High microwave susceptibility of NaH2PO4 center dot 2H(2)O: Rapid synthesis of crystalline and glassy phosphates with NASICON-type chemistry

High microwave susceptibility of NaH2PO4 . 2H(2)O has been discovered, This hydrated acid phosphate of sodium can be heated upto 1000 K or more when exposed to 2.45 GHz microwaves. Using this, a novel microwave-assisted preparation of a number of important crystalline and glassy materials with NASICON-type chemistry has been accomplished in less than 8 min which is only a fraction of the time required for conventional synthetic procedures, The present single-shot approach to the preparation of phosphates is attractive in terms of its simplicity, rapidity, and general applicability, A ''step-ladder'' heating mechanism has been proposed to account for the high microwave absorbing ability of NaH2PO4 . 2H(2)O.

Metabolism of Plasmodium bergheistar, open: II. 32Pi incorporation into high-energy phosphates

Free parasites of Plasmodium berghei were found to incorporate labeled inorganic phosphate into high-energy phosphates by substrate linked and oxidative hosphorylation. But the parasites also appear to utilize the reserve ATP of the host cells when they are within the host cells which may indicate the dependence of the parasite on the host cells for provision of energy. This investigation formed part of the thesis submitted in 1965 for the doctoral degree at the Indian Institute of Science, Bangalore 12, India, and was supported in part by the Council of Scientific and Industrial Research, India.

Computer modeling studies on the binding of 2',5'-linked dinucleoside phosphates to ribonuclease T1-influence of subsite interactions on the substrate specificity

The modes of binding of Gp(2',5')A, Gp(2',5')C, Gp(2',5')G and Gp(2',5')U to RNase T1 have been determined by computer modelling studies. All these dinucleoside phosphates assume extended conformations in the active site leading to better interactions with the enzyme. The 5'-terminal guanine of all these ligands is placed in the primary base binding site of the enzyme in an orientation similar to that of 2'-GMP in the RNase T1-2'-GMP complex. The 2'-terminal purines are placed close to the hydrophobic pocket formed by the residues Gly71, Ser72, Pro73 and Gly74 which occur in a loop region. However, the orientation of the 2'-terminal pyrimidines is different from that of 2'-terminal purines. This perhaps explains the higher binding affinity of the 2',5'-linked guanine dinucleoside phosphates with 2'-terminal purines than those with 2'-terminal pyrimidines. A comparison of the binding of the guanine dinucleoside phosphates with 2',5'- and 3',5'-linkages suggests significant differences in the ribose pucker and hydrogen bonding interactions between the catalytic residues and the bound nucleoside phosphate implying that 2',5'-linked dinucleoside phosphates may not be the ideal ligands to probe the role of the catalytic amino acid residues. A change in the amino acid sequence in the surface loop region formed by the residues Gly71 to Gly74 drastically affects the conformation of the base binding subsite, and this may account for the inactivity of the enzyme with altered sequence i.e., with Pro, Gly and Ser at positions 71 to 73 respectively. These results thus suggest that in addition to recognition and catalytic sites, interactions at the loop regions which constitute the subsite for base binding are also crucial in determining the substrate specificity.

Molecular dynamics studies on nucleoside 2',3'-cyclic phosphates

2',3'-cyclic nucleotides are intermediates and substrates of Ribonuclease (RNase)-catalysed reactions. The characterization of the equilibrium conformation as well as the flexibility inherent in these molecules helps in understanding the enzymatic action of RNases. The present study explores parameters like phase angle, glycosydic torsion angle and hydrogen bond to find possible interrelationship between them through Molecular Dynamics (MD) simulations on 3'-GMP, 3'-UMP, A>p, G>p, U>p, C>p, GpA>p and UpA>p. Interesting results of the effect of cyclisation and other constraints such as hydrogen bond between certain groups on the equilibrium ribose conformation have emerged from this study.

