Calcium ions, reactions

The efhciency of this methodology was also apphed to the synthesis of D-myo-inosi-tol-l,4,5-triphosphate (1,4,5-1P3) from 245. 1,4,5-IP3 has been recognized as a second messenger to mobilize intracellular calcium ions. Reaction of 245 wi(h benzoic acid in the presence of Pd2dba3 and (5,5)-44 afforded the dibenzoate, 246 in 80% yield and >99% enantiomeric excess. Dihydroxylation followed by chemoselective ranoval of the Troc groups with zinc dust gave 73% yield of the tetraol 247 (two steps). Completion of the synthesis as described in the hterature afforded pure 1,4,5-IP3. 

Typical examples of losses of an inhibitor due to these factors are precipitation of phosphates by the calcium ion, reaction of chromates with sulfides or organics, adsorption of inhibitors on suspended solids, and injection of a poorly soluble inhibitor without an adequate dispersing agent. 

This produces sufficient concentrations of magnesium and calcium ions to render the water hard. The above reaction is readily reversed by boiling the water when the magnesium and calcium ions responsible for the hardness are removed as the insoluble carbonate. 

Calcium ion plays an important role in many aqueous environmental systems. A useful direct analysis takes advantage of its reaction with the ligand ethylenedi-aminetetraacetic acid (EDTA), which we will represent as... 

This reaction is relatively fast and readily reversible so that in drainage basins in carbonate-dominated terranes the stream water commonly will have near-equihbrium concentrations of hydrogen, bicarbonate, and calcium ions. At equiUbrium, the rates of forward and reverse processes represented in equation 5 are equal. 

Water. The character of the water has a great influence on the character of the beer and the hardness of water (alkalinity) manifests itself by the extent of its reaction with the weak acids of the mash. Certain ions are harm fill to brewing nitrates slow down fermentation, iron destroys the colloidal stabihty of beer, and calcium ions give beer a purer flavor than magnesium or sodium ions (Table 7). 

Phosphates, which react with calcium to reduce the calcium ion activity, assist in stabilizing calcium-sensitive proteins, eg caseinate and soy proteinate, during processing. Phosphates also react with milk proteins. The extent of the reaction depends upon chain length. Casein precipitates upon addition of pyrophosphates, whereas whey proteins do not. Longer-chain polyphosphates cause the precipitation of both casein and whey proteins. These reactions are complex and not fully understood. Functions of phosphates in different types of dairy substitutes are summarized in Table 9 (see also Food additives). 

Lime is somewhat different from the hydrolyzing coagulants. When added to wastewater it increases pH and reacts with the carbonate alkalinity to precipitate calcium carbonate. If sufficient lime is added to reach a high pH, approximately 10.5, magnesium hydroxide is also precipitated. This latter precipitation enhances clarification due to the flocculant nature of the Mg(OH)2. Excess calcium ions at high pH levels may be precipitated by the addition of soda ash. The preceding reactions are shown as follows ... 

In this reaction, the nickel ions of the nickel sulfate (NiSO ) are exchanged for the calcium ions of the calcium hydroxide [Ca(OH)2 ] molecule. Similarly, a resin with hydrogen ions available for exchange will exchange those ions for nickel ions from solution. The reaction can be written as follows ... 

Mammals synthesize phosphatidylserine (PS) in a calcium ion-dependent reaction involving aminoalcohol exchange (Figure 25.21). The enzyme catalyzing this reaction is associated with the endoplasmic reticulum and will accept phosphatidylethanolamine (PE) and other phospholipid substrates. A mitochondrial PS decarboxylase can subsequently convert PS to PE. No other pathway converting serine to ethanolamine has been found. 

Chemical Analysis. Standard chemical analyses have been developed for determining the concentration of various ions present in the mud [23]. Test for concentration of chloride, hydroxide and calcium ions are required to fill out the API drilling mud report. The tests are based on filtration, i.e., reaction of a known volume of mud filtrate sample with a standard solution of known volume and concentration. The end of chemical reaction is usually indicated by the change of color. The concentration of the ion being tested then can be determined from a knowledge of the chemical reaction taking place [7]. 

