W; Dudwadkar, N L; Kannan, R; Achuthan, P V; Dakshinamoorthy, A; Jambunathan, U; Munshi, S K; Dey, P K [Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai (India); Pandey, Usha; Venkatesh, Meera [Radiopharmaceuticals Division, Bhabha Atomic Research Centre, Mumbai (India)

2007-07-01

A two stage supported liquid membrane system is developed for the separation of carrier free {sup 90}Y from {sup 90}Sr for therapeutic applications. The feed containing {sup 90}Sr-{sup 90}Y in nitric acid solution at pH 2 is placed in the feed compartment and transported across a polytetrafluoroethylene membrane containing 2-ethyhexyl2ethylhexyl phosphonic acid to a 4M HNO{sub 3} receiver phase. This is then transported across another polytetrafluoroethylene membrane containing octyl phenyl N,N-diisobutylcarbamoyl methylphosphene oxide to another receiving phase, 1 M acetic acid. This has been implemented on simultaneous and sequential modes with very good yield. The second stage will act as a barrier for {sup 90}Sr, and will improve the product purity. (author)

The Impact and Oxidation Survival of Selected Meteoritic Compounds: Signatures of Asteroid Organic Material on Planetary Surfaces

Science.gov (United States)

Cooper, George; Horz, Fred; Oleary, Alanna; Chang, Sherwood

2013-01-01

Polar, non-volatile organic compounds may be present on the surfaces (or near surfaces) of multiple Solar System bodies. If found, by current or future missions, it would be desirable to determine the origin(s) of such compounds, e.g., asteroidal or in situ. To test the possible survival of meteoritic compounds both during impacts with planetary surfaces and under subsequent (possibly) harsh ambient conditions, we subjected known meteoritic compounds to relatively high impact-shock pressures and/or to varying oxidizing/corrosive conditions. Tested compounds include sulfonic and phosphonic acids (S&P), polyaromatic hydrocarbons (PAHs) amino acids, keto acids, dicarboxylic acids, deoxy sugar acids, and hydroxy tricarboxylic acids (Table 1). Meteoritic sulfonic acids were found to be relatively abundant in the Murchison meteorite and to possess unusual S-33 isotope anomalies (non mass-dependent isotope fractionations). Combined with distinctive C-S and C-P bonds, the S&P are potential signatures of asteroidal organic material.

The physical and chemical characteristics of 175Yb-EDTMP labelled compound

International Nuclear Information System (INIS)

Azmairit Aziz; Marlina; Muhammad Basit Febrian

2010-01-01

Bone pain is a common complication for patient with bone metastases from breasts, prostate and lung cancers. The derivative of phosphonate groups, i.e. diphosphonate as well as poly phosphonate ligands e.g. EDTMP have high affinity in bone matrix. The labeled compound of 175 Yb-EDTMP can be used as an alternative radiopharmaceutical for bone pain palliation. The compound of 175 Yb-EDTMP can be produced by labeling of ethylenediamine tetramethylene phosphonic acid (EDTMP) with itterbium-175 ( 175 YbCl 3 ). Before 175 Yb-EDTMP is used for bone pain palliation in nuclear medicine, the compound have to be characterized to full fill the criteria of the good radiopharmaceutical. The physical and chemical characteristics of 175 Yb-EDTMP had been studied. It consists of: pH, solution clearity, the radiochemical purity that was determined by paper chromatography and paper electrophoresis techniques, electricity charge was determined by paper electrophoresis, stability, lipophilicity of 175 Yb-EDTMP was obtained by determination of octanol-water partition and the plasma binding protein was in-vitro investigated with precipitation method using 5% of trichloroacetic acid solution, and the binding to hydroxyapatite. From the experiment, it was obtained that the 175 Yb-EDTMP solution has the pH of 7, clear, the radiochemical purity of 98.66 ± 0.53%, and the negative electric charge. The compound of 175 Yb-EDTMP has lipophilicity (P) of 0.0135 ± 0.003%, the human plasma binding protein of 8.94 ± 0.66%, and the hydroxyapatite binding of 94.78 ± 2.16%. Stability evaluation indicated that 175 Yb-EDTMP solution was still stable for nine days at room temperature with the radiochemical purity more than 95% (98.62 ± 0.83%). This study expects that 175 Yb-EDTMP compound can fulfill the requirement as radiopharmaceutical for use in palliative treatment of painful bone metastases and supports the development of nuclear medicine in Indonesia. (author)

Synthesis and X-ray Powder Structure of a New Pillared Layered Cadmium Phosphonate, Giving Evidence that the Intercalation of Alkylamines into Cd(O(3)PR).H(2)O Is Topotactic.

Science.gov (United States)

Fredoueil, Florence; Massiot, Dominique; Janvier, Pascal; Gingl, Franz; Bujoli-Doeuff, Martine; Evain, Michel; Clearfield, Abraham; Bujoli, Bruno

1999-04-19

A new pillared layered phosphonate, cadmium 2-aminoethylphosphonate, Cd(O(3)PC(2)H(4)NH(2)) (1), has been synthesized, and its structure was solved ab initio from X-ray powder diffraction data and refined by Rietveld methods. Compound 1 is orthorhombic: space group Pna2(1), a = 15.4643(2) Å, b = 5.16512(7) Å, c = 6.27650(8) Å, and Z = 4. Its layer arrangement is similar to that in Cd(O(3)PR).H(2)O, except that the water molecule coordinated to cadmium in Cd(O(3)PR).H(2)O is replaced by the nitrogen atom from the amino ends of the ethyl chains borne by phosphorus of the upper and lower layers. The strong similarity of the IR, (31)P, and (113)Cd NMR data for Cd(O(3)PC(2)H(4)NH(2)) and Cd(O(3)PCH(3)).n-NH(2)C(4)H(9) clearly shows the topotactic character of the intercalation of n-alkylamines in the dehydrated form of Cd(O(3)PR).H(2)O to yield Cd(O(3)PR).n-NH(2)R'.

Determination of acid-base dissociation constants of amino- and guanidinopurine nucleotide analogues and related compounds by capillary zone electroforesis

Czech Academy of Sciences Publication Activity Database

Šolínová, Veronika; Kašička, Václav; Koval, Dušan; Česnek, Michal; Holý, Antonín

2006-01-01

Roč. 27, č. 5/6 (2006), s. 1006-1019 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA203/03/0716; GA ČR(CZ) GA203/04/0098; GA AV ČR(CZ) 1QS400550501; GA MŠk(CZ) 1M0508; GA ČR(CZ) GA203/05/2539 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * capillary electrophoresis * dissociation constant Subject RIV: CC - Organic Chemistry Impact factor: 4.101, year: 2006

DAPPA grafted polymer: an efficient solid phase extractant for U(VI), Th(IV) and La(III) from acidic waste streams and environmental samples.

Science.gov (United States)

Raju, Ch Siva Kesava; Subramanian, M S

2005-07-15

A new class of polymeric resin has been synthesized by grafting Merrifield chloromethylated resin with (dimethyl amino-phosphono-methyl)-phosphonic acid (MCM-DAPPA), for the preconcentration of U(VI), Th(IV) and La(III) from both acidic wastes and environmental samples. The various chemical modification steps involved during grafting process are characterized by FT-IR spectroscopy, (31)P and (13)C-CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNS/O elemental analysis. The water regain capacity data for the grafted polymer are obtained from thermo-gravimetric (TG) analysis. The influence of various physico-chemical parameters during the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The significant feature of this grafted polymer is its ability to extract both actinides and lanthanides from high-level acidities as well as from near neutral conditions. The resin shows very high sorption capacity values of 2.02, 0.89 and 0.54mmolg(-1) for U(VI), 1.98, 0.63 and 0.42mmolg(-1) for Th(IV) and 1.22, 0.39 and 0.39mmolg(-1) for La(III) under optimum pH, HNO(3) and HCl concentration, respectively. The grafted polymer shows faster phase exchange kinetics (99.5% recovery using 1M (NH(4))(2)CO(3), as eluent. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) from sea water and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.9% R.S.D. reflecting the reproducibility and reliability of the developed method.

Research on performance evaluation and anti-scaling mechanism of green scale inhibitors by static and dynamic methods

International Nuclear Information System (INIS)

Liu, D.

2011-01-01

Increasing environmental concerns and discharge limitations have imposed additional challenges in treating process waters. Thus, the concept of 'Green Chemistry' was proposed and green scale inhibitors became a focus of water treatment technology. Finding some economical and environmentally friendly inhibitors is one of the major research focuses nowadays. In this dissertation, the inhibition performance of different phosphonates as CaCO 3 scale inhibitors in simulated cooling water was evaluated. Homo-, co-, and ter-polymers were also investigated for their performance as Ca-phosphonate inhibitors. Addition of polymers as inhibitors with phosphonates could reduce Ca-phosphonate precipitation and enhance the inhibition efficiency for CaCO 3 scale. The synergistic effect of poly-aspartic acid (PASP) and Poly-epoxy-succinic acid (PESA) on inhibition of scaling has been studied using both static and dynamic methods. Results showed that the anti-scaling performance of PASP combined with PESA was superior to that of PASP or PESA alone for CaCO 3 , CaSO 4 and BaSO 4 scale. The influence of dosage, temperature and Ca 2+ concentration was also investigated in simulated cooling water circuit. Moreover, SEM analysis demonstrated the modification of crystalline morphology in the presence of PASP and PESA. In this work, we also investigated the respective inhibition effectiveness of copper and zinc ions for scaling in drinking water by the method of Rapid Controlled Precipitation (RCP). The results indicated that the zinc ion and copper ion were high efficient inhibitors of low concentration, and the analysis of SEM and IR showed that copper and zinc ions could affect the calcium carbonate germination and change the crystal morphology. Moreover, the influence of temperature and dissolved CO 2 on the scaling potential of a mineral water (Salvetat) in the presence of copper and zinc ions was studied by laboratory experiments. An ideal scale inhibitor should be a solid form

Selectivity in stripping of alkali-metal cations from crown ether carboxylate complexes

International Nuclear Information System (INIS)

Bartsch, R.A.; Walkowiak, W.; Robison, T.W.

1992-01-01

To probe the effect of structural variations within the ionophore upon the efficiency and selectivity of solvent extraction, a variety of crown ether carboxylic acids and phosphonic acid monoesters have been synthesized. In other studies the influence of the organic diluent upon extraction efficiency and selectivity has been probed for such proton-ionizable crown ethers. In the present investigation, attention is focused upon selectivity in the stripping step. Although the efficiency of metal ion stripping is often examined in solvent extraction studies, the selectivity of competitive metal ion release under different conditions is much less frequently considered. In this study, competitive stripping of metal ions from chloroform solutions of five-alkali-metal crown ether carboxylates by varying concentrations of aqueous hydrochloric acid is examined. Alkali metals used were Li, Na, K, Rb, and Cs

COOH-functionalisation of silica particles

Energy Technology Data Exchange (ETDEWEB)

Majewski, Peter, E-mail: peter.majewski@unisa.edu.au [School of Advanced Manufacturing and Mechanical Engineering, Mawson Institute, University of South Australia, Adelaide (Australia); Albrecht, Trent [Ian Wark Research Institute, University of South Australia, Adelaide (Australia); Weber, Siegfried [Department of Biotechnology, University of Applied Sciences, Mannheim (Germany)

2011-09-01

In this study COOH-functionalised silica is synthesised using phosphonateN-(phosphonomethyl)iminodiacetic acid (PMIDA) in an aqueous solution. The presence of PMIDA on the silica particles was verified using Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and titration. Experimentally, surface concentrations of COOH functional groups of up to about 3 mmol/g{sub silica} were achieved, whereas theoretical calculation of the maximum COOH functional group concentration gave about 1 mmol/g{sub silica}. The discrepancy may be caused by PMIDA multilayer formation on the particle.

Synthesis, solubilization, and surface functionalization of highly fluorescent quantum dots for cellular targeting through a small molecule

Science.gov (United States)

Galloway, Justin F.

To achieve long-term fluorescence imaging with quantum dots (QDs), a CdSe core/shell must first be synthesized. The synthesis of bright CdSe QDs is not trivial and as a consequence, the role of surfactant in nucleation and growth was investigated. It was found that the type of surfactant used, either phosphonic or fatty acid, played a pivotal role in the size of the CdSe core. The study of surfactant on CdSe synthesis, ultimately led to an electrical passivation method that utilized a short-chained phosphonic acid and highly reactive organometallic precursors to achieve high quantum yield (QY) as has been previously described. The synthesis of QDs using organometallic precursors and a phosphonic acid for passivation resulted in 4 out of 9 batches of QDs achieving QYs greater than 50% and 8 out of 9 batches with QYs greater than 35%. The synthesis of CdSe QDs was done in organic solutions rendering the surface of the particle hydrophobic. To perform cell-targeting experiments, QDs must be transferred to water. The transfer of QDs to water was successfully accomplished by using single acyl chain lipids. A systematic study of different lipid combinations and coatings demonstrated that 20-40 mol% single acyl chained lipids were able to transfer QDs to water resulting in monodispersed, stable QDs without adversely affecting the QY. The advantage to water solubilization using single acyl chain lipids is that the QD have a hydrodynamic radius less than 15 nm, QYs that can exceed 50% and additional surface functionalization can be down using the reactive sites incorporated into the lipid bilayer. QDs that are bright and stable in water were studied for the purpose of targeting G protein-coupled Receptors (GPCR). GPCRs are transmembrane receptors that internalize extracellular cues, and thus mediate signal transduction. The cyclic Adenosine Monophosphate Receptor 1 of the model organism Dictyostelium disodium was the receptor of interest. The Halo protein, a genetically

Bone marrow ablation with Ho-166 pharmaceuticals as preparation for bone marrow transplants

International Nuclear Information System (INIS)

Parks, N.J.; Kawakami, T.; Avila, M.; White, R.; Cain, G.; Moore, P.F.

1991-01-01

Bone marrow ablation is required preparation for leukemia patients where bone marrow transplantation is to be the therapeutic modality. Presently, the total body irradiation that is used produces appreciable morbidity in terms of radiation sickness, but an evenly distributed dose to marrow. The authors have shown in Beagles that bone-seeking radiolanthanide (Ho-166, t 1/2 = 25 h, 1.8 MeB beta, carrier added) phosphonic acid chelates can be used to completely ablate bone marrow with little morbidity. The research plan, incorporating bone marrow ablation with bone-seeking radionuclides and in vitro purging of aspirated leukemic marrow for use in autologous marrow transplants, is presented. Phosphonic acid complexes of Sm-153 also localize in the skeleton and have found use in the palliation of bone pain. However, the dose distribution is uneven because these radiopharmaceuticals distribute according to available surface; 2-4 times the skeletal average in trabecular vs cortical bone. Thus, the marrow dose can vary. The authors' research group and the Radiation Interactions Division of NIST have announced the discovery that beta radiation-induced excited electrons are trapped in the hydroxyapatite mineral of bone and provide a potential direct dosimetric method for marrow dose when combined with routine bone marrow (and included bone) biopsies. The overall research plan sets the hypothesis that reduced morbidity marrow ablation can be successfully followed by bone marrow transplantation (BMT) with autologous marrow purged in vitro by antibody-targeted alpha emitters

Study of Ca-ATMP precipitation in the presence of magnesium ion.