Transformations of two-dimensional layered zinc phosphates to three-dimensional and one-dimensional structures

Transformations of the layered zinc phosphates of the compositions [C6N4H22](0.5) [Zn-2 (HPO4)(3)], I, [C3N2H12][Zn-2 (HPO4)(3)], II and [C3N2OH12][Zn-2 (HPO4)(3)], III, containing triethylenetetramine, 1,3-diaminopropane, and 1,3-diamino-2-hydroxypropane, respectively, have been investigated under different conditions. On heating in water, I transforms to a one-dimensional (1-D) ladder and a three-dimensional (3-D) structure, while II gives rise to only a two-dimensional (2-D) layered structure. In the transformation reaction of I with zinc acetate, the same ladder and 3-D structures are obtained along with a tubular layer. Under similar conditions II gives a layered structure formed by the joining of two ladder motifs. III, on the other hand, is essentially unreactive when heated with water and zinc acetate, probably because the presence of the hydroxy group in the amine which hydrogen bonds to the framework. In the presence of piperazine, I, II and III give rise to a four-membered, corner-shared linear chain which is likely to be formed via the ladder structure. In addition, 2-D and 3-D structures derived from the 1-D linear chain or ladder structures are also formed. The primary result from the study is that the layers produce 1-D ladders, which then undergo other transformations. It is noteworthy that in the various transformations carried out, most of the products are single-crystalline.

One-dimensional zinc phosphates with linear chain structure

Three one-dimensional zinc phosphates, [C5N2H14][Zn(HPO4)2], I, [C10N4H26][Zn(HPO4)2].2H2O II, and [C4N2H6]2[Zn(HPO4)], III, have been prepared employing hydro/solvothermal methods in the presence of organic amines. While I and II consist of linear chains of corner-shared four-membered rings, III is a polymeric wire where the amine molecule is directly bonded to the metal center. The wire, as well as the chain in these structures, are held together by hydrogen bond interactions involving the amine and the framework oxygens. The polymeric zinc phosphate with wire-like architecture, III, is only the second example of such architecture. Crystal data: I, monoclinic, P21/c (no. 14), a=8.603(2), b=13.529(2), c=10.880(1) Å, β=94.9(1)°, V=1261.6(1) Å3, Z=4, ρcalc.=1.893 gcm−3, μ(MoKα)=2.234 mm−1, R1=0.032, wR2=0.086, [1532 observed reflections with I>2σ(I)], II, orthorhombic, Pbca (no. 61), a=8.393(1), b=15.286(1), c=22.659(1) Å, V=2906.9(2) Å3, Z=8, ρcalc.=1.794 gcm−3, μ(MoKα)=1.957 mm−1, R1=0.055, wR2=0.11, [1565 observed reflections with I>2σ(I) and III, monoclinic, P21/c (no. 14), a=8.241(1), b=13.750(2), c=10.572(1) Å, β=90.9(1)°, V=1197.7(2) Å3, Z=4, ρcalc.=1.805 gcm−3, μ(MoKα)=2.197 mm−1, R1=0.036, wR2=0.10, [1423 observed reflections with I>2σ(I)].

Understanding the building-up process of three dimensional open-framework metal phosphates: Acid degradation of the 3D structures to lower dimensional structures

Acid degradation of 3D zinc phosphates primarily yields a one-dimensional ladder compound, an observation that is significant considering that the latter forms 3D structures on heating in water.

Regulation of lipid biosynthesis by phosphatidylinositol-specific phospholipase C through the transcriptional repression of upstream activating sequence inositol containing genes

The regulation of phospholipid biosynthesis in Saccharomyces cerevisiae through cis-acting upstream activating sequence inositol (UAS(ino)) and trans-acting elements, such as the INO2-INO4 complex and OPI1 by inositol supplementation in growth is thoroughly studied. In this study, we provide evidence for the regulation of lipid biosynthesis by phosphatidylinositol-specific phospholipase C (PLC) through UAS(ino) and the trans-acting elements. Gene expression analysis and radiolabelling experiments demonstrated that the overexpression of rice PLC in yeast cells altered phospholipid biosynthesis at the levels of transcriptional and enzyme activity. This is the first report implicating PLC in the direct regulation of lipid biosynthesis. (C) 2012 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Quantitative interactions between the A-type K+ current and inositol trisphosphate receptors regulate intraneuronal Ca2+ waves and synaptic plasticity

