Polyphosphate

Polyphosphates. The force field of the triphosphate ion P3Oi05- has been estimated, leading to the forms of the normal vibrations and assignment of 

The distribution of phosphate units in sodium sulphato-phosphate glasses can be determined by 31P n.m.r. spectroscopy.561 

Propionibacteria contain large amounts of polyphosphates. High-molecular-weight (acid-insoluble) compounds containing from 70 to 500 residues of 

Salt-soluble polyphosphates may be involved in nucleic acid synthesis. The content of salt-soluble polyphosphates in P. shermanii reached a maximum at 72 h (3 mg/g of biomass), and subsequently decreased (Fig. 4.16). The content of polyphosphates soluble in alkali, after an insignificant decrease in the first days of incubation, increased constantly in culture and reached 4 mg/g of biomass at 120 h. The main species is represented by high-molecular-weight polyphosphates, soluble in hot IN perchloric acid their cellular content gradually increased up to 11 mg/g of biomass at 96 h (Fig. 4.16) (Konovalova and Vorobjeva, 1972). 

Kulaev (1979) showed that such evolutionary conserved organisms as Micrococcus lysodeicticus and P. shermanii possess a glycolysis-dependent polyphosphate synthesis system in addition to the ATP-dependent one. It has been established (Bobic, 1971 Kulaev et al, 1973) that the biosynthesis of polyphosphates in propionibacteria can proceed both via the terminal phosphate of ATP as well as that of 1,3-diphosphoglyceric acid (1,3-DPGA)  

The fate of polyphosphates was traced in cells of P. shermanii incubated in a medium deprived of nitrogen sources these cells modeled nitrogen-starved immobilized cells. We observed that in nitrogen-starved cells incubated with lactate there was an increase in the content of all three fractions of polyphosphates during the first 3 days (Fig. 4.17). Afterwards the most polymeric fraction (extracted with hot perchloric acid) remained at 

Cultivation time, h Biomass, mg/ml Medium lactate, mg/ml Cellular ATP, pmol/ g dry weight 

A second factor which determines the maximum chain lengths of the polyphosphates which are able to crystallize is the increase in polarity of the molecules which takes place as the degree of polymerization increases. 

Two factors thus appear to be responsible for the failure so far to obtain linear polyphosphates containing 6-200 phosphorus atoms in a crystalline state (1) the difficulty of crystallization from a mixture of similar compounds, and (2) the effect of polar groups on the molecules. 

The conformations of polyphosphate chains in the crystals depend on the nature of the metal cations. The period of the recurring unit changes depending on the charge, shape and electronic envelope structure of the metal cations. The structures of some crystalline 

All high-molecular-weight products remain in equilibrium with cyclic, oligomeric metaphosphates and cross-linked network polyphosphates. In the latter, at least two of the O groups per chain are replaced by other 

The fraction of individual groups depends on the Na/P ratio and the water content. Hydroxyl and 0 groups can occur as end groups. 

According to V. Knorre, sodium polyphosphate, called Madrell s salt, is obtained by heating the residue from evaporation of a solution of NaN03 and phosphoric acid. 

A solution of 20 g. of NaN03 in 25 ml. of water is prepared, mixed with 42 ml, of phosphoric acid (d 1.3) and evaporated on a water bath. The residue is then heated for four hours at 330°C and the melt is extracted with water. The salt is obtained as a practically insoluble white powder. The yield is about 95%. For unknown reasons, the preparation sometimes proves unsuccessful. 

Karbe and G. Jander. Kolloid-Beihefte 54, 80-91 (1942). A. Kh. Bronnikov. Zh. Prikladnoy Khlmll 1, 1287 (1939) (cited in Karbe and Jander). 

The preparation starts with the production of seed crystals. Thus 85 g. of NajgHPO and 15 g. of NH4H3PO4 are heated at 800-900°C until all water and NH3 are removed. Then the mixture is allowed to cool and kept at a constant temperature between 650 and 550°C for a few hours. The melt solidifies almost completely to a fibrous product, which is still somewhat Impure, since an excess of phosphoric acid was used. The fibrous mass is pulverized, washed several times with water and dried with alcohol and ether. 

in the Pascal method, a melt of Graham s salt is allowed to cool to 600°C, the seed crystals are strewn on its surface, and the melt is kept for another half hour at 550°C, during which it solidifies to a completely pure material. 

During research for anticorrosive pigments with improved performance properties compared to zinc phosphate, the development of so-caUed modified polyphosphate pigments was a further focus. 

Orthophosphates are manufactured using the reaction of orthophosphoric acid with basic and/or amphoteric substances. Polyphosphates are obtained by condensation of acidic orthophosphates at higher temperatures [5.54]  

Modified polyphosphate pigments, which are of practical importance today, are predominantly reaction products of acidic aluminum tripolyphosphate with compounds based upon zinc, strontium, calcium, and magnesium (Table 5.7). 

Development activities in conjunction with polyphosphate pigments have been focused on the high chelate building potential of acidic aluminum tripolyphosphate with metal ions [5.87]. 

Zinc aluminum phosphates with aluminum phosphate ]5.75, 5.87] 

Kinetic studies of the nucleotide analogs, y-phenylpropyl di- and triphosphate, have been undertaken to define the role of the adenosine residue in the chemical and enzymic reactions of adenosine triphosphate. A catalytic function associated with binding of metal ions at the adenine nitrogens has been ascribed to the adenosine moiety in phosphate transfer reactions in which adenosine di- or triphosphates function as the phosphate source109- 2. The pH-rate profile (Fig. 6) for the hydrolysis of -y-phenylpropyl diphosphate 

This attractive hypothesis may prove difficult to substantiate owing to the high probability of forming nonproductive complexes or dimeric chelates11 121. Supporting evidence for a similar pathway in phosphate monoesters will be discussed under Section 2.5. 

