出典(authority):フリー百科事典『ウィキペディア(Wikipedia)』「2016/01/18 13:00:04」(JST)
The isoelectric point (pI, pH(I), IEP), is the pH at which a particular molecule carries no net electrical charge. The standard nomenclature to represent the isoelectric point is pH(I),[1] although pI is also commonly seen,[2] and is used in this article for brevity. The net charge on the molecule is affected by pH of its surrounding environment and can become more positively or negatively charged due to the gain or loss, respectively, of protons (H+).
Surfaces naturally charge to form a double layer. In the common case when the surface charge-determining ions are H+/OH−, the net surface charge is affected by the pH of the liquid in which the solid is submerged.
The pI value can affect the solubility of a molecule at a given pH. Such molecules have minimum solubility in water or salt solutions at the pH that corresponds to their pI and often precipitate out of solution. Biological amphoteric molecules such as proteins contain both acidic and basic functional groups. Amino acids that make up proteins may be positive, negative, neutral, or polar in nature, and together give a protein its overall charge. At a pH below their pI, proteins carry a net positive charge; above their pI they carry a net negative charge. Proteins can, thus, be separated by net charge in a polyacrylamide gel using either QPNC-PAGE or isoelectric focusing, which uses a pH gradient to separate proteins. Isoelectric focusing is also the first step in 2-D gel polyacrylamide gel electrophoresis.
For an amino acid with only one amine and one carboxyl group, the pI can be calculated from the mean of the pKas of this molecule.[3]
The pH of an electrophoretic gel is determined by the buffer used for that gel. If the pH of the buffer is above the pI of the protein being run, the protein will migrate to the positive pole (negative charge is attracted to a positive pole). If the pH of the buffer is below the pI of the protein being run, the protein will migrate to the negative pole of the gel (positive charge is attracted to the negative pole). If the protein is run with a buffer pH that is equal to the pI, it will not migrate at all. This is also true for individual amino acids.
glycine pK = 2.72, 9.60 | adenosine monophosphate pK = 0.9, 3.8, 6.1 |
In these two examples the isoelectric point is shown by the green vertical line. In glycine the pK values are separated by nearly 7 units so the concentration of the neutral species, glycine (GlyH), is effectively 100% of the analytical glycine concentration. Glycine may exist as a zwitterion at the isoelectric point, but the equilibrium constant for the isomerization reaction in solution
is not known.
The other example, adenosine monophosphate is shown to illustrate the fact that a third species may, in principle, be involved. In fact the concentration of (AMP)H32+ is negligible at the isoelectric point in this case. If the pI is greater than the pH, the molecule will have a positive charge.
The isoelectric points (IEP) of metal oxide ceramics are used extensively in material science in various aqueous processing steps (synthesis, modification, etc.). In the absence of chemisorbed or physisorbed species[4] particle surfaces in aqueous suspension are generally assumed to be covered with surface hydroxyl species, M-OH (where M is a metal such as Al, Si, etc.). At pH values above the IEP, the predominate surface species is M-O−, while at pH values below the IEP, M-OH2+ species predominate. Some approximate values of common ceramics are listed below (Haruta[5] and Brunelle,[6] except where noted). The exact value can vary widely, depending on material factors such as purity and phase as well as physical parameters such as temperature. In addition, precise measurement of isoelectric points is difficult and requires careful techniques, even with modern methods. Thus, many sources often cite differing values for isoelectric points of these materials.
The following list gives the pH25 °C of isoelectric point at 25 °C for selected materials in water:
Note: The list is ordered by increasing pH values.
Mixed oxides may exhibit isoelectric point values that are intermediate to those of the corresponding pure oxides. For example, Jara et al.[13] measured an IEP of 4.5 for a synthetically prepared amorphous aluminosilicate (Al2O3-SiO2). The researchers noted that the electrokinetic behavior of the surface was dominated by surface Si-OH species, thus explaining the relatively low IEP value. Significantly higher IEP values (pH 6 to 8) have been reported for 3Al2O3-2SiO2 by others (see Lewis[10]). Lewis[10] also lists the IEP of barium titanate, BaTiO3 as being between pH 5 and 6, while Vamvakaki et al.[14] reported a value of 3, although these authors note that a wide range of values have been reported, a result of either residual barium carbonate on the surface or TiO2-rich surfaces.
The farther the pH of an Amino Acid solution is from its pl the greater the electric charge on that population of molecules.
The terms isoelectric point (IEP) and point of zero charge (PZC) are often used interchangeably, although under certain circumstances, it may be productive to make the distinction.
In systems in which H+/OH− are the interface potential-determining ions, the point of zero charge is given in terms of pH. The pH at which the surface exhibits a neutral net electrical charge is the point of zero charge at the surface. Electrokinetic phenomena generally measure zeta potential, and a zero zeta potential is interpreted as the point of zero net charge at the shear plane. This is termed the isoelectric point.[15] Thus, the isoelectric point is the value of pH at which the colloidal particle remains stationary in an electrical field. The isoelectric point is expected to be somewhat different than the point of zero charge at the particle surface, but this difference is often ignored in practice for so-called pristine surfaces, i.e., surfaces with no specifically adsorbed positive or negative charges.[4] In this context, specific adsorption is understood as adsorption occurring in a Stern layer or chemisorption. Thus, point of zero charge at the surface is taken as equal to isoelectric point in the absence of specific adsorption on that surface.
According to Jolivet,[8] in the absence of positive or negative charges, the surface is best described by the point of zero charge. If positive and negative charges are both present in equal amounts, then this is the isoelectric point. Thus, the PZC refers to the absence of any type of surface charge, while the IEP refers to a state of neutral net surface charge. The difference between the two, therefore, is the quantity of charged sites at the point of net zero charge. Jolivet uses the intrinsic surface equilibrium constants, pK− and pK+ to define the two conditions in terms of the relative number of charged sites:
For large ΔpK (>4 according to Jolivet), the predominant species is MOH while there are relatively few charged species - so the PZC is relevant. For small values of ΔpK, there are many charged species in approximately equal numbers, so one speaks of the IEP.
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リンク元 | 「等電点」 |
関連記事 | 「point」「pointing」「isoelectric」 |
塩基性タンパク質 | 酸性タンパク質 | |
優勢なアミノ酸 | 塩基性アミノ酸 | 酸性アミノ酸 |
想定される側鎖の末端 | NH2 | COOH |
等電点(pI) | <7.4 酸性側 |
>7.4 アルカリ性側 |
pH7.4での電荷 | - | + |
代表的な蛋白質 | アルブミン | ヒストン |
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