Key points center dot Active calcium signal propagation occurs when an initial calcium trigger elicits calcium release through endoplasmic reticulum (ER) receptors. A high concentration of the calcium trigger in thin-calibre dendrites would suppress release of calcium through hippocampal inositol trisphosphate receptors (InsP3Rs). center dot Could the high-density expression of A-type K+ channels in thin-calibre dendrites be a mechanism for inhibiting this suppression, thereby restoring the utility of the ER as a substrate for active calcium propagation? center dot Quantitative analyses involving experimentally constrained models reveal a bell-shaped dependence of calcium released through InsP3Rs on the A-type K+ channel density, during the propagation of a calcium wave. center dot A-type K+ channels regulated the relative contribution of ER calcium to the induction of synaptic plasticity in the presence of model metabotropic glutamate receptors. center dot These results identify a novel form of interaction between active dendrites and the ER membrane and suggest that A-type K+ channels are ideally placed for inhibiting the suppression of InsP3Rs in thin-calibre dendrites. Abstract The A-type potassium current has been implicated in the regulation of several physiological processes. Here, we explore a role for the A-type potassium current in regulating the release of calcium through inositol trisphosphate receptors (InsP3R) that reside on the endoplasmic reticulum (ER) of hippocampal pyramidal neurons. To do this, we constructed morphologically realistic, conductance-based models equipped with kinetic schemes that govern several calcium signalling modules and pathways, and constrained the distributions and properties of constitutive components by experimental measurements from these neurons. Employing these models, we establish a bell-shaped dependence of calcium release through InsP3Rs on the density ofA-type potassium channels, during the propagation of an intraneuronal calcium wave initiated through established protocols. Exploring the sensitivities of calcium wave initiation and propagation to several underlying parameters, we found that ER calcium release critically depends on dendritic diameter and that wave initiation occurred at branch points as a consequence of a high surface area to volume ratio of oblique dendrites. Furthermore, analogous to the role ofA-type potassium channels in regulating spike latency, we found that an increase in the density ofA-type potassium channels led to increases in the latency and the temporal spread of a propagating calcium wave. Next, we incorporated kinetic models for the metabotropic glutamate receptor (mGluR) signalling components and a calcium-controlled plasticity rule into our model and demonstrate thatthe presence of mGluRs induced a leftward shift in a BienenstockCooperMunro-like synaptic plasticity profile. Finally, we show that the A-type potassium current could regulate the relative contribution of ER calcium to synaptic plasticity induced either through 900 pulses of various stimulus frequencies or through theta burst stimulation. Our results establish a novel form of interaction between active dendrites and the ER membrane, uncovering a powerful mechanism that could regulate biophysical/biochemical signal integration and steer the spatiotemporal spread of signalling microdomains through changes in dendritic excitability.

Dialkyl (3-Aryl- 1,2,4-oxadiazol-5-yl)phosphonates: Synthesis and Thermal Behavior-Evidence for Monomeric Alkyl Metaphosphate

Dialkyl (3-aryl-l,2,4-oxadiazol-5-yl)phosphonate6sa -h have been obtained by 1,3-dipolar cycloaddition of arenenitrile oxides 5a-f to dialkyl phosphorocyanidates (4a and 4b) in yields ranging between 30% and 58%. A standardized method for obtaining cyanidates 4a and 4b has been established. The diethyl thiophosphorocyanidate (4c) is less reactive than 4a and 4b, only the 3-(4'-nitrophenyl) derivative 6i being obtainable. While the IR and NMFt spectra of 6a-i were unexceptional, their UV spectra showed evidence of conjugative interaction in high degrees between the phosphonate and heterocyclic moieties as well as a varying conjugative interaction between the heterocyclic and aryl moieties. The oxadiazoles 6a-h are thermally labile and yield trialkyl phosphates 7 as the only identifiable products. A mechanism based on the intermediacy of monomeric alkyl metaphosphate 11 in the formation of trialkyl phosphate was postulated, and supportive evidence in the form of trapping the metaphosphate with acetophenone has been obtained.