Science.gov (United States)

Tantayakom, V; Fogler, H Scott; de Moraes, F F; Bualuang, M; Chavadej, S; Malakul, P

2004-03-16

ATMP (aminotri(methylenephosphonic acid)), a phosphonate scale inhibitor used in the petroleum industry, was used as a model scale inhibitor in this study. One of the goals of this work was to determine the range of conditions under which Mg ions, which are formed in reservoir formations containing dolomite, modulate the formation of Ca-ATMP precipitate as a scale inhibitor. The results revealed that the amount of ATMP precipitated decreased with addition of Mg ions in solution at all values of the solution pH. Furthermore, an increase in both the solution pH and the concentration of the divalent cations in solution resulted in a change of the molar ratio of (Ca + Mg) to ATMP in the precipitates. At a low solution pH (pH 1.5), Mg ions had little effect on the composition of the Ca-ATMP precipitate. However, at higher values of the solution pH (pH 4 and 7), the Ca to ATMP molar ratio in the precipitates decreased with increasing concentration of the Mg. Here it was found that Mg ions replaced Ca ions on available reactive sites of ATMP molecules. These results determined the limits of the Mg ion concentration, which affects the precipitation of Ca-ATMP, Mg-ATMP, and (Ca + Mg)-ATMP. The dissolution of the scale inhibitors was studied using a rotating disk reactor. These experiments showed that the total divalent cation molar ratio (Ca + Mg) to ATMP in the precipitates is the primary factor that controls the rate of dissolution (release) of the phosphonate precipitates. The phosphonate precipitate dissolution rates decreased as the molar ratio of divalent cations to ATMP in the precipitates increased.

Complexes of palladium(II with 1-phenyl-1-hydroxymethylene bisphosphoniс acid and their antitumor activity

Directory of Open Access Journals (Sweden)

O. M. Kozachkova

2017-02-01

Full Text Available Complex formation of K2[PdCl4] with 1-phenyl-1-hydroxymethylene bisphosphonic acid (PhHMBP, H4L has been studied by pH potentiometry, electron and NMR spectroscopy. It was found that in aqueous solution with physiological concentration of chlorine anions (0.15 mol/l KCl, anionic complexes of the equimolar compositions [PdHLCl2]3- (lgβ = 24.51 (0.3 and [PdLCl2]4- (lgβ = 20.74 (0.02 are formed. In the first coordination sphere palladium was surrounded by two oxygen atoms of two phosphonic groups of the bidentately coordinated ligand with closure of six-membered [O, O] ring, and two chlorine anions. The formation of palladium(II equimolar complexes with PhHMBP and bidentate coordination of the ligand to the central metal cation was confirmed by 31P NMR spectroscopy. Cytotoxic activity (IC50 based on metal content of the synthesized Pd(II complexes with PhHMBP against human MG-63 osteosarcoma and MCF-7 mammary tumor cells was compared with cisplatin on in vitro models. It was established that cytotoxic activity of the Pd complexes was lower than that of cisplatin. The acute toxicity (LD50 based on metal content of solutions of Pd(II complexes with PhHMBP was found to be lower compared to cisplatin. It was shown that the use of solutions of palladium(II complexes with PhHMBP inhibited tumor growth in mice with sarcoma 180.

Characterization of linear alkyl phosphonate self-assembled on perovskite substrate

Science.gov (United States)

Lazauskas, A.; Baltrusaitis, J.; Grigaliūnas, V.; Prosyčevas, I.

2015-07-01

In recent years, functional material surface functionalization has grown into an expanding area of research due to the development and design of advanced systems and devices for key areas in biotechnology, smart sensing, environmental applications and manufacturing. In this work, NdNiO3 surface was functionalized with octadecylphosphonic acid (ODP) using liquid phase reaction to attain superhydrophobic properties. The resulting ODP modified surface exhibited dual-scale roughness with a stable static contact angle of 170 ± 2°. Electron microscopy micrographs of ODP crystals formed revealed a non-uniform lateral growth characteristics. The presence of ODP hydrocarbon chains was confirmed using Fourier transform infrared spectroscopy with characteristic peaks at 2924 cm-1 and 2851 cm-1.

Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

KAUST Repository

Ma, Ting

2011-03-09

A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

Magnesium doped gallium phosphonates Ga{sub 1-x}Mg{sub x}[H{sub 3+x}(O{sub 3}PCH{sub 2}){sub 3}N] (x = 0, 0.20) and the influence on proton conductivity

Energy Technology Data Exchange (ETDEWEB)

Homburg, Thomas; Reinsch, Helge; Stock, Norbert [Institut fuer Anorganische Chemie, Christian-Albrechts-Universitaet, Kiel (Germany); Tschense, Carsten B.L.; Senker, Juergen [Dept. of Inorganic Chemistry III, University of Bayreuth (Germany); Wolkersdoerfer, Konrad; Wark, Michael [Institut fuer Chemie, Carl von Ossietzky Universitaet Oldenburg (Germany); Toebbens, Daniel; Zander, Stefan [Helmholtz-Zentrum Berlin fuer Materialien und Energie GmbH, Berlin (Germany)

2018-02-01

In our contribution to the development of new proton conductive coordination polymers (CPs) we focus on the impact of a partial replacement of Ga{sup 3+} by Mg{sup 2+}. This approach should come along with the introduction of additional protons due to charge balances. In a first step we have synthesized an isostructural compound to the literature known compound AlH{sub 3}P3N [H{sub 6}P3N = nitrilotris(methylene)triphosphonic acid], where Al{sup 3+} is replaced by Ga{sup 3+}, since all attempts to incorporate Mg{sup 2+} ions directly into AlH{sub 3}P3N were not successful. The relative amount of Mg{sup 2+} and Ga{sup 3+} was established by EDX analysis. Rietveld refinement of the synchrotron data located the Ga{sup 3+} and Mg{sup 2+} ions on a split position, proving the disordered incorporation of the Mg{sup 2+} ions. Solid-state NMR spectroscopy confirms a disordered protonation of the phosphonate groups as well and shows that all amine groups are protonated. In order to investigate the effect on the proton conductivity the compounds Ga[H{sub 3}(O{sub 3}PCH{sub 2}){sub 3}N], denoted GaH{sub 3}P3N as well as Ga{sub 0.80}Mg{sub 0.20}[H{sub 3.20}(O{sub 3}PCH{sub 2}){sub 3}N], denoted GaMgH{sub 3.20}P3N, were characterized by electrochemical impedance spectroscopy (EIS). Arrhenius behavior in the investigated temperature range (70-130 C) was found for both compounds (activation energies of E{sub a} = 0.15 eV for GaH{sub 3}P3N and 0.17 eV for GaMgH{sub 3.20}P3N). The GaMgH{sub 3.20}P3N sample shows a reduced proton mobility (σ = 1.2 x 10{sup -4} S.cm{sup -1}) of about one order of magnitude in comparison to GaH{sub 3}P3N (σ = 1.0 x 10{sup -3} S.cm{sup -1}). (copyright 2018 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Bone uptake by di and tetraphosphonates labeled with Rhenium-188

International Nuclear Information System (INIS)

Faintuch, B.L.; Osso, J.A. Jr.; Muramoto, E.; Faintuch, S.

2002-01-01

MDP (methylenediphosphonate) and HEDP (hydroxyethylidenediphosphonate), both diphosphonates, and EDTMP (ethylenediamine tetramethylene phosphonic acid) a tetraphosphonate ligand, have been labeled with 188 Re for use in metastatic bone-pain palliation. The aim of this study was a comparison between the three complexes 188 Re-MDP, 188 Re-HEDP and 188 Re-EDTMP concerning the complexation conditions, in order to achieve maximum yield, stability and bone uptake. Methods: MDP was dissolved in water and HEDP and EDTMP were dissolved in NaOH 1N followed by decreasing pH with HCl 1N. To all mixtures stannous chloride and 188 ReO 4 were added in a nitrogen atmosphere. The preparations were heated in a boiling water bath for 15 min. The yields as well as the radiochemical stability were estimated by ITLC. Different concentrations of phosphonates and stannous chloride were evaluated. Biodistribution studies in swiss mice were done for the three 188 Re-phosphonates that presented the best radiochemical yield. Results: For 188 Re-MDP and 188 Re-HEDP the optimal ligand concentration for maximum complexation was 30 mg whereas for 188 Re-EDTMP, it was 40 mg. The best amount of SnCl 2 .2H 2 O was 2 mg/mL for MDP, 3 mg/mL for HEDP and 1 mg/mL for EDTMP. In these conditions the three complexes showed a complexation yield above 95%. All of them presented 4-hour radiochemical stability without the need for ascorbic acid solution, but for 24 hours this stability existed only in the presence of that substance otherwise re-oxidation of 188 Re occurred. All products showed a great uptake by the kidneys. 188 Re-EDTMP had the greatest uptake by the bone (3.13 ± 0.18% ID/g) followed by 188 Re-MDP (1.18 ± 0.05%ID/g) and 188 Re-HEDP (1.03 ± 0.12 %ID/g), 4 hour postinjection. 188 Re-EDTMP displayed a bone/muscle ratio of 28.5, 188 Re-MDP 4.9 and 188 Re-HEDP 4.9. Conclusion: 188 Re-EDTMP demonstrated the best potential as a radiopharmaceutical for bone cancer pain relief, encouraging further

Extraction of U(VI), Th(IV), and La(III) from acidic streams and geological samples using AXAD-16-POPDE polymer

Energy Technology Data Exchange (ETDEWEB)

Prabhakaran, D.; Subramanian, M.S. [Indian Institute of Technology, Department of Chemistry, Chennai 600 036 (India)

2004-10-01

A new chromatographic extraction method has been developed using Amberlite XAD-16 (AXAD-16) resin chemically modified with (3-hydroxyphosphinoyl-2-oxo-propyl)phosphonic acid dibenzyl ester (POPDE). The chemically modified polymer was characterized by {sup 13}C CPMAS and {sup 31}P solid-state NMR, Fourier Transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis. Extraction studies performed for U(VI), Th(IV), and La(III) showed good distribution ratio (D) values of approximately 10{sup 3}, even under high acidities (1-4 M). Various physiochemical parameters that influence the quantitative metal ion extraction were optimized by static and dynamic methods. Data obtained from kinetic studies revealed that a time duration of {<=}10 min was sufficient to achieve complete metal ion extraction. Maximum metal sorption capacity values under optimum pH conditions were found to be 1.38, 1.33, and 0.75 mmol g{sup -1} for U(VI), Th(IV), and La(III), respectively. Interference studies performed in the presence of concentrated diverse ions and electrolyte species showed quantitative analyte recovery with lower limits of analyte detection being 10 and 20 ng cm{sup -3} for U(VI) and both Th(IV) and La(III), respectively. Sample breakthrough studies performed on the extraction column showed an enrichment factor value of 330 for U(VI) and 270 for Th(IV) and La(III), respectively. Analyte desorption was effective using 15 cm{sup 3} of 1 M (NH{sub 4}){sub 2}CO{sub 3} with >99.8% analyte recovery. The analytical applicability of the developed resin was tested with synthetic mixtures mimicking nuclear spent fuels, seawater compositions and real water and geological samples. The rsd values of the data obtained were within 5.2%, thereby reflecting the reliability of the developed method. (orig.)

Thermodynamic and microscopic equilibrium constants of molecular species formed from pyridoxal 5'-phosphate and 2-amino-3-phosphonopropionic acid in aqueous and D2O solution

International Nuclear Information System (INIS)

Szpoganicz, B.; Martell, A.E.

1984-01-01

Schiff base formation between pyridoxal 5'-phosphate (PLP) and 2-amino-3-phosphonopropionic acid (APP) has been investigated by measurement of the corresponding NMR and electronic absorption spectra. A value of 0.26 was found for the formation constant of the completely deprotonated Schiff base species, and is much smaller than the values reported for pyridoxal-β-chloroalanine and pyridoxal-O-phosphoserine. The protonation constants for the aldehyde and hydrate forms of PLP were determined in D 2 O by measurement of the variation of chemical shifts with pD (pH in D 2 O). The hydration constants of PLP were determined in a pD range 2-12, and species distributions were calculated. The protonation constants of the APP-PLP Schiff base determined by NMR in D 2 O were found to have the log values 12.54, 8.10, 6.70, and 5.95, and the species distributions were calculated for a range of pD values. Evidence is reported for hydrogen bonding involving the phosphate and phosphonate groups of the diprotonated Schiff base. The cis and trans forms of the Schiff bases were distinguished with the aid of the nuclear Overhauser effect. 43 references, 9 figures, 3 tables

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

Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyltrimethylsilane and triphenylphosphine

Directory of Open Access Journals (Sweden)

Fei Wang

2014-02-01

Full Text Available Background: 1,1-Difluoroalkenes cannot only be used as valuable precursors for organic synthesis, but also act as bioisosteres for enzyme inhibitors. Among various methods for their preparation, the carbonyl olefination with difluoromethylene phosphonium ylide represents one of the most straightforward methods.Results: The combination of (chlorodifluoromethyltrimethylsilane (TMSCF2Cl and triphenylphosphine (PPh3 can be used for the synthesis of gem-difluoroolefins from carbonyl compounds. Comparative experiments demonstrate that TMSCF2Cl is superior to (bromodifluoromethyltrimethylsilane (TMSCF2Br and (trifluoromethyltrimethylsilane (TMSCF3 in this reaction.Conclusion: Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective.

Forms of organic phosphorus in wetland soils

Science.gov (United States)

Cheesman, A. W.; Turner, B. L.; Reddy, K. R.

2014-12-01

Phosphorus (P) cycling in freshwater wetlands is dominated by biological mechanisms, yet there has been no comprehensive examination of the forms of biogenic P (i.e., forms derived from biological activity) in wetland soils. We used solution 31P NMR spectroscopy to identify and quantify P forms in surface soils of 28 palustrine wetlands spanning a range of climatic, hydrogeomorphic, and vegetation types. Total P concentrations ranged between 51 and 3516 μg P g-1, of which an average of 58% was extracted in a single-step NaOH-EDTA procedure. The extracts contained a broad range of P forms, including phosphomonoesters (averaging 24% of the total soil P), phosphodiesters (averaging 10% of total P), phosphonates (up to 4% of total P), and both pyrophosphate and long-chain polyphosphates (together averaging 6% of total P). Soil P composition was found to be dependant upon two key biogeochemical properties: organic matter content and pH. For example, stereoisomers of inositol hexakisphosphate were detected exclusively in acidic soils with high mineral content, while phosphonates were detected in soils from a broad range of vegetation and hydrogeomorphic types but only under acidic conditions. Conversely inorganic polyphosphates occurred in a broad range of wetland soils, and their abundance appears to reflect more broadly that of a "substantial" and presumably active microbial community with a significant relationship between total inorganic polyphosphates and microbial biomass P. We conclude that soil P composition varies markedly among freshwater wetlands but can be predicted by fundamental soil properties.

{sup 166} Ho-EDTMP in detecting bone metastases: preliminary results

Energy Technology Data Exchange (ETDEWEB)

Achando, S.S.; Fernandes, L.; Herrerias, R.; Muramoto, E.; Almeida, M.A.T.; Pereira, N.S. de; Mengatti, J. [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)

1995-12-31

Holmium-166-EDTMP (ethylene-dimine-tetra methylene phosphonic acid) due to its promising biological properties, has proved to be a palliating therapeutic agent for bone cancer in human beings. In a basic medium, {sup 166} Ho-EDTMP can be readily prepared with a complexing molar ratio EDTMP/Ho 4.34. The radiochemical purity of the complex was higher than 98%. The biodistribution in rats and mice, showed a high skeletal uptake, a fast blood clearance and a low soft tissue uptake and a lesion to normal bone ratio equal to 2. (author). 3 refs., 4 tabs.

Glyphosate Utilization as the Source of Carbon: Isolation and Identification of new Bacteria

Directory of Open Access Journals (Sweden)

M. Mohsen Nourouzi

2011-01-01

Full Text Available Mixed bacteria from oil palm plantation soil (OPS were isolated to investigate their ability to utilize glyphosate as carbon source. Results showed that approximately all of the glyphosate was converted to aminomethyl-phosphonic acid (AMPA (99.5%. It is worthy to note that mixed bacteria were able to degrade only 2% of AMPA to further metabolites. Two bacterial strains i.e. Stenotrophomonas maltophilia and Providencia alcalifaciens were obtained from enrichment culture. Bacterial isolates were cultured individually on glyphosate as a sole carbon source. It was observed that both isolates were able to convert glyphosate to AMPA.