General structure of polyphosphoesters where R = divalent organic groups. 

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Polyphosphates are used as detergents (calgon) but disposal of the residual phosphate causes major problems Phosphates are of importance as flame-proofing agents. See also phosphorus. 

Br , citrate, CE, 2,3-dimercaptopropanol, dithizone, EDTA, E, OH , NagP30io, SCN , tartrate, thiosulfate, thiourea, triethanolamine BE4, citrate, V,V-dihydroxyethylglycine, EDTA, E , polyphosphates, tartrate Citrate, CN , 2,3-dimercaptopropanol, dimercaptosuccinic acid, dithizone, EDTA, glycine, E, malonate, NH3, 1,10-phenanthroline, SCN , 820 , tartrate Citrate, V,V-dihydroxyethylglycine, EDTA, E , PO , reducing agents (ascorbic acid), tartrate, tiron... 

When 20% of the phosphoms was polyphosphate, the compounds ia the product were ia the ratio of 3.5 mole MAP per mole of the pyrophosphate. The principal use of the material was ia the production of suspension fertilizers. In this appHcation the polyphosphate content imparted improved storage properties to the suspensions. The granular soHd APP, however, also had excellent storage properties and was a good material for use ia bulk blends and for direct appHcation. 

Fig. 22. Effects of polyphosphate level and N P20 weight ratio on solubility of ammoniated phosphoric acids at 0°C, where A represents 70% of total P20 as polyphosphate B, 45% and C, 0%, and the various crystallizing phases are (1), (NH H2PO (2), (NH 2HPO (3), (NH g HEgO -HgO) (4),...

Orthophosphate Hquid mixtures are ineffective as micronuttient carriers because of the formation of metal ammonium phosphates such as ZnNH PO. However, micronutrients are much more soluble in ammonium phosphate solutions in which a substantial proportion of the phosphoms is polyphosphate. The greater solubiHty results from the sequestering action of the polyphosphate. The amounts of Zn, Mn, Cu, and Fe soluble in base solution with 70% of its P as polyphosphate are 10 to 60 times their solubiHties in ammonium orthophosphate solution. When a mixture of several micronutrients is added to the same solution, the solubiHty of the individual metals is lowered significantly. In such mixtures the total micronuttient content should not exceed 3% and the storage time before precipitates appear may be much shorter than when only one micronuttient is present. 

Synthetic organic chelates and natural organic complexes are sometimes more effective agronomically per unit of micronuttient than inorganic forms, but the organic materials are more expensive. The chelates can be used with both orthophosphate and polyphosphate Hquids and suspensions. 

Insoluble Ammonium Polyphosphate. When ammonium phosphates are heated ia the presence of urea (qv), or by themselves under ammonia pressure, relatively water-iasoluble ammonium polyphosphate [68333-79-9] is produced (49). There are several crystal forms and the commercial products, avaUable from Monsanto, Albright WUson, or Hoechst-Celanese, differ ia molecular weight, particle size, solubUity, and surface coating. Insoluble ammonium polyphosphate consists of long chains of repeating 0P(0)(0NH units. 

A series of compounded flame retardants, based on finely divided insoluble ammonium polyphosphate together with char-forming nitrogenous resins, has been developed for thermoplastics (52—58). These compounds are particularly useful as iatumescent flame-retardant additives for polyolefins, ethylene—vinyl acetate, and urethane elastomers (qv). The char-forming resin can be, for example, an ethyleneurea—formaldehyde condensation polymer, a hydroxyethylisocyanurate, or a piperazine—triazine resin. 

A newer self-intumescent phosphoric acid salt has been introduced by Albright WHson as Amgard EDAP, mainly as an additive for polyolefins. It is a finely divided soHd, mp 250°C, having a reported phosphoms content of 63 wt % as H PO. It appears to be the ethylenediamine salt of phosphoric acid (1 1). Unlike ammonium polyphosphate, it does not require a char-forming synergist (62). 

A bicychc pentaerythritol phosphate, CN-1197, has more recently been introduced by Great Lakes Chemical for use in thermosets, preferably in combination with melamine or ammonium polyphosphate (89). It is a high melting soHd befleved to have the following stmcture [5301-78-0] (87) ... 

Related esters of this alcohol are disclosed by Ak2o as useflil flame retardants for polypropylene, particularly in combination with ammonium polyphosphate (90). 

Usage of phosphoms-based flame retardants for 1994 in the United States has been projected to be 150 million (168). The largest volume use maybe in plasticized vinyl. Other use areas for phosphoms flame retardants are flexible urethane foams, polyester resins and other thermoset resins, adhesives, textiles, polycarbonate—ABS blends, and some other thermoplastics. Development efforts are well advanced to find appHcations for phosphoms flame retardants, especially ammonium polyphosphate combinations, in polyolefins, and red phosphoms in nylons. Interest is strong in finding phosphoms-based alternatives to those halogen-containing systems which have encountered environmental opposition, especially in Europe. 

Zeohtes have high potential for protecting ecosystems, from faciUtating wastewater and gas treatment to providing water softeners in detergents to replace the undesirable polyphosphate. 

Other. A large variety of additives are used in paper-coatiag colors primarily to modify the physical properties of the colors (102). At high soHds concentrations in water, mineral pigment particles tend to associate and form viscous pastes. Dispersants (qv) are used to prevent this and to provide low viscosity slurries. Common dispersants include polyphosphates and sodium polyacrylate [9003-04-7]. Various water-soluble polymers are added to coatiag colors and act as water-retention agents and as rheology modifiers. 

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