Immunological studies on nucleic acids and their components.8.Antibodies specific to a deoxyribotrinucleotide sequence

Bovine serum albumin conjugates of two trinucleotides, dpTpTpA and dTpTpAp, were prepared by linking the trinucleotides through their end phosphates by the ‘carbodiimide method’. Antibodies were raised in rabbits by injecting the trinucleotide-bovine serum albumin conjugates. Analysis by double diffusion in agar gel, quantitative precipitin reaction and its inhibition by haptens showed clearly the presence of antibodies specific to the whole trinucleotide molecule. The titre of antibodies obtained by the trinucleotide-rabbit serum albumin conjugates with their respective antisera was approximately the same, indicating that linking the trinucleotide through either 5′ or 3′ phosphate does not have an appreciable effect on the titre of antibodies. The results also demonstrate that the nucleotide(s) away from the carrier protein is more immunodominant than the one linked directly to the protein.

Flotation of calcareous Mussorie phosphate ore

Separation of Mussorie rock phosphate (P2O5 = 20%) from Uttar Pradesh, India, containing pyrite, calcite and other carbonaceous impurities by flotation has been successfully attempted to upgrade the phosphate values. Based on Hallimond cell flotation results of single and synthetic mineral mixtures of calcite and apatite using oleic acid and potassium phosphate, conditions were obtained for the separation of calcite from apatite which is considered to be the most difficult step in the beneficiation of calcareous phosphates. Further studies using 250 g of the mineral (−60 +150 and −150 mesh fractions, deslimed) in laboratory size Fagergren subaeration machine employed a stagewise flotation viz. carbonaceous materials using terpineol, pyrite using potassium-ethyl xanthate and calcite using oleic acid respectively. Separation was, however, found to be unsatisfactory in the absence of a depressant. Among starch, hydrofluosilicic acid and dipotassium hydrogen phosphate, which were tried as depressants for apatite in the final flotation stage, dipotassium hydrogen phosphate proved to be superior to others. However, the tests with the above fractions did not yield the required grade. This was possibly due to insufficient liberation of the phosphate mineral from the ore body and different experimental conditions due to scale up operations. Experiments conducted using −200 mesh deslimed fractions has yielded an acceptable grade of 27.6% P2O5 with a recovery of about 60%. The results have been explained in terms of the specific adsorption characteristics of phosphate ions on apatite and the liberation size of the mineral.

Mechanistic studies on the action of ammonium phosphate on polymer fire retardancy

The mechanism of fire retardant action of mono- and diammonium phosphates on polystyrene has been investigated. Ignition delay and mass burning rate studies reveal that the phosphates bring down both parameters considerably though to different extents. This has been adequately explained on the basis of the existing combustion models and physicochemical behavior of the material. Similar to their action on cellulosic materials, phosphates bring about fire retardancy in polystyrene via char formation. This is suggested to occur through a series of processes consisting of initial peroxide formation, decomposition to alcohols and aldehydes, formation of alkyl-phosphate esters, dehydration and subsequent char formation. Infrared and mass spectral studies support this mechanism.

The Structure of Monosodium Phosphoenolpyruvate

CDH406P-.Na +.H20 , M r = 208.0, is monoclinic, Cc, a = 11.423 (2), b = 23.253 (5), c - 6.604 (1) A, fl = 123.63 (1) °, U = 1460.6 A 3, D x =. 1.89 Mg m -a, Z = 8, 2(Mo Ka) = 0.7107 A, p(Mo Ka) = 0.44 mm -~, F(000) = 840. Final R = 0.063 for 1697 reflections.The two crystallographically independent molecules of phosphoenolpyruvate (PEP) (A and B) are almost mirror images of each other, the mirror being the planar enolpyruvate group. The torsion angle C(3)-C(2)- O(1)-P(1) is 122.6 in A and -112.0 ° in B, in contrast to -209.1 ° in PEP.K. The enolic C(2)-O(1) has a partial double-bond character [1.401 (A), 1.386A (B)]. The high-energy P~O bond (1.595 and 1.610A) is comparable to that in PEP.K (1.612 A). Na(1) has six nearest neighbours while Na(2) has only five. The Na + ions are involved in binding only the phosphates of different molecules, in contrast to the K ÷ ion in PEP. K, which binds to both the phosphate and carboxyl ends of the same molecule. The planar carboxyl groups stack on each other at an average distance of 3.2 A instead of forming hydrogen-bonded dimers usually found in carboxylate structures.