Synthesis of isoprenoid bisphosphonate ethers through C–P bond formations: Potential inhibitors of geranylgeranyl diphosphate synthase

Directory of Open Access Journals (Sweden)

Xiang Zhou

2014-07-01

Full Text Available A set of bisphosphonate ethers has been prepared through sequential phosphonylation and alkylation of monophosphonate ethers. After formation of the corresponding phosphonic acid salts, these compounds were tested for their ability to inhibit the enzyme geranylgeranyl diphosphate synthase (GGDPS. Five of the new compounds show IC50 values of less than 1 μM against GGDPS with little to no activity against the related enzyme farnesyl diphosphate synthase (FDPS. The most active compound displayed an IC50 value of 82 nM when assayed with GGDPS, and no activity against FDPS even at a 10 μM concentration.

Some observations on phosphate based corrosion inhibitors in preventing carbon steel corrosion

International Nuclear Information System (INIS)

Anupkumar, B.; Satpathy, K.K.

2000-01-01

Among the various types of phosphonic acid based inhibitors assayed, namely HEDP, ATMP and a commercial corrosion inhibitor (code named Betz), it was found that Betz has the maximum amount of organic phosphate followed by HEDP and ATMP. The corrosion rate studies show that Betz gives the highest inhibition efficiency followed by HEDP and ATMP. This shows that organic phosphate plays a significant role in corrosion protection. However, it was observed that due to synergestic effect, HEDP in the presence of Zn 2+ gave a better corrosion protection than Betz. The results are discussed in the light of available literature. (author)

Mechanism of the Formation of Organic Derivatives of gamma-Zirconium Phosphate by Topotactic Reactions with Phosphonic Acids in Water and Water-Acetone Media.

Science.gov (United States)

Alberti, G.; Giontella, E.; Murcia-Mascarós, S.

1997-06-18

The rates of the topotactic reactions between gamma-zirconium phosphate and phenylphosphonic acid in water and water-acetone mixtures at various temperatures were investigated. The slow rates of the process in aqueous medium or in water-acetone mixtures at temperatures lower than 50 degrees C were attributed to a slow interdiffusion of O(2)P(OH)(2)(-) and O(2)P(OH)(C(6)H(5))(-) groups in the interlayer region of gamma-ZrP. Similar to ion-exchange processes, the replacement begins in the external part of the interlayer region and progresses toward the central region with the formation of an advancing phase boundary. In water-acetone mixtures at temperatures higher than 60 degrees C an exfoliation of gamma-ZrP was found. Thus, the initial process is very fast since the substitution can take place directly on the surface of the exfoliated gamma-lamellae. However, after a certain degree of substitution, a flocculation of the colloidal dispersion, which slows down the rate of the further topotactic substitution, was observed. Some considerations on the topotactic substitution occurring on the surface of the exfoliated lamellae and on the mechanism of the diffusion of the exchanging species in the interlayer region are also reported.

Selective extraction of U(VI), Th(IV), and La(III) from acidic matrix solutions and environmental samples using chemically modified Amberlite XAD-16 resin

Energy Technology Data Exchange (ETDEWEB)

Prabhakaran, D.; Subramanian, M.S. [Department of Chemistry, Indian Institute of Technology, 600 036, Chennai (India)

2004-06-01

A new grafted polymer has been developed by the chemical modification of Amberlite XAD-16 (AXAD-16) polymeric matrix with [(2-dihydroxyarsinoylphenylamino)methyl]phosphonic acid (AXAD-16-AsP). The modified polymer was characterized by a combination of {sup 13}C CPMAS and {sup 31}P solid-state NMR, Fourier transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis (TGA). The distribution studies for the extraction of U(VI), Th(IV), and La(III) from acidic solutions were performed using an AXAD-16-AsP-packed chromatographic column. The influences of various physiochemical parameters on analyte recovery were optimized by both static and dynamic methods. Accordingly, even under high acidities (>4 M), good distribution ratio (D) values (10{sup 2}-10{sup 4}) were achieved for all the analytes. Metal ion desorption was effective using 1 mol L{sup -1} (NH{sub 4}){sub 2}CO{sub 3}. From kinetic studies, a time duration of <15 min was sufficient for complete metal ion saturation of the resin phase. The maximum metal sorption capacities were found to be 0.25, 0.13, and 1.49 mmol g{sup -1} for U(VI); 0.47, 0.39, and 1.40 mmol g{sup -1} for Th(IV); and 1.44, 1.48, and 1.12 mmol g{sup -1} for La(III), in the presence of 2 mol L{sup -1} HNO{sub 3}, 2 mol L{sup -1} HCl, and under pH conditions, respectively. The analyte selectivity of the grafted polymer was tested in terms of interfering species tolerance studies. The system showed an enrichment factor of 365, 300, and 270 for U(VI), Th(IV), and La(III), and the limit of analyte detection was in the range of 18-23 ng mL{sup -1}. The practical applicability of the polymer was tested with synthetic nuclear spent fuel and seawater mixtures, natural water, and geological samples. The RSD of the total analytical procedure was within 4.9%, thus confirming the reliability of the developed method. (orig.)

Long-term stability assessment of AlGaN/GaN field effect transistors modified with peptides: Device characteristics vs. surface properties

Energy Technology Data Exchange (ETDEWEB)

Rohrbaugh, Nathaniel; Bryan, Isaac; Bryan, Zachary; Collazo, Ramon; Ivanisevic, Albena, E-mail: ivanisevic@ncsu.edu [Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC 27695 (United States)

2015-09-15

AlGaN/GaN Field Effect Transistors (FETs) are promising biosensing devices. Functionalization of these devices is explored in this study using an in situ approach with phosphoric acid etchant and a phosphonic acid derivative. Devices are terminated on peptides and soaked in water for up to 168 hrs to examine FETs for both device responses and surface chemistry changes. Measurements demonstrated threshold voltage shifting after the functionalization and soaking processes, but demonstrated stable FET behavior throughout. X-ray photoelectron spectroscopy and atomic force microscopy confirmed peptides attachment to device surfaces before and after water soaking. Results of this work point to the stability of peptide coated functionalized AlGaN/GaN devices in solution and support further research of these devices as disposable, long term, in situ biosensors.

Crystalline TiO{sub 2} grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China); Huang Nan, E-mail: zhaoyc7320@163.com [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China)

2010-12-15

Crystalline TiO{sub 2} films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO{sub 2} films by self-assembling, and the HUPA on TiO{sub 2} films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO{sub 2} films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

Crystalline TiO2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

International Nuclear Information System (INIS)

Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian; Huang Nan

2010-01-01

Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

Crystalline TiO 2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

Science.gov (United States)

Zhao, Yuancong; Tu, Qiufen; Wang, Jin; Huang, Qiongjian; Huang, Nan

2010-12-01

Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

Anhydrous proton conductor based on composites of PEO and ATMP

International Nuclear Information System (INIS)

Sun Baoying; Qiu Xinping; Zhu Wentao

2011-01-01

A new type anhydrous PEM material based on Poly (ethylene oxide) (PEO)/Amino Trimethylene Phosphonic Acid (ATMP) composite was prepared. In this study, PEO assumed to 'grab' protons via hydrogen bond between PEO and ATMP. Based on this point, the PEO/ATMP composites were prepared firstly as the preliminary study to verify this proton conducting system. Then, PVDF was added to enhance the membrane's stability. The PVDF/PEO/ATMP composite membranes were thermally stable up to 200 o C in the studied composition ranges. The membrane had relatively compact structure by SEM images. Proton conductivity of 59% PVDF/29% PEO/12% ATMP was up to 6.71 x 10 -3 S cm -1 at 86 o C after doping with 7.9 wt% phosphoric acid without extra humidification.

Biological Cleavage of the C–P Bond in Perfluoroalkyl Phosphinic Acids in Male Sprague-Dawley Rats and the Formation of Persistent and Reactive Metabolites

Science.gov (United States)

Yeung, Leo W.Y.; Mabury, Scott A.

2017-01-01

Background: Perfluoroalkyl phosphinic acids (PFPiAs) have been detected in humans, wildlife, and various environmental matrices. These compounds have been used with perfluoroalkyl phosphonic acids (PFPAs) as surfactants in consumer products and as nonfoaming additives in pesticide formulations. Unlike the structurally related perfluoroalkyl sulfonic and carboxylic acids, little is known about the biological fate of PFPiAs. Objectives: We determined the biotransformation products of PFPiAs and some pharmacokinetic parameters in a rat model. Methods: Male Sprague-Dawley rats received an oral gavage dose of either C6/C8PFPiA, C8/C8PFPiA, or C8PFPA. Blood was sampled over time, and livers were harvested upon sacrifice. Analytes were quantified using ultra-high-performance liquid chromatography–tandem mass spectrometry or gas chromatography–mass spectrometry. Results: PFPiAs were metabolized to the corresponding PFPAs and 1H-perfluoroalkanes (1H-PFAs), with 70% and 75% biotransformation 2 wk after a single bolus dose for C6/C8PFPiA and C8/C8PFPiA, respectively. This is the first reported cleavage of a C-P bond in mammals, and the first attempt, with a single-dose exposure, to characterize the degradation of any perfluoroalkyl acid. Elimination half-lives were 1.9±0.5 and 2.8±0.8 days for C6/C8PFPiA and C8/C8PFPiA, respectively, and 0.95±0.17 days for C8PFPA. Although elimination half-lives were not determined for 1H-PFAs, concentrations were higher than the corresponding PFPAs 48 h after rats were dosed with PFPiAs, suggestive of slower elimination. Conclusions: PFPiAs were metabolized in Sprague-Dawley rats to form persistent PFPAs as well as 1H-PFAs, which contain a labile hydrogen that may undergo further metabolism. These results in rats produced preliminary findings of the pharmacokinetics and metabolism of PFPiAs, which should be further investigated in humans. If there is a parallel between the disposition of these chemicals in humans and rats, then

Long Alkyl Chain Organophosphorus Coupling Agents for in Situ Surface Functionalization by Reactive Milling

Directory of Open Access Journals (Sweden)

Annika Betke

2014-08-01

Full Text Available Innovative synthetic approaches should be simple and environmentally friendly. Here, we present the surface modification of inorganic submicrometer particles with long alkyl chain organophosphorus coupling agents without the need of a solvent, which makes the technique environmentally friendly. In addition, it is of great benefit to realize two goals in one step: size reduction and, simultaneously, surface functionalization. A top-down approach for the synthesis of metal oxide particles with in situ surface functionalization is used to modify titania with long alkyl chain organophosphorus coupling agents. A high energy planetary ball mill was used to perform reactive milling using titania as inorganic pigment and long alkyl chain organophosphorus coupling agents like dodecyl and octadecyl phosphonic acid. The final products were characterized by IR, NMR and X-ray fluorescence spectroscopy, thermal and elemental analysis as well as by X-ray powder diffraction and scanning electron microscopy. The process entailed a tribochemical phase transformation from the starting material anatase to a high-pressure modification of titania and the thermodynamically more stable rutile depending on the process parameters. Furthermore, the particles show sizes between 100 nm and 300 nm and a degree of surface coverage up to 0.8 mmol phosphonate per gram.

Combination of Micro nutrients for Bone (COMB) Study: Bone Density after Micro nutrient Intervention

International Nuclear Information System (INIS)

Genuis, S.J.; Bouchard, Th.P.

2012-01-01

Along with other investigations, patients presenting to an environmental health clinic with various chronic conditions were assessed for bone health status. Individuals with compromised bone strength were educated about skeletal health issues and provided with therapeutic options for potential amelioration of their bone health. Patients who declined pharmacotherapy or who previously experienced failure of drug treatment were offered other options including supplemental micro nutrients identified in the medical literature as sometimes having a positive impact on bone mineral density (BMD). After 12 months of consecutive supplemental micro nutrient therapy with a combination that included vitamin D3, vitamin K2, strontium, magnesium and docosahexaenoic acid (DHA), repeat bone densitometry was performed. The results were analyzed in a group of compliant patients and demonstrate improved BMD in patients classified with normal, osteopenic and osteoporotic bone density. According to the results, this combined micro nutrient supplementation regimen appears to be at least as effective as bis phosphonates or strontium ranelate in raising BMD levels in hip, spine, and femoral neck sites. No fractures occurred in the group taking the micro nutrient protocol. This micro nutrient regimen also appears to show efficacy in individuals where bis phosphonate therapy was previously unsuccessful in maintaining or raising BMD. Prospective clinical trials are required to confirm efficacy

Study of the action of a phosphonate additive on steel scale deposit and corrosion in the hydrodynamic conditions of a channel flow cell; Etude de l'action d'un additif phosphone sur l'entartrage et sur la corrosion de l'acier dans les conditions hydrodynamiques d'une cellule a canal

Energy Technology Data Exchange (ETDEWEB)

Garcia, C.

2000-10-17

In cooling systems, an improved control of scale deposit and corrosion processes is a major challenge and an realistic evaluation tool for water treatments is of the utmost economic importance. In this study, a channel flow cell was used to allow in-situ electrochemical measurements in well defined electrolyte tube flowing conditions. An expression of the mass transfer towards the electrode was established where the diffusion-limited current is a function of Re{sup 1/3} in the laminar regime and was verified experimentally using the redox couples Fe[CN]{sub 6}{sup 4-}/ Fe[CN]{sub 6}{sup 3-} and O{sub 2}/OH{sup -}. This hydrodynamically controlled experimental device was developed to investigate scale deposit processes and to evaluate scale inhibitor efficiency using a electrochemical quartz crystal microbalance. Experiments were performed on three different waters, at various flow rates and temperatures. The efficiency of a well known phosphonate (HEDP) was tested at different concentrations and an optimum concentration could be established (0.7 mg dm{sup -3}). The effect of additive injection during the scale formation as well as the influence of flow rate on the inhibiting efficiency were evaluated. The anti-scale additive was shown to be more effective in the turbulent regime. HEDP has shown a strong effect on inhibiting crystal growth and that affected the morphology of CaCO{sub 3} crystals. The HEDP effect on protecting carbon steel against corrosion was also studied in mineral water containing Ca{sup 2+} ions. It was found that anti-corrosion effect of HEDP is enhanced by the presence of calcium in solution and that is due to the formation of an HEDP-Ca{sup 2+} complex, which adsorbs onto the metallic surface and protects it from dissolution. (author)

Fosfonátové a fosfonothioátové oligonukleotidy připravené z (H)-fosfinátových monomerů

Czech Academy of Sciences Publication Activity Database

Kostov, Ondřej; Rosenberg, Ivan

2015-01-01

Roč. 13, č. 1 (2015), s. 21 ISSN 2336-7202. [Mezioborové setkání mladých biologů, biochemiků a chemiků /15./. 12.05.2015-15.5.2015, Milovy] R&D Projects: GA ČR GA13-26526S Institutional support: RVO:61388963 Keywords : oligonucleotides * H-phosphonate method * phosphotriester method * synthesis on solid phase * phosphonate Subject RIV: CC - Organic Chemistry

Design, Synthesis and Antiviral Activity of 5-Hydroxymethyl-3-phosphonyl-4,5-dihydrofuran Analogs of Nucleotides

International Nuclear Information System (INIS)

Lee, Hee Yoon; Lee, Ki Ho; Hah, Jung Hwan; Moon, Deuk Kyu; Lee, Chong Kyo

2010-01-01

We have designed and synthesized functionalized dihydrofurylphosphonates that are constrained analogs of 1-alkenyl-phosphonate derivatives of purine/pyrimidine nucleotides as they bear phosphonyl groups at the 3-position and bases at the methyl group of the 5-position of the furan ring. This newly designed dihydrofurylphosphonate analogs of nucleotide showed antiviral activity. Through the current synthetic strategy, structural diversification can be easily attainable for structure activity relationship study and for the better antiviral compounds. Phosphonate esters play an important role in studying the biological system as a hydrolytically stable replacement of phosphate groups and as prodrugs of phosphonates. In continuation of our study on the chemistry of 1-alkenylphosphonates, we were interested in designing and developing versatile synthetic routes to conformationally constrained structures of al-kenylphosphonate nucleotide analogs

Two novel metal-organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

Science.gov (United States)

Niu, Qing-Jun; Zheng, Yue-Qing; Zhou, Lin-Xia; Zhu, Hong-Lin

2015-07-01

Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H2en)[Co3(H2zdn)2(ox)(H2O)2] (1) and Cd2(H2zdn)(ox)0.5(H2O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H5zdn; oxalic acid=H2ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O-P-O units of H5zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property.

