PH sensitivity

By far the most widely known classes of pH-sensitive materials are the classes of chemical compounds that iaclude the acids, bases, and iadicators. The most interesting of these are the iadicators. These materials change colors as a function of pH and usually are totally reversible (see Hydrogen-ION concentration). 

The immersion of glass electrodes in strongly dehydrating media should be avoided. If the electrode is used in solvents of low water activity, frequent conditioning in water is advisable, as dehydration of the gel layer of the surface causes a progressive alteration in the electrode potential with a consequent drift of the measured pH. Slow dissolution of the pH-sensitive membrane is unavoidable, and it eventually leads to mechanical failure. Standardization of the electrode with two buffer solutions is the best means of early detection of incipient electrode failure. 

Buffers are frequently added to emulsion recipes and serve two main purposes. The rate of hydrolysis of vinyl acetate and some comonomers is pH-sensitive. Hydrolysis of monomer produces acetic acid, which can affect the initiator, and acetaldehyde which as a chain-transfer agent may lower the molecular weight of the polymer undesirably. The rates of decomposition of some initiators are affected by pH and the buffer is added to stabilize those rates, since decomposition of the initiator frequently changes the pH in an unbuffered system. Vinyl acetate emulsion polymerization recipes are usually buffered to pH 4—5, eg, with phosphate or acetate, but buffering at neutral pH with bicarbonate also gives excellent results. The pH of most commercially available emulsions is 4—6. 

Rosin is commonly modified with maleic or fumaric acid to improve efficiency. Since the 1970s, dispersions of unsaponifted rosin have become more popular as a result of their improved sizing efficiency, lower alum requirements, and reduced pH sensitivity vs saponified rosins. Cationic dispersed rosin size, which can be effective at near-neutral and neutral papermaking conditions, is also available (63—65). Commercially available rosin sizes include Pexol, Neuphor, and Hi-pHase (Hercules Inc.), Plasmine and NeuRos (Plasmine), Stafor (Westvaco), Novaplus, and Novasize (Georgia Pacific), and NeuRos and Roscol (Akzo Nobel). 

Delivery systems that respond to changes in pH have been known to the pharmaceutical industry for more than a century. The pH-sensitive enteric coating is probably the oldest controUed-release technology. Unna introduced an enteric tablet coating based on keratin in 1884 (108). Enteric coatings are used primarily to protect the gastric mucosa from local irritation or to ensure that tablets do not dissolve until they reach the intestine. 

The anthocyanins are pH sensitive. Their color, in part, is deterrnined by the pH of the sap. Cyanin, for example, is red at pH 3, violet at 8, and blue at 11. However, there are other factors that affect the colors of the anthocyanins metallic salts, notably iron and aluminum, react with those anthocyanins containing vicinal hydroxy groups and produce highly colored complex compounds. Other factors are the colloidal condition of the cell sap and copigmentation (91). 

Because of tfiek pH sensitivity, antiiocyanins have found littie use as industtial dyes. However, a few having the quinoidal form of anthocyanidin (28) were formedy used as dyes. Two of these were carajurin [491 -93-OJ (29) and dracorhodin [643-56-1] (30) ... 

Carotenoids have two general characteristics of importance to the food iadustry they are not pH sensitive ia the normal 2—7 range found ia foods, and they are not affected by vitamin C, making them especially important for beverages. They are more expensive than synthetic food dyes and have a limited color range. In their natural environment they are quite stable, but they become more labile when heated or when they are ia solution. Under those conditions, there is a tendency for the trans-double bonds to isomerize to the cis-stmcture with a subsequent loss of color iatensity. The results of controlled tolerance and toxicity tests, usiag pure carotenoids, iadicate that they are perfecdy safe as food colors (132). 

Potentiometric Titrations. If one wishes to analyze electroactive analytes that are not ions or for which ion-selective electrodes are not available, two problems arise. First, the working electrodes, such as silver, platinum, mercury, etc, are not selective. Second, metallic electrodes may exhibit mixed potentials, which may arise from a variety of causes. For example, silver may exchange electrons with redox couples in solution, sense Ag" via electron exchange with the external circuit, or tarnish to produce pH-sensitive oxide sites or Ag2S sites that are sensitive to sulfide and haUde. On the other... 