Scale formation Controlled scale deposition by the Langelier approach or by the proper use of polyphosphates or silicates is a useful method of corrosion control, but uncontrolled scale deposition is a disadvantage as it will screen the metal surfaces from contact with the inhibitor, lead to loss of inhibitor by its incorporation into the scale and also reduce heat transfer in cooling systems. Apart from scale formation arising from constituents naturally present in waters, scaling can also occur by reaction of inhibitors with these constituents. Notable examples are the deposition of excess amounts of phosphates and silicates by reaction with calcium ions. The problem can be largely overcome by suitable pH control and also by the additional use of scale-controlling chemicals. 

An electrolytic method for removing CaO from CaCl2 was suggested by Barletta, et.al.17 The salt is electrolyzed in a cell with a graphite consumable anode. Oxygen is removed at the anode where it reacts with carbon to form CO and C02. Calcium ions are reduced to metal at the cathode. Thus, the electrolytic reduction reaction should be... 

The enzyme had a requirement for calcium. The addition of EDTA to the reaction mixtures, resulted in complete loss of activity, whereas the addition of CaCl2 increased the activity (figure 8). Presumably, sufficient contaminating calcium ions were present in the dialyzed enzyme and substrate mixture to permit the limited activity of the controls, but apparently these were removed by chelation with EDTA. The optimum concentration was in the range of 5 to 15 M, and higher concentration resulted in a decrease in activity. Phoma medicaginis var. pinodella synthesizes a pectin lyase that lacked an absolute requirement for calcium ions but maximum enzyme activity required the presence of 1 mM Ca [25]. The lyase from Fusarium solani f sp. phaseoli, that is active on pectin and pectic acid, is calcium-dependent [30]. Most of the pectate lyases characterized are calcium-dependent the pectate lyase from Rhizoctonia solani [34] and the endopectate lyase fi om Fusarium solani f sp. pisi [31]. 

When calcium carbonate goes into solution, it releases basic carbonate ions (COf ), which react with hydrogen ions to form carbon dioxide (which will normally remain in solution at deep-well-injection pressures) and water. Removal of hydrogen ions raises the pH of the solution. However, aqueous carbon dioxide serves to buffer the solution (i.e., re-forms carbonic acid in reaction with water to add H+ ions to solution). Consequently, the buffering capacity of the solution must be exceeded before complete neutralization will take place. Nitric acid can react with certain alcohols and ketones under increased pressure to increase the pH of the solution, and this reaction was proposed by Goolsby41 to explain the lower-than-expected level of calcium ions in backflowed waste at the Monsanto waste injection facility in Florida. 

This solution is added to 10 times its volume of 2-propanone and the polymer is recovered by filtration. The solids are redissolved in water. To remove calcium ion from the product, an amount of Na2Cp0. equal to the moles of CaCl2 added to the reaction is placed in the solution. The CaC20. precipitate is removed by filtration. 

Little more need be said here about the simple ion-exchange reactions such as that between sodium hexametaphosphate and calcium ions (Scheme 10.7). It is useful, however, to consider in more detail those reactions involving chelation (Scheme 10.8). This is a reversible reaction, the equilibrium being dependent on the process pH and the concentrations of the reacting species (Equation 10.2). While chelated complexes are less stable at higher temperatures, this effect can be ignored in practice. The factors involved have been discussed in some considerable detail by Engbers and Dierkes [20,23]. 

In the presence of sucrose alone as the single substrate, initial reaction rates follow Michaelis-Menten kinetics up to 200 mM sucrose concentration, but the enzyme is inhibited by higher concentrations of substrate.30 The inhibitor constant for sucrose is 730 mM. This inhibition can be overcome by the addition of acceptors.31,32 The enzyme activity is significantly enhanced, and stabilized, by the presence of dextran, and by calcium ions. 

Obelin is a Ca2+-activated bioluminescent photoprotein that has been isolated from the marine polyp Obelia longissima. Binding of calcium ions determines a luminescent emission. The protein consists of 195 amino acid residues [264] and is composed of apoobelin, coelenterazine, and oxygen. As aequorin, it contains three EF-hand Ca2+-binding sites and the luminescent reaction may be the result of coelenterazine oxidation by way of an intramolecular reaction that produces coelenteramide, C02, and blue light. As for aequorin, the luminescent reaction of obelin is sensitive to calcium and the protein was used in the past as an intracellular Ca2+ indicator. More recently, the cloning of cDNA for apoobelin led to the use of recombinant obelin as a label in different analytical systems. 