Inhibition effect of phosphorus-based chemicals on corrosion of carbon steel in secondary-treated municipal wastewater.

Science.gov (United States)

Shen, Zhanhui; Ren, Hongqiang; Xu, Ke; Geng, Jinju; Ding, Lili

2013-01-01

Secondary-treated municipal wastewater (MWW) could supply a viable alternative water resource for cooling water systems. Inorganic salts in the concentrated cooling water pose a great challenge to corrosion control chemicals. In this study, the inhibition effect of 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), trimethylene phosphonic acid (ATMP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) on corrosion of carbon steel in secondary-treated MWW was investigated by the means of potentiodynamic polarization and electrochemical impedance spectroscopy. The inhibition effect increased with increasing concentration of inhibitors. The corrosion rates of carbon steel were 1.5, 0.8, 0.2 and 0.5 mm a(-1) for blank, HEDP, ATMP and PBTCA samples at 50 mg L(-1), respectively. The phosphorus-based chemicals could adsorb onto the surface of the carbon steel electrode, form a coat of protective film and then protect the carbon steel from corrosion in the test solution.

Phenolic metabolites in carnivorous plants: Inter-specific comparison and physiological studies.

Science.gov (United States)

Kováčik, Jozef; Klejdus, Bořivoj; Repčáková, Klára

2012-03-01

Despite intensive phytochemical research, data related to the accumulation of phenols in carnivorous plants include mainly qualitative reports. We have quantified phenolic metabolites in three species: Drosera capensis, Dionaea muscipula and Nepenthes anamensis in the "leaf" (assimilatory part) and the "trap" (digestive part). For comparison, commercial green tea was analysed. Phenylalanine ammonia-lyase (PAL) activities in Dionaea and Nepenthes were higher in the trap than in the leaf while the opposite was found in Drosera. Soluble phenols and majority of phenolic acids were mainly accumulated in the trap among species. Flavonoids were abundant in Drosera and Dionaea traps but not in Nepenthes. Phenolic acids were preferentially accumulated in a glycosidically-bound form and gallic acid was the main metabolite. Green tea contained more soluble phenols and phenolic acids but less quercetin. In vitro experiments with Drosera spathulata revealed that nitrogen deficiency enhances PAL activity, accumulation of phenols and sugars while PAL inhibitor (2-aminoindane-2-phosphonic acid) depleted phenols and some amino acids (but free phenylalanine and sugars were elevated). Possible explanations in physiological, biochemical and ecological context are discussed. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

A dual-task design of corrosion-controlling and osteo-compatible hexamethylenediaminetetrakis- (methylene phosphonic acid) (HDTMPA) coating on magnesium for biodegradable bone implants application.

Science.gov (United States)

Zhao, Sheng; Chen, Yingqi; Liu, Bo; Chen, Meiyun; Mao, Jinlong; He, Hairuo; Zhao, Yuancong; Huang, Nan; Wan, Guojiang

2015-05-01

Magnesium as well as its alloys appears increasingly as a revolutionary bio-metal for biodegradable implants application but the biggest challenges exist in its too fast bio-corrosion/degradation. Both corrosion-controllable and bio-compatible Mg-based bio-metal is highly desirable in clinic. In present work, hexamethylenediaminetetrakis (methylenephosphonic acid) [HDTMPA, (H2 O3 P-CH2 )2 -N-(CH2 )6 -N-(CH2 -PO3 H2 )2 ], as a natural and bioactive organic substance, was covalently immobilized and chelating-deposited onto Mg surface by means of chemical conversion process and dip-coating method, to fullfill dual-task performance of corrosion-protective and osteo-compatible functionalities. The chemical grafting of HDTMPA molecules, by participation of functional groups on pretreated Mg surface, ensured a firmly anchored base layer, and then sub-sequential chelating reactions of HDTMPA molecules guaranteed a homogenous and dense HDTMPA coating deposition on Mg substrate. Electrochemical corrosion and immersion degradation results reveal that the HDTMPA coated Mg provides a significantly better controlled bio-corrosion/degradation behavior in phosphate buffer saline solution as compared with untreated Mg from perspective of clinic requirement. Moreover, the HDTMPA coated Mg exhibits osteo-compatible in that it induces not only bioactivity of bone-like apatite precipitation but also promotes osteoblast cells adhesion and proliferation. Our well-controlled biodegradable and biocompatible HDTMPA modified Mg might bode well for next generation bone implant application. © 2014 Wiley Periodicals, Inc.

A new hydrometallurgical process for extracting rare earths from apatite using solvent extraction with P35

International Nuclear Information System (INIS)

Li Hongfei; Guo Fuqiang; Zhang Zhifeng; Li Deqian; Wang Zhonghuai

2006-01-01

In this paper, a new process is proposed to recover rare earths from nitric acid leaching of apatite without interfering with the normal route for fertilizer production using solvent extraction with dimethyl heptyl methyl phosphonate CH 3 P(O)(OC 8 H 17 ) 2 (P 35 , B). In the present work, the leaching conditions are studied. In selected condition, apatite was dissolved in 20% (v/v) nitric acid solution at 60-70 deg. C while agitating. The most suitable acidity for extraction is 0.4 M HNO 3 . More than 98% of rare earths in apatite can be recovered using countercurrent extraction process with six stages when phase ratio = 0.5, and defluorination is unnecessary. The influences of phase ratio, stage number, acidity and salting-out agent on extractabilities of P 35 are studied. The results show that rare earths can be separated with P 35 from Ca, P, Fe and other impurities. Mixed rare earth oxides (REO) of which purity is more than 95% with yield over 98% can be obtained

Phosphorylated derivatives of anabasine: synthesis, constitution and complex forming properties

International Nuclear Information System (INIS)

Babaev, B.N.

2004-01-01

Full text: With the purpose of detection of new effective extra gents of metals from number of sulphur containing derivatives of acids of phosphorus with different functional groups, analysis of effect of the different factors on selectivity of allocation of metals, installation of optimum conditions of an extraction, the detections of effective extra gents of noble metals from industrial sewage waters, are synthesized phosphorylated derivatives of the anabasine - O-alkyl-O-(anaba-sinoisopropyl)- and O-alkyl-O-(anabasinobutyn-2-yl)phenyl phosphonates and O-(anabasinoisopropyl)- and O-(anabasinobutyn-2-yl)diphenyl phosphonates In an IR-spectrum about O-pentyl-O-[anabasinoisopropyl]phenylphosphonate There are absorption band of the following functional groups (ν, cm -1 ): (P-O-C 5 H 11 ) 990-1000, (P = 0) 1250, (P-C 6 H 5 )1450, (C-N in cycle) 1550. In a spectrum PMR O-(anabasinobutyn-2-yl)phenylphosphonate in the field of a weak field apart from signals of two phenylic radicals the signals of a b-displaced pyridine, reference for a molecule anabasine are observed: Hαa-8,46 p.m., H α '-8,41 p.m., H γ -7,60 p.m. And H β -7,15 p.m. A double triplet at 4,70 p.m. And triplet at 3,05 p.m. Belong to signals OCH 2 and N-CH 2 of groups, accordingly, separated by acetylene bond. The signals of piperidine cycle of anabasine have the following chemical shifts: H 2a -3,27 p.m., H 6e -2,78 p.m., H 6a -2,45 p.m., and remaining protons (6H, m, CH 2 ) are in resonance in the field of 1,1-1,9 p.m. The analysis of mass-spectrometer decay of the synthesized connections has shown, that the mass-spectrometer fragmentation M * about - O-alkyl-O- (anabasinoisopropyl) phenylphosphonates flows past in different directions and is characterized, as against about O-alkyl-O-(anabasinobutyn-2-yl)phenyl-phosphonates, large number of phosphor containing ions; the availability of the second phenylic radical in molecules anabasincontaining derivatives of a diphenyl phosphinic acid essentially

Phosphonic drugs: Experimental and theoretical spectroscopic studies of fosfomycin

Science.gov (United States)

Chruszcz-Lipska, Katarzyna; Zborowski, Krzysztof K.; Podstawka-Proniewicz, Edyta; Liu, Shaoxuan; Xu, Yizhuang; Proniewicz, Leonard M.

2011-02-01

pH and time-dependant changes of fosfomycin molecular structure in an aqueous solution are studied by Raman, NMR, and generalized 2D correlation spectroscopies. Interpretation of the experimental spectra is based on the assumption of formation of different species running on applied physicochemical conditions. Geometries of all possible structures were entirely optimized with the 6-311++G(2df,p) basis set at the B3LYP theoretical level using procedures implemented in the Gaussian '03 set of programs. Harmonic frequency calculations verified the nature of the studied structures and allowed to simulate obtained Raman spectra. The theoretical NMR shielding was calculated using the GIAO method at the same computational level. In addition, in some cases PCM model was used to monitor the influence of water molecules on the NMR spectra. It is shown that in the pH range of 1-2 of fosfomycin aqueous solution oxirane ring is open sequent to nucleophilic attack and forms 1,2-dihydroxyphosphonic acid with small content of its monodeprotonated species. On the other hand, in pH 7 and higher it appears either as 1,2-epoxypropylphosphonic or 1,2-dihydroxyphosphonic dianion depending upon whether hydrolysis took place or not. It is also discussed that Raman marker bands originating from the individual species of fosfomycin can be used to detect and/or to monitor this antibiotic in an aqueous medium (for example urine samples). Hence, depending upon the structure found in urine one can tell about metabolic processes of this antibiotic in the body.

Systems and strippable coatings for decontaminating structures that include porous material

Science.gov (United States)

Fox, Robert V [Idaho Falls, ID; Avci, Recep [Bozeman, MT; Groenewold, Gary S [Idaho Falls, ID

2011-12-06

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Methods for removing contaminant matter from a porous material

Science.gov (United States)

Fox, Robert V [Idaho Falls, ID; Avci, Recep [Bozeman, MT; Groenewold, Gary S [Idaho Falls, ID

2010-11-16

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Polyphosphazine-based polymer materials

Science.gov (United States)

Fox, Robert V.; Avci, Recep; Groenewold, Gary S.

2010-05-25

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Anhydrous proton conductor based on composites of PEO and ATMP

Energy Technology Data Exchange (ETDEWEB)

Sun Baoying [Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China); Qiu Xinping, E-mail: qiuxp@tsinghua.edu.c [Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China); Zhu Wentao [Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084 (China)

2011-04-15

A new type anhydrous PEM material based on Poly (ethylene oxide) (PEO)/Amino Trimethylene Phosphonic Acid (ATMP) composite was prepared. In this study, PEO assumed to 'grab' protons via hydrogen bond between PEO and ATMP. Based on this point, the PEO/ATMP composites were prepared firstly as the preliminary study to verify this proton conducting system. Then, PVDF was added to enhance the membrane's stability. The PVDF/PEO/ATMP composite membranes were thermally stable up to 200 {sup o}C in the studied composition ranges. The membrane had relatively compact structure by SEM images. Proton conductivity of 59% PVDF/29% PEO/12% ATMP was up to 6.71 x 10 {sup -3} S cm{sup -1} at 86 {sup o}C after doping with 7.9 wt% phosphoric acid without extra humidification.

Radiopharmaceuticals developed at the University of Missouri research reactor

International Nuclear Information System (INIS)

Ketring, A.R.; Ehrhardt, G.J.; Day, D.E.

1997-01-01

The University of Missouri Research Reactor (MURR) has put a great deal of effort in the last two decades into development of radiotherapeutic beta emitters as nuclear medicine radiotherapeutics for malignancies. This paper describes the development of two of these drugs, 153 Sm ethylenediaminetetra-methylene phosphonic acid (EDTMP) (Quadramet trademark) and 90 Y glass microspheres (TheraSphere trademark). Samarium-153 EDTMP is a palliative used to treat the pain of metastatic bone cancer without the side effects of narcotic pain killers. Yttrium-90 glass microspheres are delivered via hepatic artery catheter to embolize the capillaries of liver tumors and deliver a large radiation dose for symptom palliation and life prolonging purposes

In situ synchrotron X-ray diffraction study of surface scale formation during CO2 corrosion of carbon steel at temperatures up to 90 oC

International Nuclear Information System (INIS)

Ingham, B.; Ko, M.; Kear, G.; Kappen, P.; Laycock, N.; Kimpton, J.A.; Williams, D.E.

2010-01-01

In situ synchrotron X-ray diffraction was used to follow the formation of corrosion product scales on carbon steel in CO 2 saturated brine at temperatures from 40 to 90 o C. The corrosion process was accelerated by applying a small anodic current, and in selected tests a scale inhibitor, amino trimethylene phosphonic acid (ATMPA), was added. Siderite was identified as the major phase in the scale formed in all conditions. With increasing temperature, the scale formation rate increased, while the scale thickness and crystallite size decreased. Above 60 o C, the scale became increasingly protective. The scale thickness and crystallite size decreased with increasing ATMPA concentration.

Regulatory activity of azabisphosphonate-capped dendrimers on human CD4+ T cell proliferation enhances ex-vivo expansion of NK cells from PBMCs for immunotherapy

Directory of Open Access Journals (Sweden)

Caminade Anne-Marie

2009-09-01

Full Text Available Abstract Background Adoptive cell therapy with allogenic NK cells constitutes a promising approach for the treatment of certain malignancies. Such strategies are currently limited by the requirement of an efficient protocol for NK cell expansion. We have developed a method using synthetic nanosized phosphonate-capped dendrimers allowing such expansion. We are showing here that this is due to a specific inhibitory activity towards CD4+ T cell which could lead to further medical applications of this dendrimer. Methods Mononuclear cells from human peripheral blood were used to investigate the immunomodulatory effects of nanosized phosphonate-capped dendrimers on interleukin-2 driven CD4+T cell expansion. Proliferation status was investigated using flow cytometry analysis of CFSE dilution and PI incorporation experiments. Magnetic bead cell sorting was used to address activity towards individual or mixed cell sub-populations. We performed equilibrium binding assay to assess the interaction of fluorescent dendrimers with pure CD4+ T cells. Results Phosphonate-capped dendrimers are inhibiting the activation, and therefore the proliferation; of CD4+ T cells in IL-2 stimulated PBMCs, without affecting their viability. This allows a rapid enrichment of NK cells and further expansion. We found that dendrimer acts directly on T cells, as their regulatory property is maintained when stimulating purified CD4+ T cells with anti-CD3/CD28 microbeads. Performing equilibrium binding assays using a fluorescent analogue, we show that the phosphonate capped-dendrimers are specifically interacting with purified CD4+ T cells. Ultimately, we found that our protocol prevents the IL-2 related expansion of regulatory T cells that would be deleterious for the activity of infused NK cells. Conclusion High yield expansion of NK cells from human PBMCs by phosphonate-capped dendrimers and IL-2 occurs through the specific inhibition of the CD4+ lymphocyte compartment. Given the

ATMP-stabilized iron nanoparticles: chelator-controlled nanoparticle synthesis

Science.gov (United States)

Greenlee, Lauren F.; Rentz, Nikki S.

2014-11-01

In this study, we characterize iron nanoparticles synthesized in water in the presence of a phosphonate chelator, amino tris(methylene phosphonic acid) (ATMP) for a range of molar ratios of ATMP to iron. An increase in the molar ratio from 0.05 to 0.8 decreases nanoparticle size from approximately 150 nm to less than 10 nm. Zeta potential measurements were used to evaluate colloidal stability. Zeta potential values varied as a function of pH, and zeta potential values decreased with increasing pH. At lower molar ratios of ATMP to iron, the zeta potential varied between 15 and -40 mV, passing through an isoelectric point at pH 7.5. At higher ratios, the zeta potential was negative across the measured pH range of 2-12 and varied from -2 to -55 mV. Diffraction analysis indicates that ATMP-stabilized iron nanoparticles may have a nano-crystalline structure, potentially with regions of amorphous iron. Characterization results of ATMP-stabilized iron nanoparticles are compared to results obtained for carboxymethyl cellulose (CMC)-stabilized iron nanoparticles. CMC stabilization caused similar peak broadening in diffraction spectra as for ATMP, suggesting similar nano-crystalline/amorphous structure; however, an increase in the molar ratio of CMC to iron did not cause the same reduction in nanoparticle size as was observed for ATMP-stabilized iron nanoparticles.

Preparation of Affinity Column Based on Zr{sup 4+} Ion for Phosphoproteins Isolation

Energy Technology Data Exchange (ETDEWEB)

Lee, Seon Mi; Bae, In Ae; Park, Jung Hyen; Kim, Tae Dong; Choi, Seong Ho [Hannam University, Daejeon (Korea, Republic of)

2009-06-15

This paper has described about preparation of Zr{sup 4+} affinity column based on the poly(styreneco- glycidyl methacrylate) prepared by emulsion polymerization of styrene and glycidyl methacrylate in order to isolate phosphopeptide. The Zr{sup 4+} ions were introduced after the phophonation of an epoxy group on polymeric microspheres. The successful preparation of Zr{sup 4+}-immobilized polymeric microsphere stationary phase was confirmed through Fourier transform infrared spectra, optical microscopy, scanning electron microscopy, X-ray photoelectron spectra and inductively coupled plasma-atomic emission spectrometer. The separation efficiency for Zr{sup 4+} affinity column prepared by slurry packing was tested to phosphonated casein and dephosphonated casein. The resolution time (min) of the phosphonated casein was higher than that of dephosphated casein for Zr{sup 4+} affinity polymeric microsphere by liquid chromatography. This Zr{sup 4+} affinity column can be used for isolation of phosphonated casein from casein using liquid chromatography.

Preparation of Affinity Column Based on Zr4+ Ion for Phosphoproteins Isolation

International Nuclear Information System (INIS)

Lee, Seon Mi; Bae, In Ae; Park, Jung Hyen; Kim, Tae Dong; Choi, Seong Ho

2009-01-01

This paper has described about preparation of Zr 4+ affinity column based on the poly(styreneco- glycidyl methacrylate) prepared by emulsion polymerization of styrene and glycidyl methacrylate in order to isolate phosphopeptide. The Zr 4+ ions were introduced after the phophonation of an epoxy group on polymeric microspheres. The successful preparation of Zr 4+ -immobilized polymeric microsphere stationary phase was confirmed through Fourier transform infrared spectra, optical microscopy, scanning electron microscopy, X-ray photoelectron spectra and inductively coupled plasma-atomic emission spectrometer. The separation efficiency for Zr 4+ affinity column prepared by slurry packing was tested to phosphonated casein and dephosphonated casein. The resolution time (min) of the phosphonated casein was higher than that of dephosphated casein for Zr 4+ affinity polymeric microsphere by liquid chromatography. This Zr 4+ affinity column can be used for isolation of phosphonated casein from casein using liquid chromatography

78 FR 20029 - Castor Oil, Polymer With Adipic Acid, Linoleic Acid, Oleic Acid and Ricinoleic Acid; Tolerance...

Science.gov (United States)

2013-04-03

..., Polymer With Adipic Acid, Linoleic Acid, Oleic Acid and Ricinoleic Acid; Tolerance Exemption AGENCY... from the requirement of a tolerance for residues of castor oil, polymer with adipic acid, linoleic acid... pesticide formulation. Advance Polymer Technology submitted a petition to EPA under the Federal Food, Drug...

Tuning the hybridization properties of modified oligonucleotides: from flexible to conformationally constrained phosphonate internucleotide linkages

Czech Academy of Sciences Publication Activity Database

Páv, Ondřej; Barvík, I.; Liboska, Radek; Petrová, Magdalena; Šimák, Ondřej; Rosenbergová, Šárka; Novák, Pavel; Buděšínský, Miloš; Rosenberg, Ivan

2017-01-01

Roč. 15, č. 3 (2017), s. 701-707 ISSN 1477-0520 R&D Projects: GA ČR GA13-26526S; GA MZd NV15-31604A Institutional support: RVO:61388963 Keywords : molecular dynamics simulations * sugar phosphate backbone * nucleic acid recognition Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.564, year: 2016

[Studies on interaction of acid-treated nanotube titanic acid and amino acids].

Science.gov (United States)

Zhang, Huqin; Chen, Xuemei; Jin, Zhensheng; Liao, Guangxi; Wu, Xiaoming; Du, Jianqiang; Cao, Xiang

2010-06-01

Nanotube titanic acid (NTA) has distinct optical and electrical character, and has photocatalysis character. In accordance with these qualities, NTA was treated with acid so as to enhance its surface activity. Surface structures and surface groups of acid-treated NTA were characterized and analyzed by Transmission Electron Microscope (TEM) and Fourier Transform Infrared Spectrometry (FT-IR). The interaction between acid-treated NTA and amino acids was investigated. Analysis results showed that the lengths of acid-treated NTA became obviously shorter. The diameters of nanotube bundles did not change obviously with acid-treating. Meanwhile, the surface of acid-treated NTA was cross-linked with carboxyl or esterfunction. In addition, acid-treated NTA can catch amino acid residues easily, and then form close combination.

Development of a New Process for the Selective Extraction of Uranium from Phosphate Rocks

International Nuclear Information System (INIS)

Bernier, G.; Miguirditchian, M.; Pacary, V.; Balaguer, C.; Bertrand, M.; Camès, B.; Hérès, X.; Mokhtari, H.

2014-01-01

Conclusions: • Amido-phosphonate DEHCNPB is very promising for U extraction from phosphoric acid – Selective extraction of U even among high concentrations of iron in genuine 5 M H3PO4 solution : [Fe]/[U] reduced from 30 (feed) to 4.3 10-4 (product); • Parametric laboratory studies: – Characterize the stoichiometry of extracted complex in organic phase; – Propose extraction mechanisms; • Model developed and implemented in CEA PAREX code: – Modelling and flowsheet design; • Counter-current test on PROUST platform in G1 facility with genuine industrial phosphoric solution: – Treatment of an industrial phosphoric acid in laboratory-scale mixer-settlers; – Very promising performances of the run with good U recovery (91%) and good decontamination ([Fe] / [U] < ASTM specifications); – Experimental and calculated profiles of U and Fe in good agreement; • Experiments in progress to optimize this flowsheet

Studies on up-gradation of Erbium from a heavy fraction of rare earths with EHEHPA

International Nuclear Information System (INIS)

Singh, D.K.; Anitha, M.; Yadav, K.K.; Kotekar, M.K.; Vijayalakshmi, R.; Singh, H.

2014-01-01

Erbium is an important heavy rare earth element, which finds wide applications. Recently, use of Erbium oxide as structural coating material in fusion reactor has stimulated the interest in obtaining Erbium in pure form. The separation of Erbium from other rare earths such as Dy, Ho, Y, Yb, Tm etc is very difficult due to low separation factor owing to their similar chemical properties. Additionally due to very low concentration ( 2 O 3 : 1.09, Dy 2 O 3 : 58.07, Er 2 O 3 : 22.0, Ho 2 O 3 : 13.33, Yb 2 O 3 : 4.74, Tm 2 O 3 :0.67 is obtained during purification of Y by Aliquat 336 from thiocyanate medium. In the present investigation this HRE fraction is taken as the feed material for up-gradation of Er by an acidic extractant namely 2 ethyl hexyl - 2 ethyl hexyl phosphonic acid (EHEHPA)

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

Prevention of refinery tower plugging by residual oil gellant chemicals in crude-pilot plant evaluation of alternative oil gellants

Energy Technology Data Exchange (ETDEWEB)

Taylor, R.S.; Fyten, G.C.; Cheng, A. [Halliburton Energy Services, Calgary, AB (Canada); Stemler, P.S. [Petro-Canada Oil and Gas Inc., Calgary, AB (Canada); Lemieux, A. [Omnicon Consultants Inc., Calgary, AB (Canada)

2006-07-01

Tower fouling at petroleum refineries is related to background volatile phosphorus components originating from phosphate ester oil gellants. In an attempt to reduce the cost of unplanned refinery shut downs, the Canadian Association of Petroleum Producers (CAPP) may institute a new specification in July 2006 of 0.5 ppm maximum volatile phosphorus in crude. In concept, volatile phosphorus can be removed from phosphate esters by eliminating volatile components in the original phosphate ester gellant. However, the issue of of whether modified phosphate esters can really reduce refinery tower fouling has been questioned. For that reason, this study focused on water hydrolysis which may occur in a distillation tower, causing localized areas of acidity and causticity. Halogenation reactions could occur in the presence of acid at high temperatures if halogen ions are present. The source of halide ions could be any salts that have not been removed in the de-salters. Full-scale testing at a pilot plant facility was conducted over several days with flowback captured after actual fracturing treatments. Fouling of distillation tower trays was measured along with fouling of the packing material. The study examined how fouling was influenced by changes in operating parameters such as rate, temperature, or pressure during each test. Three full-scale pilot evaluations were conducted using actual flowback fluids from fracturing treatments conducted with 3 different oil gellants: conventional phosphate ester, modified phosphate and phosphonate ester. The comparison of actual tower fouling between these alternative gellants can be used as a guide when choosing oil gellant systems to reduce refinery tower and heat exchanger fouling. It was concluded that phosphonate gellants are hydrolytically stable at higher temperatures and should minimize volatile phosphorus created through the hydrolysis of phosphate esters. However, they are more expensive since they are more complex to create

Durability of polymer/metal interfaces under cyclic loading

Science.gov (United States)

Du, Tianbao

Fatigue crack growth along metal/epoxy interface was examined in an aqueous environment and under mixed-mode conditions. A stress corrosion cracking mechanism was identified in this process. The fatigue crack growth rate in an aqueous environment was increased by several orders of magnitude and the fatigue threshold decreased by a factor of 10. The loss of adhesion in the aqueous environment was induced by the hydration of the surface oxide which resulted in a hydroxide with poor adhesion to the substrate metal. Self-assembled monolayer of long chain alkyl phosphonic acid and amino phosphonic acid were synthesized to enhance the adhesion and improve the durability of Al/epoxy interfacial bonding system. The same approach was taken to promote adhesion between copper and epoxy, where a two-component coupling system of 11-mercapto-1-undercanol and 3-aminopropyltriethoxysilane provided the most significant improvement in the copper/epoxy adhesion. The mixed-mode was applied by a piezoelectric actuator. Subcritical crack growth was observed along the epoxy/aluminum interface and the growth rate was found to depend on the magnitude of the applied electric field. Kinetics of the crack growth was correlated with the piezoelectric driving force. The resulting crack growth behavior was compared with the results from the conventional mechanical testing technique. Large differences were found between these two methods. Using this newly developed technique, effects of loading mode and frequency were studied. The fatigue resistance was found to increase with the mode II component and was expressed as a function of the KII/K I ratio. A strong frequency effect was observed for the subcritical crack growth along the Al/Epoxy interface, their fatigue resistance increased with the testing frequency.

Estimation of human absorbed dose for (166)Ho-PAM: comparison with (166)Ho-DOTMP and (166)Ho-TTHMP.

Science.gov (United States)

Vaez-Tehrani, Mahdokht; Zolghadri, Samaneh; Yousefnia, Hassan; Afarideh, Hossein

2016-10-01

In this study, the human absorbed dose of holmium-166 ((166)Ho)-pamidronate (PAM) as a potential agent for the management of multiple myeloma was estimated. (166)Ho-PAM complex was prepared at optimized conditions and injected into the rats. The equivalent and effective absorbed doses to human organs after injection of the complex were estimated by radiation-absorbed dose assessment resource and methods proposed by Sparks et al based on rat data. The red marrow to other organ absorbed dose ratios were compared with these data for (166)Ho-DOTMP, as the only clinically used (166)Ho bone marrow ablative agent, and (166)Ho-TTHMP. The highest absorbed dose amounts are observed in the bone surface and bone marrow with 1.11 and 0.903 mGy MBq(-1), respectively. Most other organs would receive approximately insignificant absorbed dose. While (166)Ho-PAM demonstrated a higher red marrow to total body absorbed dose ratio than (166)Ho-1,4,7,10-tetraazacyclo dodecane-1,4,7,10 tetra ethylene phosphonic acid (DOTMP) and (166)Ho-triethylene tetramine hexa (methylene phosphonic acid) (TTHMP), the red marrow to most organ absorbed dose ratios for (166)Ho-TTHMP and (166)Ho-PAM are much higher than the ratios for (166)Ho-DOTMP. The result showed that (166)Ho-PAM has significant characteristics than (166)Ho-DOTMP and therefore, this complex can be considered as a good agent for bone marrow ablative therapy. In this work, two separate points have been investigated: (1) human absorbed dose of (166)Ho-PAM, as a potential bone marrow ablative agent, has been estimated; and (2) the complex has been compared with (166)Ho-DOTMP, as the only clinically used bone marrow ablative radiopharmaceutical, showing significant characteristics.

Ibotenic acid and thioibotenic acid

DEFF Research Database (Denmark)

Hermit, Mette B; Greenwood, Jeremy R; Nielsen, Birgitte

2004-01-01

In this study, we have determined and compared the pharmacological profiles of ibotenic acid and its isothiazole analogue thioibotenic acid at native rat ionotropic glutamate (iGlu) receptors and at recombinant rat metabotropic glutamate (mGlu) receptors expressed in mammalian cell lines....... Thioibotenic acid has a distinct pharmacological profile at group III mGlu receptors compared with the closely structurally related ibotenic acid; the former is a potent (low microm) agonist, whereas the latter is inactive. By comparing the conformational energy profiles of ibotenic and thioibotenic acid...... with the conformations preferred by the ligands upon docking to mGlu1 and models of the other mGlu subtypes, we propose that unlike other subtypes, group III mGlu receptor binding sites require a ligand conformation at an energy level which is prohibitively expensive for ibotenic acid, but not for thioibotenic acid...

Surface functionalization of microwave plasma-synthesized silica nanoparticles for enhancing the stability of dispersions

Science.gov (United States)

Sehlleier, Yee Hwa; Abdali, Ali; Schnurre, Sophie Marie; Wiggers, Hartmut; Schulz, Christof

2014-08-01

Gas phase-synthesized silica nanoparticles were functionalized with three different silane coupling agents (SCAs) including amine, amine/phosphonate and octyltriethoxy functional groups and the stability of dispersions in polar and non-polar dispersing media such as water, ethanol, methanol, chloroform, benzene, and toluene was studied. Fourier transform infrared spectroscopy showed that all three SCAs are chemically attached to the surface of silica nanoparticles. Amine-functionalized particles using steric dispersion stabilization alone showed limited stability. Thus, an additional SCA with sufficiently long hydrocarbon chains and strong positively charged phosphonate groups was introduced in order to achieve electrosteric stabilization. Steric stabilization was successful with hydrophobic octyltriethoxy-functionalized silica nanoparticles in non-polar solvents. The results from dynamic light scattering measurements showed that in dispersions of amine/phosphonate- and octyltriethoxy-functionalized silica particles are dispersed on a primary particle level. Stable dispersions were successfully prepared from initially agglomerated nanoparticles synthesized in a microwave plasma reactor by designing the surface functionalization.

[Acids in coffee. XI. The proportion of individual acids in the total titratable acid].