The reaction rate of sodium acid pyrophosphate can be controlled by adding calcium ions. While this process happens anyway in the presence of skim milk solids, manufacturers deliberately add calcium ions to sodium acid pyrophosphate to give grades with slower dissolution. 

Adults require 1-2 mg of copper per day, and eliminate excess copper in bile and feces. Most plasma copper is present in ceruloplasmin. In Wilson s disease, the diminished availability of ceruloplasmin interferes with the function of enzymes that rely on ceruloplasmin as a copper donor (e.g. cytochrome oxidase, tyrosinase and superoxide dismutase). In addition, loss of copper-binding capacity in the serum leads to copper deposition in liver, brain and other organs, resulting in tissue damage. The mechanisms of toxicity are not fully understood, but may involve the formation of hydroxyl radicals via the Fenton reaction, which, in turn initiates a cascade of cellular cytotoxic events, including mitochondrial dysfunction, lipid peroxidation, disruption of calcium ion homeostasis, and cell death. 

Where only univalent cations are considered, the activities calculated by Equations 9.27 and 9.28 are equivalent in value, but this is not the case if divalent ions are included. The reaction describing exchange of sodium for calcium ions,... 

A different application of visible microscopy was pioneered by Gomori. In 1941 he showed that alkaline phosphatase could be specifically located by its hydrolysis of soluble phosphate esters (initially glycerophosphate). If calcium ions were present in the medium in which the sections were incubated, insoluble calcium phosphate precipitated as a result of the action of the hydrolase. The site of the precipitate could be visualized if cobalt or lead salts were subsequently added to replace calcium and the sections exposed to hydrogen sulfide. In principle many hydrolases and other enzymes could be studied using the appropriate substrates and precipitants. It was important to ensure that the products of the enzyme reactions did not diffuse from the sites where the enzymes were located. It was also essential that the reagents could reach the enzyme site. 

Synthesis of noradrenaline (norepinephrine) is shown in Figure 4.7. This follows the same route as synthesis of adrenaline (epinephrine) but terminates at noradrenaline (norepinephrine) because parasympathetic neurones lack the phenylethanolamine-N-methyl transferase required to form adrenaline (epinephrine). Acetylcholine is synthesized from acetyl-Co A and choline by the enzyme choline acetyltransferase (CAT). Choline is made available for this reaction by uptake, via specific high-affinity transporters, within the axonal membrane. Following their synthesis, noradrenaline (norepinephrine) or acetylcholine are stored within vesicles. Release from the vesicle occurs when the incoming nerve impulse causes an influx of calcium ions resulting in exocytosis of the neurotransmitter. 

In addition to 1-a-hydroxylase, the kidney also possesses a 24-hydroxylase which uses calcidiol as substrate the product of the reaction, 24,25 dihydroxy D3, is biologically inactive. This represents an important control point in the pathway. The activity of the 1-a-hydroxylase is promoted by calcium ions and the action of PTH acting via a G-protein/cAMP cascade. However, calcitriol itself simultaneously induces the 24-hydroxylase and suppresses 1-a-hydroxylase creating an effective feedback loop (Figure 8.12). 

To understand the inhibition of a-amylase by peptide inhibitors it is crucial to first understand the native substrate-enzyme interaction. The active site and the reaction mechanism of a-amylases have been identified from several X-ray structures of human and pig pancreatic amylases in complex with carbohydrate-based inhibitors. The structural aspects of proteinaceous a-amylase inhibition have been reviewed by Payan. The sequence, architecture, and structure of a-amylases from mammals and insects are fairly homologous and mechanistic insights from mammalian enzymes can be used to elucidate inhibitor function with respect to insect enzymes. The architecture of a-amylases comprises three domains. Domain A contains the residues responsible for catalytic activity. It complexes a calcium ion, which is essential to maintain the active structure of the enzyme and the presence of a chloride ion close to the active site is required for activation. 

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