Science.gov (United States)

Engelhardt, U H; Maier, H G

1985-07-01

22 acids in ground roast coffees and instant coffees were determined by GLC of their silyl derivatives (after preseparation by gel electrophoresis) or isotachophoresis. The contribution to the total acidity (which was estimated by titration to pH 8 after cation exchange of the coffee solutions) was calculated for each individual acid. The mentioned acids contribute with 67% (roast coffee) and 72% (instant coffee) to the total acidity. In the first place citric acid (12.2% in roast coffee/10.7% in instant coffee), acetic acid (11.2%/8.8%) and the high molecular weight acids (8%/9%) contribute to the total acidity. Also to be mentioned are the shares of chlorogenic acids (9%/4.8%), formic acid (5.3%/4.6%), quinic acid (4.7%/5.9%), malic acid (3.9%/3%) and phosphoric acid (2.5%/5.2%). A notable difference in the contribution to total acidity between roast and instant coffee was found for phosphoric acid and pyrrolidonecarboxylic acid (0.7%/1.9%). It can be concluded that those two acids are formed or released from e.g. their esters in higher amounts than other acids during the production of instant coffee.

Bivalent alkyne-bisphosphonate as clickable and solid anchor to elaborate multifunctional iron oxide nanoparticles with microwave enhancement

International Nuclear Information System (INIS)

Guénin, Erwann; Hardouin, Julie; Lalatonne, Yoann; Motte, Laurence

2012-01-01

We report the elaboration of clickable superparamagnetic nanoparticles that act as a scaffold for further modifications by click chemistry. This nano platform is easily obtained by coating iron oxide nanoparticle γ-Fe 2 O 3 , with a new bifunctional molecule (1-hydroxy-1-phosphonopent-4-ynyl)phosphonic acid (HMBPyne). The HMBP and the alkyne functions act respectively as anchoring surface group and click chemistry functionality. We evaluate the functionalization of this new “clickable” nanoplateform using Huisgen 1,3-cycloaddition as model reaction and demonstrate the potential of microwave irradiation to increase the grafting yield. The effectiveness of click chemistry for the modification of mNPs is explored with a diverse array of functional species.

Radiopharmaceuticals developed at the University of Missouri research reactor

Energy Technology Data Exchange (ETDEWEB)

Ketring, A.R.; Ehrhardt, G.J. [Univ. of Missouri, Columbia, MO (United States); Day, D.E. [Univ. of Missouri, Rolla, MO (United States)

1997-12-01

The University of Missouri Research Reactor (MURR) has put a great deal of effort in the last two decades into development of radiotherapeutic beta emitters as nuclear medicine radiotherapeutics for malignancies. This paper describes the development of two of these drugs, {sup 153}Sm ethylenediaminetetra-methylene phosphonic acid (EDTMP) (Quadramet{trademark}) and {sup 90}Y glass microspheres (TheraSphere{trademark}). Samarium-153 EDTMP is a palliative used to treat the pain of metastatic bone cancer without the side effects of narcotic pain killers. Yttrium-90 glass microspheres are delivered via hepatic artery catheter to embolize the capillaries of liver tumors and deliver a large radiation dose for symptom palliation and life prolonging purposes.

Novel organophosphorus scaffolds of urease inhibitors obtained by substitution of Morita-Baylis-Hillman adducts with phosphorus nucleophiles.

Science.gov (United States)

Ntatsopoulos, Vassilis; Vassiliou, Stamatia; Macegoniuk, Katarzyna; Berlicki, Łukasz; Mucha, Artur

2017-06-16

The reactivity of Morita-Baylis-Hillman allyl acetates was employed to introduce phosphorus-containing functionalities to the side chain of the cinnamic acid conjugated system by nucleophilic displacement. The proximity of two acidic groups, the carboxylate and phosphonate/phosphinate groups, was necessary to form interactions in the active site of urease by recently described inhibitor frameworks. Several organophosphorus scaffolds were obtained and screened for inhibition of the bacterial urease, an enzyme that is essential for survival of urinary and gastrointestinal tract pathogens. α-Substituted phosphonomethyl- and 2-phosphonoethyl-cinnamate appeared to be the most potent and were further optimized. As a result, one of the most potent organophosphorus inhibitors of urease, α-phosphonomethyl-p-methylcinnamic acid, was identified, with K i  = 0.6 μM for Sporosarcina pasteurii urease. High complementarity to the enzyme active site was achieved with this structure, as any further modifications significantly decreased its affinity. Finally, this work describes the challenges faced in developing ligands for urease. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

Science.gov (United States)

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Phosphorus recovery and leaching of trace elements from incinerated sewage sludge ash (ISSA).

Science.gov (United States)

Fang, Le; Li, Jiang-Shan; Guo, Ming Zhi; Cheeseman, C R; Tsang, Daniel C W; Donatello, Shane; Poon, Chi Sun

2018-02-01

Chemical extraction of phosphorus (P) from incinerated sewage sludge ash (ISSA) is adversely influenced by co-dissolution of metals and metalloids. This study investigated P recovery and leaching of Zn, Cu, Pb, As and Ni from ISSA using inorganic acids (sulphuric acid and nitric acid), organic acids (oxalic acid and citric acid), and chelating agents (ethylenediaminetetraacetic acid (EDTA) and ethylene diamine tetramethylene phosphonate (EDTMP)). The aim of this study was to optimize a leaching process to recover P-leachate with high purity for P fertilizer production. The results show that both organic and inorganic acids extract P-containing phases but organic acids leach more trace elements, particularly Cu, Zn, Pb and As. Sulphuric acid was the most efficient for P recovery and achieved 94% of total extraction under the optimal conditions, which were 2-h reaction with 0.2 mol/L H 2 SO 4 at a liquid-to-solid ratio of 20:1. EDTA extracted only 20% of the available P, but the leachates were contaminated with high levels of trace elements under optimum conditions (3-h reaction with EDTA at 0.02 mol/L, pH 2, and liquid-to-solid ratio of 20:1). Therefore, EDTA was considered an appropriate pre-treatment agent for reducing the total metal/metalloid content in ISSA, which produced negligible changes in the structure of ISSA and reduced contamination during subsequent P extraction using sulphuric acid. Copyright © 2017 Elsevier Ltd. All rights reserved.

The acidic functional groups of humic acid

Energy Technology Data Exchange (ETDEWEB)

Shanxiang, Li; Shuhe, Sun; Zhai Zongxi, Wu Qihu

1983-09-01

The acidic functional groups content, pK value, DELTAH and DELTAS of humic acid (HA) and nitro-humic acid (NHA) were determined by potentiometry, conductometry and calorimetric titration. The thermodynamic parameters of carboxylic groups and phenolic hydroxyl groups of humic acid are similar to that of simple hydroxy-benzoic acid. The configuration sites of acidic functional groups in humic acid from different coals are different. The carbonyl groups on aromatic rings are probably ortho to phenolic -OH for HA and NHA extracted from Huangxian's brown coal and Japanese lignite, while those from Lingshi's weathered coal are not. The weak -COOH groups of the latter possess higher chemical activity. The -COOH content in HA increases, phenolic -OH group decreases and the chemical acidity of acidic functional groups increases when HA is oxidized by nitric acid. (14 refs.)

Multicentre trial on the efficacy and toxicity of single-dose samarium-153-ethylene diamine tetramethylene phosphonate as a palliative treatment for painful skeletal metastases in China

International Nuclear Information System (INIS)

Tian Jia-he; Zhang Jin-ming; He Yi-jie; Hou Qing-tian; Oyang Qiao-hong; Wang Jian-min; Chuan Ling

1999-01-01

A multicentre trial was organized in China as part of an international coordinated research project to study the efficacy and toxicity of single-dose samarium-153 ethylene diamine tetramethylene phosphonate (EDTMP) as a palliative treatment for painful skeletal metastases. One hundred and five patients with painful bone metastases from various primaries were treated with 153 Sm-EDTMP at a dose of 37 MBq/kg(group I) or 18.5 MBq/kg (group II). The effects were evaluated according to change in daily analgesic consumption, pain score, sum of effect product (SEP), Physician's Global Assessment (PGA), blood counts, and organ function tests conducted regularly for 16 weeks. Fifty-eight of 70 patients in group I and 30 of 35 in group II had a positive response, with SEPs of 22.29±14.47 and 20.13±13.90 respectively. Of 72 patients who had been receiving analgesics, 63 reduced their consumption. PGA showed that the Karnofsky score (KS) increased from 58.54±25.90 to 71.67±26.53, indicating improved general condition, but the difference was not significant. Among subgroups of patients, only those with breast cancer showed a significant change in the Karnofsky score after treatment. Inter-group differences were found for net change in KS between patients with lung and patients with breast cancer, and between patients with lung and patients with oesophageal cancer. Seventeen patients showed no response. No serious side-effects were noted, except for falls in the white blood cell (nadir 1.5 x 10 9 /l) and platelet (nadir 6.0 x 10 10 /l) counts in 44/105 and 34/105 cases, respectively. Ten patients had an abnormal liver function test. Response and side-effects were both independent of dose. In conclusion, 153 Sm-EDTMP provided effective palliation in 83.8% of patients with painful bone metastases; the major toxicity was temporary myelosuppression. Further studies are needed to identify better ways of determining the appropriate dose in the individual case and the efficacy of

The Acid-Base Titration of a Very Weak Acid: Boric Acid

Science.gov (United States)

Celeste, M.; Azevedo, C.; Cavaleiro, Ana M. V.

2012-01-01

A laboratory experiment based on the titration of boric acid with strong base in the presence of d-mannitol is described. Boric acid is a very weak acid and direct titration with NaOH is not possible. An auxiliary reagent that contributes to the release of protons in a known stoichiometry facilitates the acid-base titration. Students obtain the…

Investigation of the hydrolytic and radiolytic degradation of HEH[EHP

International Nuclear Information System (INIS)

Peterman, Dean Richard; McDowell, Rocklan George; Zarzana, Christopher Andrew; Johnson, Kristyn Marie; Rowe, Salene Marie; Groenewold, Gary Steven

2016-01-01

The extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) is a component used in both the Advanced TALSPEAK and ALSEP solvent extraction processes. The most likely compound formed via hydrolytic or radiolytic degradation of HEH[EHP] would be the phosphonic acid 2-ethylhexylphosphonic acid (H2EHP) that is formed by cleavage of the P-O-R bond. Thus far, attempts to detect H2EHP by gas chromatography or mass spectrometry have not been successful. The inability to detect this proposed degradation product in analytical samples is likely due to inadequate analysis techniques, lack of H2EHP production, further decomposition of H2EHP forming products not detectable by the employed analytical techniques, or a combination of all of the above scenarios. In order to address this problem, commercially available alkylphosphonic acids were acquired and used as surrogates for H2EHP in the gas chromatography and mass spectrometry analysis of samples. Once the ability to detect alkylphosphonic acid compounds was confirmed, these analytical techniques were used to confirm the production of H2EHP in samples of HEH[EHP] exposed to nitric acid and nitric acid plus gamma radiation. This report provides a brief summary of results and serves as documentation of the completion the level four milestone M4FT-16IN030102025 “Investigate the hydrolytic and radiolytic degradation of HEH[EHP]”.

Usnic acid controls the acidity tolerance of lichens

International Nuclear Information System (INIS)

Hauck, Markus; Juergens, Sascha-Rene

2008-01-01

The hypotheses were tested that, firstly, lichens producing the dibenzofuran usnic acid colonize substrates characterized by specific pH ranges, secondly, this preferred pH is in a range where soluble usnic acid and its corresponding anion occur in similar concentrations, and thirdly, usnic acid makes lichens vulnerable to acidity. Lichens with usnic acid prefer an ambient pH range between 3.5 and 5.5 with an optimum between 4.0 and 4.5. This optimum is close to the pK a1 value of usnic acid of 4.4. Below this optimum pH, dissolved SO 2 reduces the chlorophyll fluorescence yield more in lichens with than without their natural content of usnic acid. This suggests that usnic acid influences the acidity tolerance of lichens. The putative mechanism of the limited acidity tolerance of usnic acid-containing lichens is the acidification of the cytosol by molecules of protonated usnic acid shuttling protons through the plasma membrane at an apoplastic pH a1 . - Combined field and experimental data suggest that usnic acid makes lichens sensitive to acidity at pH <3.5

Lanthanide-organic frameworks constructed from multi-functional ligands: Syntheses, structures, near-infrared and visible photoluminescence properties

International Nuclear Information System (INIS)

Li Xinfa; Xie Zailai; Lin Jingxiang; Cao Rong

2009-01-01

A series of multi-functional ligands supported lanthanide-organic frameworks, formulated as [Ln(HL 1 )(H 2 L 2 ) 0.5 (H 4 L 2 ) 0.5 (H 2 O)].(H 2 O) 1.5 .{Ln=La (1), Pr (2), Nd (3), Sm (4), Eu (5); H 3 L 1 =5-Sulfosaclicylic acid; H 4 L 2 =N,N'-piperazine (bis-methylene phosphonic acid)}, have been synthesized by hydrothermal reactions. Single crystal X-ray diffractions and powder XRD patterns confirm they are isostructural. They feature 3D framework structures based on extension of a 'zigzag' inorganic chain by organic linkers. Moreover, the photoluminescence properties of 5 and 3 have been investigated, and they show strong solid-state emissions in the visible and near-infrared (IR) regions at room temperature. - Graphical abstract: Five multi-functional ligands supported 3D lanthanide-organic frameworks have been synthesized and structurally characterized. Compounds 5 and 3 displayed strong solid-state emissions in the visible and near-infrared region at room temperature.

[Teichoic acids from lactic acid bacteria].

Science.gov (United States)

Livins'ka, O P; Harmasheva, I L; Kovalenko, N K

2012-01-01

The current view of the structural diversity of teichoic acids and their involvement in the biological activity of lactobacilli has been reviewed. The mechanisms of effects of probiotic lactic acid bacteria, in particular adhesive and immunostimulating functions have been described. The prospects of the use of structure data of teichoic acid in the assessment of intraspecific diversity of lactic acid bacteria have been also reflected.

Preparation of fulvic acid and low-molecular organic acids by oxidation of weathered coal humic acid

Energy Technology Data Exchange (ETDEWEB)

Shinozuka, T.; Ito, A.; Sasaki, O.; Yazawa, Y.; Yamaguchi, T. [Chiba Institute of Technolgy, Chiba (Japan). Dept. of Industrial Chemistry

2002-07-01

Weathered coal contains much humic acid and a little fulvic acid. Therefore, the production of fulvic acid, the most valuable humic substance because of its water-solubility, was examined by ozone and hydrogen peroxide oxidation of humic acid extracted form Xinjiang (China) weathered coal. The resulting products of the oxidation were water soluble fulvic acid and organic acids, mainly formic acid and oxalic acid. The product yield of fulvic acid was 20 (C%) and that of organic acids were 39 (C%) for formic and acid 13 (C%) for oxalic acid. The formed fulvic acid showed a higher content of oxygen and carboxyl groups, than those of the extracted one from the original weathered coal.

Acid Rain

Science.gov (United States)

Bricker, Owen P.; Rice, Karen C.

1995-01-01

Although acid rain is fading as a political issue in the United States and funds for research in this area have largely disappeared, the acidity of rain in the Eastern United States has not changed significantly over the last decade, and it continues to be a serious environmental problem. Acid deposition (commonly called acid rain) is a term applied to all forms of atmospheric deposition of acidic substances - rain, snow, fog, acidic dry particulates, aerosols, and acid-forming gases. Water in the atmosphere reacts with certain atmospheric gases to become acidic. For example, water reacts with carbon dioxide in the atmosphere to produce a solution with a pH of about 5.6. Gases that produce acids in the presence of water in the atmosphere include carbon dioxide (which converts to carbonic acid), oxides of sulfur and nitrogen (which convert to sulfuric and nitric acids}, and hydrogen chloride (which converts to hydrochloric acid). These acid-producing gases are released to the atmosphere through natural processes, such as volcanic emissions, lightning, forest fires, and decay of organic matter. Accordingly, precipitation is slightly acidic, with a pH of 5.0 to 5.7 even in undeveloped areas. In industrialized areas, most of the acid-producing gases are released to the atmosphere from burning fossil fuels. Major emitters of acid-producing gases include power plants, industrial operations, and motor vehicles. Acid-producing gases can be transported through the atmosphere for hundreds of miles before being converted to acids and deposited as acid rain. Because acids tend to build up in the atmosphere between storms, the most acidic rain falls at the beginning of a storm, and as the rain continues, the acids "wash out" of the atmosphere.

Enzymatic formation of hexadecenoic acid from palmitic acid

International Nuclear Information System (INIS)

Nakano, Masao; Fujino, Yasuhiko

1975-01-01

Desaturation of palmitic acid was investigated in an enzyme system prepared from rat liver. 2-trans-Hexadecenoic acid as well as 9-cis-gexadecenoic acid (palmitoleic acid) were found to be formed as monoenoic acid in this system. (author)

Sequential injection redox or acid-base titration for determination of ascorbic acid or acetic acid.

Science.gov (United States)

Lenghor, Narong; Jakmunee, Jaroon; Vilen, Michael; Sara, Rolf; Christian, Gary D; Grudpan, Kate

2002-12-06

Two sequential injection titration systems with spectrophotometric detection have been developed. The first system for determination of ascorbic acid was based on redox reaction between ascorbic acid and permanganate in an acidic medium and lead to a decrease in color intensity of permanganate, monitored at 525 nm. A linear dependence of peak area obtained with ascorbic acid concentration up to 1200 mg l(-1) was achieved. The relative standard deviation for 11 replicate determinations of 400 mg l(-1) ascorbic acid was 2.9%. The second system, for acetic acid determination, was based on acid-base titration of acetic acid with sodium hydroxide using phenolphthalein as an indicator. The decrease in color intensity of the indicator was proportional to the acid content. A linear calibration graph in the range of 2-8% w v(-1) of acetic acid with a relative standard deviation of 4.8% (5.0% w v(-1) acetic acid, n=11) was obtained. Sample throughputs of 60 h(-1) were achieved for both systems. The systems were successfully applied for the assays of ascorbic acid in vitamin C tablets and acetic acid content in vinegars, respectively.

Glycosyltransferase glycosylating flavokermesic acid and/or kermesic acid

DEFF Research Database (Denmark)

2016-01-01

An isolated glycosyltransferase (GT) polypeptide capable of: (I) : conjugating glucose to flavokermesic acid (FK); and/or (II) : conjugating glucose to kermesic acid (KA) and use of this GT to e.g. make Carminic acid.......An isolated glycosyltransferase (GT) polypeptide capable of: (I) : conjugating glucose to flavokermesic acid (FK); and/or (II) : conjugating glucose to kermesic acid (KA) and use of this GT to e.g. make Carminic acid....

GLYCOSYLTRANSFERASE GLYCOSYLATING FLAVOKERMESIC ACID AND/OR KERMESIC ACID

DEFF Research Database (Denmark)

2015-01-01

An isolated glycosyltransferase (GT) polypeptide capable of: (I): conjugating glucose to flavokermesic acid (FK); and/or (II): conjugating glucose to kermesic acid (KA) and use of this GT to e.g. make Carminic acid.......An isolated glycosyltransferase (GT) polypeptide capable of: (I): conjugating glucose to flavokermesic acid (FK); and/or (II): conjugating glucose to kermesic acid (KA) and use of this GT to e.g. make Carminic acid....

New Estimation of the Dosage of Scale Inhibitor in the Cooling Water System

Directory of Open Access Journals (Sweden)

Jiang Jiaomei

2011-01-01

Full Text Available In the cooling water system, excessive use of organic phosphate scale inhibitors is harmful to environment. Reducing the dosage of the organic phosphate scale inhibitor is important. A self-made jacketed crystallizer was used in this experiment. The critical pH values have been determined in cooling water systems with series of Ca2+ concentrations by adding different concentration of the scale inhibitor ATMP (Amino Trimethylene Phosphonic Acid according to the calcium carbonate Metastable zone theory. A model equation at 45 °C and pH=9 was proposed to estimate the lowest dose of the scale inhibitor ATMP. The measured pH value was approximate to the expected pH value in two cooling water systems through verification test.

Anion embedded sol-gel films on Al for corrosion protection

International Nuclear Information System (INIS)

Sheffer, Mari; Groysman, Alec; Starosvetsky, David; Savchenko, Natali; Mandler, Daniel

2004-01-01

We report here on the successful incorporation of organic anions into a sol-gel film on Al as a means of enhancing the protection against corrosion. Following our previous study where we showed that hydrophobic sol-gel films provided pronounced corrosion inhibition, we studied the corrosion inhibition that phenylphosphonic acid (PPA) has when embedded inside a thin sol-gel coating on Al. The anion of this organic anion tends to stay inside a phenyltrimethoxysilane (PTMOS) based sol-gel film due to π-interactions. Our findings, which are derived primarily from potentiodynamic polarization measurements, electrochemical noise, scanning electron microscopy measurements and Auger electron spectroscopy (AES), clearly show that the organic phosphonate adds to the protection efficiency of the sol-gel film

An ICP-AES method for the determination of trace metals in uranium by solvent extraction using KSM-17

International Nuclear Information System (INIS)

Jacob, Mary; Radhakrishnan, K.; Dhami, P.S.; Kulkarni, V.T.; Joshi, M.V.; Patwardhan, A.B.; Ramanujam, A.; Mathur, J.N.

1994-01-01

This paper describes the studies carried out for the determination of trace metallic impurities in uranium solutions. Uranium matrix is separated from the impurity elements by its selective extraction using 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (KSM-17, equivalent to PC88A). The aqueous phase is analysed for trace impurities by inductively coupled argon plasma atomic emission spectrometry. The studies also include recovery of impurities at various acidities and spectral interferences of uranium over the analyte element channels. Based on the above studies, a method has been standardised for the analysis of nineteen elements in uranium solutions. The relative standard deviation of the method for various elements is in the range of +- 1-5%. (author). 7 refs., 8 tabs., 1 fig

Specific bile acid radioimmunoassays for separate determinations of unconjugated cholic acid, conjugated cholic acid and conjugated deoxycholic acid in serum and their clinical application

International Nuclear Information System (INIS)

Matern, S.; Gerok, W.

1977-01-01

Specific radioimmunoassays for separate determinations of serum unconjugated cholic, conjugated cholic and conjugated deoxycholic acids have been developed. Prior to the radioimmunoassay, extraction of serum bile acids was performed with Amberlite XAD-2. Unconjugated cholic acid was separated from glyco- and taurocholic acids by thin-layer chromatography. At 50% displacement of bound labeled glyco[ 3 H]cholic acid using antiserum obtained after immunization with cholic acid-bovine serum albumin-conjugate the cross-reactivity of taurocholic acid was 100%, cholic acid 80%, glycochenodeoxycholic acid 10%, chenodeoxycholic acid 7%, conjugated deoxycholic acid 3%, and conjugated lithocholic acid 3 H]cholic acid was linear on a logit-log plot from 5 to 80 pmol of unlabeled glycocholic acid. Fasting serum conjugated cholic acid in healthy subjects was 0.68 +- 0.34 μmol/l. Unconjugated cholic acid was determined by a solid phase radioimmunoassay using the cholic acid antibody chemically bound to Sepharose. The displacement curve of [ 3 H]cholic acid in the solid phase radioimmunoassay was linear on a logit-log plot from 5 to 200 pmol of unlabeled cholic acid. The coefficient of variation between samples was 5%. Fasting serum conjugated deoxycholic acid concentrations in 10 healthy subjects ranged from 0.18 to 0.92 μmol/l determined by a radioimmunoassay using antiserum obtained after immunization with deoxycholic acid-bovine serum albumin-conjugate. The clinical application of these bile acid radioimmunoassays is shown by an 'oral cholate tolerance test' as a sensitive indicator of liver function and by an 'oral cholyglycine tolerance test' as a useful test for bile acid absorption. (orig.) [de

Amino acids in the sedimentary humic and fulvic acids

Digital Repository Service at National Institute of Oceanography (India)

Sardessai, S.

acids in the coastal Arabian Sea sediments: whereas amino acids content of fulvic acids was lower than that of humic acids in the coastal sediments of Bay of Bengal. Slope sedimentary humic acids were relatively enriched in amino acids as compared...

Chiral recognition with enantioselective ion exchangers based on carbamoylated cinchonan derivatives as chiral selectors for the HPLC enantioseparation

International Nuclear Information System (INIS)

Laemmerhofer, M.

1996-11-01

The high-performance liquid chromatographic (HPLC) separation of enantiomers is preferentially performed using chiral stationary phases (CSPs). If the chiral auxiliary (selector, SO) contains charged or ionizable groups one gets ion exchanger type CSPs which may bind and retain oppositely charged analytes (selectands, SAs). We prepared anion exchanger type CSPs with various quinine and quinidine carbarnates as chiral SOs immobilized either on porous or non-porous silica. These CSPs are able to resolve the enantiomers of a wide spectrum of chiral carboxylic, sulfonic, phosphonic, phosphoric acids and of many other chiral acidic solutes (e.g. N-derivatized alpha-, beta- , gamma-amino acids as 2,4-dinitrophenyl, 3,5-dinitrobenzoyl, benzoyl, acetyl, formyl, t.-butoxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl, dansyl amino acids and peptides, alpha-arylalkylcarboxylic acids as profens, alpha-aryloxyalkylcarboxylic acids, alpha-arylthioalkylcarboxylic acids and acidic drugs like etodolac, proglumide, acenocournarol, leucovorin, omeprazole, pantoprazole) employing buffered aqueous mobile phases or non-aqueous mobile phases with buffer dissolved in the organic solvent. The influence of mobile phase parameters and other experimental conditions on retention and enantioselectivity has been evaluated for isocratic and gradient elution techniques, aided by the commercial method development computer software DryLab. Several 'Quantitative Structure-Retention Relationships' (QSRR) have been derived, which allowed prediction of enantioselectivity of new analytes and moreover the optimization of the SO-structure. Spectroscopic investigations as H-NMR, FTIR of certain SO-SA-complexes have been exerted to unveil the mechanism of chiral recognition. (author)

Effect of propionic acid on citric acid fermentation in an integrated citric acid-methane fermentation process.

Science.gov (United States)

Xu, Jian; Bao, Jia-Wei; Su, Xian-Feng; Zhang, Hong-Jian; Zeng, Xin; Tang, Lei; Wang, Ke; Zhang, Jian-Hua; Chen, Xu-Sheng; Mao, Zhong-Gui

2016-03-01

In this study, an integrated citric acid-methane fermentation process was established to solve the problem of wastewater treatment in citric acid production. Citric acid wastewater was treated through anaerobic digestion and then the anaerobic digestion effluent (ADE) was further treated and recycled for the next batch citric acid fermentation. This process could eliminate wastewater discharge and reduce water resource consumption. Propionic acid was found in the ADE and its concentration continually increased in recycling. Effect of propionic acid on citric acid fermentation was investigated, and results indicated that influence of propionic acid on citric acid fermentation was contributed to the undissociated form. Citric acid fermentation was inhibited when the concentration of propionic acid was above 2, 4, and 6 mM in initial pH 4.0, 4.5 and, 5.0, respectively. However, low concentration of propionic acid could promote isomaltase activity which converted more isomaltose to available sugar, thereby increasing citric acid production. High concentration of propionic acid could influence the vitality of cell and prolong the lag phase, causing large amount of glucose still remaining in medium at the end of fermentation and decreasing citric acid production.

A Direct, Biomass-Based Synthesis of Benzoic Acid: Formic Acid-Mediated Deoxygenation of the Glucose-Derived Materials Quinic Acid and Shikimic Acid

Energy Technology Data Exchange (ETDEWEB)

Arceo, Elena; Ellman, Jonathan; Bergman, Robert

2010-05-03

An alternative biomass-based route to benzoic acid from the renewable starting materials quinic acid and shikimic acid is described. Benzoic acid is obtained selectively using a highly efficient, one-step formic acid-mediated deoxygenation method.

Structural insights into the bacterial carbon - phosphorus lyase machinery

DEFF Research Database (Denmark)

Seweryn, Paulina; Van, Lan Bich; Kjeldgaard, Morten

2015-01-01

Phosphorus is required for all life and microorganisms can extract it from their environment through several metabolic pathways. When phosphate is in limited supply, some bacteria are able to use phosphonate compounds, which require specialized enzymatic machinery to break the stable carbon......–phosphorus (C–P) bond. Despite its importance, the details of how this machinery catabolizes phosphonates remain unknown. Here we determine the crystal structure of the 240-kilodalton Escherichia coli C–P lyase core complex (PhnG–PhnH–PhnI–PhnJ; PhnGHIJ), and show that it is a two-fold symmetric hetero...

Synthesis and biological activity of M6-P and M6-P analogs on fibroblast and keratinocyte proliferation.

Science.gov (United States)

Clavel, Caroline; Barragan-Montero, Véronique; Garric, Xavier; Molès, Jean-Pierre; Montero, Jean-Louis

2005-09-01

A new synthetic route to obtain the carboxylate analog of mannose 6-phosphate (M6-P) is presented. The effects of the M6-P, the carboxylate and two other analogs (the phosphonate and the alpha,beta ethylenic carboxylate) on the proliferation of human keratinocytes and dermal fibroblasts as well as on the proliferation of a murine fibroblast cell line, 3T3-J2 are tested. We observed that M6-P is a potent inhibitor of proliferation of both fibroblasts and keratinocytes. Among its analogs, the phosphonate showed a similar effect on human dermal fibroblasts but not on keratinocytes.

Catalytic acetoxylation of lactic acid to 2-acetoxypropionic acid, en route to acrylic acid

NARCIS (Netherlands)

Beerthuis, R.; Granollers, M.; Brown, D.R.; Salavagione, H.J.; Rothenberg, G.; Shiju, N.R.

2015-01-01

We present an alternative synthetic route to acrylic acid, starting from the platform chemical lactic acid and using heterogeneous catalysis. To improve selectivity, we designed an indirect dehydration reaction that proceeds via acetoxylation of lactic acid to 2-acetoxypropionic acid. This

[Lipid synthesis by an acidic acid tolerant Rhodotorula glutinis].

Science.gov (United States)

Lin, Zhangnan; Liu, Hongjuan; Zhang, Jian'an; Wang, Gehua

2016-03-01

Acetic acid, as a main by-product generated in the pretreatment process of lignocellulose hydrolysis, significantly affects cell growth and lipid synthesis of oleaginous microorganisms. Therefore, we studied the tolerance of Rhodotorula glutinis to acetic acid and its lipid synthesis from substrate containing acetic acid. In the mixed sugar medium containing 6 g/L glucose and 44 g/L xylose, and supplemented with acetic acid, the cell growth was not:inhibited when the acetic acid concentration was below 10 g/L. Compared with the control, the biomass, lipid concentration and lipid content of R. glutinis increased 21.5%, 171% and 122% respectively when acetic acid concentration was 10 g/L. Furthermore, R. glutinis could accumulate lipid with acetate as the sole carbon source. Lipid concentration and lipid yield reached 3.20 g/L and 13% respectively with the initial acetic acid concentration of 25 g/L. The lipid composition was analyzed by gas chromatograph. The main composition of lipid produced with acetic acid was palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid, including 40.9% saturated fatty acids and 59.1% unsaturated fatty acids. The lipid composition was similar to that of plant oil, indicating that lipid from oleaginous yeast R. glutinis had potential as the feedstock of biodiesel production. These results demonstrated that a certain concentration of acetic acid need not to be removed in the detoxification process when using lignocelluloses hydrolysate to produce microbial lipid by R. glutinis.

Development of Ultrafiltration Membrane-Separation Technology for Energy-Efficient Water Treatment and Desalination Process

Energy Technology Data Exchange (ETDEWEB)

Yim, Woosoon [Univ. of Nevada, Las Vegas, NV (United States); Bae, Chulsung [Rensselaer Polytechnic Inst., Troy, NY (United States)

2016-10-28

. Recently, sulfonated SEBS became commercially available and has been extensively explored for membrane-mediated water purification technology. The sulfonated block copolymer creates a well developed nano-sale phase-separated morphologies composed of hydrophilic domains (sulfonated polystyrene) and hydrophobic domains (polyethylene/polybutylene). The hydrophilic domains determines transport properties (water transport, salt and/or ion rejection, etc) and the hydrophobic domains provides mechanical stability of the membrane. Unfortunately, a high degree of sulfonation of SEBS induces excessive swelling and deterioration of mechanical stability of the membrane. In an effort to develop robust polymeric membrane materials for water purification technology, phosphonic acid-functionalized SEBS membranes are investigated during this report period. In compare to sulfonated polymers, the corresponding phosphonated polymers are known to swell less because of the formation of extensive hydrogen bonding networks between phosphonates. In addition to the expected better mechanical stability, phosphonated polymers has another advantage over sulfonated polymers for the use water purification membrane; each phosphonate can accommodate two ions while each sulfonate accommodates only one ion. Membrane properties (ion type, ionic density, etc) of new membranes will be studied and their separation performance will be evaluated in water purification and desalination process. Through systematic study of the relationship of chemical structure–surface property–membrane performance, we aim to better understand the nature of membrane fouling and develop more fouling-resistant water purification membranes. The basic understanding of this relationship will lead to the development of advanced membrane materials which can offer a solution to environmentally sustainable production of fresh water.

Synthesis and fabrication of sized-controlled nanoparticles: Using surface self-assemblies as building blocks for developing supralattices on nanocomposite materials

Science.gov (United States)

Yee, Chanel Kitmon

2001-10-01

A general one-phase synthesis for self-assembling thiols onto gold, platinum, palladium and iridium nanoparticles using tetrahydrofuran (THF) as the solvent, and lithium triethylborohydride (superhydride) as the reducing agent, is presented. Using the same synthetic procedure gold nanoparticles functionalized with 11-hydroxyundecane-1-thiol and 4'-bromo-4-mercaptobiphenyl were prepared to show that the availability and reflexibility of this method could lead to surface fabrication with various type of facial moieties. Alkyl selenide- and alkyl thiolate-functionalized gold nanoparticles were also prepared by the same method at 6°C. The properties were compared to their counterparts made at 25°C. The formation of the Se-Au bond and S-Au bonds was investigated by transmission Fourier transform infrared spectroscopy (FTIR), while the bond nature in each case was examined by x-ray photoelectron spectroscopy (XPS). Particle size was determined by Transmission Electron Microscopy (TEM), and further confirmed by ultraviolet spectroscopy (UV). Superparamagnetic Fe and Fe2O3 nanoparticles were synthesized by ultrasound irradiation and post-fabricated with alkyl sulfonic acids of various chain lengths and octadecyl phosphonic acid. TEM reveals nanoparticles of 5--10 mn in diameter. FTIR spectra suggest that the alkyl chains are packed in a solid-like assembly with packing disorder increasing with the decreasing chain length. The octadecyl sulfonic acid coating displays the lowest magnetization within the sulfonic acid series, which may be explained by the high packing and ordering of the alkyl chains on the particle surface. The smallest value of magnetization in the OPA case suggests that the spin-state of surface Fe3+ ions is affected by the bonded surfactant, and that the phosphonate empty d-orbitals increase magnetic interactions between neighboring Fe3+ spins. To build superstructures beyond the monolayer level, a general route for the attachment of amino

[Regulating acid stress resistance of lactic acid bacteria--a review].

Science.gov (United States)

Wu, Chongde; Huang, Jun; Zhou, Rongqing

2014-07-04

As cell factories, lactic acid bacteria are widely used in food, agriculture, pharmaceutical and other industries. Acid stress is one the important survival challenges encountered by lactic acid bacteria both in fermentation process and in the gastrointestinal tract. Recently, the development of systems biology and metabolic engineering brings unprecedented opportunity for further elucidating the acid tolerance mechanisms and improving the acid stress resistance of lactic acid bacteria. This review addresses physiological mechanisms of lactic acid bacteria during acid stress. Moreover, strategies to improve the acid stress resistance of lactic acid were proposed.

Preparation and characterization Al3+-bentonite Turen Malang for esterification fatty acid (palmitic acid, oleic acid and linoleic acid)

Science.gov (United States)

Abdulloh, Abdulloh; Aminah, Nanik Siti; Triyono, Mudasir, Trisunaryanti, Wega

2016-03-01

Catalyst preparation and characterization of Al3+-bentonite for esterification of palmitic acid, oleic acid and linoleic acid has been done. Al3+-bentonite catalyst was prepared from natural bentonite of Turen Malang through cation exchange reaction using AlCl3 solution. The catalysts obtained were characterized by XRD, XRF, pyridine-FTIR and surface area analyser using the BET method. Catalyst activity test of Al3+-bentonite for esterification reaction was done at 65°C using molar ratio of metanol-fatty acid of 30:1 and 0.25 g of Al3+-bentonite catalyst for the period of ½, 1, 2, 3, 4 and 5 hours. Based on the characterization results, the Al3+-bentonite Turen Malang catalyst has a d-spacing of 15.63 Ǻ, acid sites of Brönsted and Lewis respectively of 230.79 µmol/g and 99.39 µmol/g, surface area of 507.3 m2/g and the average of radius pore of 20.09 Å. GC-MS analysis results of the oil phase after esterification reaction showed the formation of biodiesel (FAME: Fatty acid methyl ester), namely methyl palmitate, methyl oleate and methyl linoleate. The number of conversions resulted in esterification reaction using Al3+-bentonite Turen Malang catalyst was 74.61%, 37.75%, and 20, 93% for the esterification of palmitic acid, oleic acid and linoleic acid respectively.

Efficacy of Lactic Acid, Lactic Acid-Acetic Acid Blends, and Peracetic Acid To Reduce Salmonella on Chicken Parts under Simulated Commercial Processing Conditions.

Science.gov (United States)

Ramirex-Hernandez, Alejandra; Brashears, Mindy M; Sanchez-Plata, Marcos X

2018-01-01

The poultry processing industry has been undergoing a series of changes as it modifies processing practices to comply with new performance standards for chicken parts and comminuted poultry products. The regulatory approach encourages the use of intervention strategies to prevent and control foodborne pathogens in poultry products and thus improve food safety and protect human health. The present studies were conducted to evaluate the efficacy of antimicrobial interventions for reducing Salmonella on inoculated chicken parts under simulated commercial processing conditions. Chicken pieces were inoculated by immersion in a five-strain Salmonella cocktail at 6 log CFU/mL and then treated with organic acids and oxidizing agents on a commercial rinsing conveyor belt. The efficacy of spraying with six different treatments (sterile water, lactic acid, acetic acid, buffered lactic acid, acetic acid in combination with lactic acid, and peracetic acid) at two concentrations was evaluated on skin-on and skin-off chicken thighs at three application temperatures. Skinless chicken breasts were used to evaluate the antimicrobial efficacy of lactic acid and peracetic acid. The color stability of treated and untreated chicken parts was assessed after the acid interventions. The lactic acid and buffered lactic acid treatments produced the greatest reductions in Salmonella counts. Significant differences between the control and water treatments were identified for 5.11% lactic acid and 5.85% buffered lactic acid in both skin-on and skin-off chicken thighs. No significant effect of treatment temperature for skin-on chicken thighs was found. Lactic acid and peracetic acid were effective agents for eluting Salmonella cells attached to chicken breasts.

Extraterrestrial Organic Compounds in Meteorites

Science.gov (United States)

Botta, Oliver; Bada, Jeffrey L.; Meyer, Michael (Technical Monitor)

2003-01-01

Many organic compounds or their precursors found in meteorites originated in the interstellar or circumstellar medium and were later incorporated into planetesimals during the formation of the solar system. There they either survived intact or underwent further processing to synthesize secondary products on the meteorite parent body. The most distinct feature of CI and CM carbonaceous chondrites, two types of stony meteorites, is their high carbon content (up to 3% of weight), either in the form of carbonates or of organic compounds. The bulk of the organic carbon consists of an insoluble macromolecular material with a complex structure. Also present is a soluble organic fraction, which has been analyzed by several separation and analytical procedures. Low detection limits can be achieved by derivatization of the organic molecules with reagents that allow for analysis by gas chromatography/mass spectroscopy and high performance liquid chromatography. The CM meteorite Murchison has been found to contain more than 70 extraterrestrial amino acids and several other classes of compounds including carboxylic acids, hydroxy carboxylic acids, sulphonic and phosphonic acids, aliphatic, aromatic and polar hydrocarbons, fullerenes, heterocycles as well as carbonyl compounds, alcohols, amines and amides. The organic matter was found to be enriched in deuterium, and distinct organic compounds show isotopic enrichments of carbon and nitrogen relative to terrestrial matter.

Investigation of uranium (VI) extraction mechanisms from phosphoric and sulfuric media by {sup 31}P-NMR

Energy Technology Data Exchange (ETDEWEB)

Fries, B.; Marie, C.; Pacary, V.; Berthon, C.; Miguirditchian, M.; Charbonnel, M.C. [CEA, Centre de Marcoule, Nuclear Energy Divison, RadioChemistry and Processes Department - DRCP, F-30207 Bagnols-sur-Ceze (France); Mokhtari, H. [AREVA Mines, Process and Analysis Department - SEPA, F-87250 Bessines-sur-Gartempe (France)

2016-07-01

Phosphate rocks contain uranium (∼1000 ppm on average) and are considered as a secondary source for uranium production. Uranium extraction using DEHCNPB (butyl-1-[N,N-bis(2-ethylhexyl)carbamoyl]nonyl phosphonic acid, a bifunctional cationic extractant) has been studied to better understand mechanism differences depending on the original acidic solution (phosphoric or sulfuric). Solvent extraction batch experiments were carried out and the organic phases were probed using {sup 31}P-NMR. This technique enabled to demonstrate that phosphoric acid is poorly extracted by DEHCNPB ([H{sub 3}PO{sub 4}]{sub org} < 2 mM), using direct quantification in the organic phase by {sup 31}P-NMR spectra integration. Moreover, in the presence of uranium in the initial phosphoric acid solution, uranyl extraction by DEHCNPB competes with H{sub 3}PO{sub 4} extraction. Average stoichiometries of U(VI)-DEHCNPB complexes in organic phases were also determined using slope analysis on uranium distribution data. Uranium seems to be extracted from a phosphoric medium by two extractant molecules, whereas more than three DEHCNPB on average would be necessary to extract uranium from a sulfuric medium. Thus, uranium is extracted according to different mechanisms depending on the nature of the initial solution. (authors)

Molecular interaction of pinic acid with sulfuric acid

DEFF Research Database (Denmark)

Elm, Jonas; Kurtén, Theo; Bilde, Merete

2014-01-01

We investigate the molecular interactions between the semivolatile α-pinene oxidation product pinic acid and sulfuric acid using computational methods. The stepwise Gibbs free energies of formation have been calculated utilizing the M06-2X functional, and the stability of the clusters is evaluated...... cluster. The involvement of more than one pinic acid molecule in a single cluster is observed to lead to the formation of favorable (pinic acid)2(H2SO4) and (pinic acid)2(H2SO4)2 clusters. The identified most favorable growth paths starting from a single pinic acid molecule lead to closed structures...

Effect of acetic acid on citric acid fermentation in an integrated citric acid-methane fermentation process.

Science.gov (United States)

Xu, Jian; Chen, Yang-Qiu; Zhang, Hong-Jian; Tang, Lei; Wang, Ke; Zhang, Jian-Hua; Chen, Xu-Sheng; Mao, Zhong-Gui

2014-09-01

An integrated citric acid-methane fermentation process was proposed to solve the problem of extraction wastewater in citric acid fermentation process. Extraction wastewater was treated by anaerobic digestion and then recycled for the next batch of citric acid fermentation to eliminate wastewater discharge and reduce water resource consumption. Acetic acid as an intermediate product of methane fermentation was present in anaerobic digestion effluent. In this study, the effect of acetic acid on citric acid fermentation was investigated and results showed that lower concentration of acetic acid could promote Aspergillus niger growth and citric acid production. 5-Cyano-2,3-ditolyl tetrazolium chloride (CTC) staining was used to quantify the activity of A. niger cells, and the results suggested that when acetic acid concentration was above 8 mM at initial pH 4.5, the morphology of A. niger became uneven and the part of the cells' activity was significantly reduced, thereby resulting in deceasing of citric acid production. Effects of acetic acid on citric acid fermentation, as influenced by initial pH and cell number in inocula, were also examined. The result indicated that inhibition by acetic acid increased as initial pH declined and was rarely influenced by cell number in inocula.

New Acid Combination for a Successful Sandstone Acidizing

Science.gov (United States)

Shafiq, M. U.; Mahmud, H. K. B.; Rezaee, R.

2017-05-01

With the development of new enhanced oil recovery techniques, sandstone acidizing has been introduced and played a pivotal role in the petroleum industry. Different acid combinations have been applied, which react with the formation, dissolve the soluble particles; thus increase the production of hydrocarbons. To solve the problems which occurred using current preflush sandstone acidizing technology (hydrochloric acid); a new acid combination has been developed. Core flooding experiments on sandstone core samples with dimensions 1.5 in. × 3 in. were conducted at a flow rate of 2 cm3/min. A series of hydrochloric-acetic acid mixtures with different ratios were tested under 150°F temperature. The core flooding experiments performed are aimed to dissolve carbonate, sodium, potassium and calcium particles from the core samples. These experiments are followed by few important tests which include, porosity-permeability, pH value, Inductively Coupled Plasma (ICP) analysis and Nuclear Magnetic Resonance (NMR measurements). All the results are compared with the results of conventional hydrochloric acid technology. NMR and porosity analysis concluded that the new acid combination is more effective in creating fresh pore spaces and thus increasing the reservoir permeability. It can be seen from the pore distribution before and after the acidizing. Prior applying acid; the large size of pores appears most frequently in the pore distribution while with the applied acid, it was found that the small pore size is most the predominant of the pore distribution. These results are validated using ICP analysis which shows the effective removal of calcium and other positive ions from the core sample. This study concludes that the combination of acetic-hydrochloric acid can be a potential candidate for the preflush stage of sandstone acidizing at high temperature reservoirs.

Application of citric acid in acid stimulation treatments

Energy Technology Data Exchange (ETDEWEB)

Alkhaldi, M.H.; Sarma, H.K. [Adelaide Univ., Adelaide (Australia); Nasr-el-Din, H.A. [Texas A and M Univ., College Station, TX (United States)

2009-07-01

A rotating disk apparatus was used to investigate mass transfer during the reaction of citric acid with calcite. The study evaluated the effects of initial acid concentrations, temperature, and disk rotational speed on the effective diffusion coefficient of citric acid. The diffusion coefficient was calculated at 25, 40, and 50 degrees C using various citric acid concentrations. The study indicated that the coefficient was a function of the interactions between calcium citrate precipitation and counter calcium ions. At high acid concentrations, the effects of calcium citrate precipitation and counter calcium ions were significant. The calculated citric acid diffusion coefficients were not comparable with measured effective diffusion coefficients using the rotating disk. At lower initial citric acid concentrations, the effects of both calcium citrate precipitation and counter calcium ions on citric acid diffusivity were minimal. It was concluded that temperature effects on the diffusion coefficient followed Arrhenius law. Activation energy was equal to 37.9 kJ/mol. 34 refs., 4 tabs., 13 figs.

Acid distribution in phosphoric acid fuel cells