In a series of detailed studies, Armand and coworkers have examined the electrochemical reduction of pyrazines (72CR(C)(275)279). The first step results in the formation of 1,4-dihydropyrazines (85), but the reaction is not electrochemically reproducible. The 1,4-dihydropyrazine is pH sensitive and isomerizes at a pH dependent rate to the 1,2-dihydro compound (83). The 1,2-dihydropyrazine then appears to undergo further reduction to 1,2,3,4-tetrahydropyrazine (88) which is again not electrochemically reproducible. Compound (88) then appears to undergo isomerization to another tetrahydro derivative, presumably (8, prior to complete reduction to piperazine (89). These results have been confirmed (72JA7295). 

Cg pH-sensitive film had a dynamic range from 6 to 8 and Cg-film responded at higher pH values (8-10).The membranes showed good reproducibility, reversibility and a short response time (<10 s). They also can be used for at least 3 months without any considerable absolution deviations. These sensors can be used for direct determination of pH in drinking water detergent and dishwasher liquid that have good agreement with pH meter data. 

In the discussion of the relative acidity of carboxylic acids in Chapter 1, the thermodynamic acidity, expressed as the acid dissociation constant, was taken as the measure of acidity. It is straightforward to determine dissociation constants of such adds in aqueous solution by measurement of the titration curve with a pH-sensitive electrode (pH meter). Determination of the acidity of carbon acids is more difficult. Because most are very weak acids, very strong bases are required to cause deprotonation. Water and alcohols are far more acidic than most hydrocarbons and are unsuitable solvents for generation of hydrocarbon anions. Any strong base will deprotonate the solvent rather than the hydrocarbon. For synthetic purposes, aprotic solvents such as ether, tetrahydrofuran (THF), and dimethoxyethane (DME) are used, but for equilibrium measurements solvents that promote dissociation of ion pairs and ion clusters are preferred. Weakly acidic solvents such as DMSO and cyclohexylamine are used in the preparation of strongly basic carbanions. The high polarity and cation-solvating ability of DMSO facilitate dissociation... 

FIGURE 14.11 The pH activity profiles of four different enzymes. Trypsin, an intestinal protease, has a slightly alkaline pH optimnm, whereas pepsin, a gastric protease, acts in the acidic confines of the stomach and has a pH optimmn near 2. Papain, a protease found in papaya, is relatively insensitive to pHs between 4 and 8. Cholinesterase activity is pH-sensitive below pH 7 but not between pH 7 and 10. The cholinesterase pH activity profile suggests that an ionizable group with a pK near 6 is essential to its activity. Might it be a histidine residue within the active site ... 

The neutral glasses are generally less resistant than the hard borosilicate type, but are more easily melted and shaped. They are formulated so that the pH of aqueous solutions is unaffected by contact with the glass, making it particularly suitable in pharmaceutical use for the storage of pH-sensitive drugs. 

A less accurate but more colorful way to measure pH uses a universal indicator, which is a mixture of acid-base indicators that shows changes in color at different pH values (Figure 13.5, p. 359). A similar principle is used with pH paper. Strips of this paper are coated with a mixture of pH-sensitive dyes these strips are widely used to test the pH of biological fluids,... 

Adie, E. J., et al. (2002). A pH-sensitive fluor CypHer 5, used to monitor agonist-induced G-proein coupled receptor internalization in live cells. Bio techniques 33 1152-1157. 

In acid-base titrations the end point is generally detected by a pH-sensitive indicator. In the EDTA titration a metal ion-sensitive indicator (abbreviated, to metal indicator or metal-ion indicator) is often employed to detect changes of pM. Such indicators (which contain types of chelate groupings and generally possess resonance systems typical of dyestuffs) form complexes with specific metal ions, which differ in colour from the free indicator and produce a sudden colour change at the equivalence point. The end point of the titration can also be evaluated by other methods including potentiometric, amperometric, and spectrophotometric techniques. 

The sensor is an ammonium ion-selective electrode surrounded by a gel impregnated with the enzyme mease (Figme 6-11) (22). The generated ammonium ions are detected after 30-60 s to reach a steady-state potential. Alternately, the changes in the proton concentration can be probed with glass pH or other pH-sensitive electrodes. As expected for potentiometric probes, the potential is a linear function of the logarithm of the urea concentration in the sample solution. 

Chitosan would not seem suitable as a pH-sensitive polymer because it is soluble at acidic pH values, and becomes insoluble approximately at pH 6.5. Nevertheless, an enteric coating can protect chitosan from the acidity of the stomach. When the preparation reaches the intestine, the en-... 

In recent years further concepts have been developed for the construction of polymer-based diodes, requiring either two conjugated polymers (PA and poly(A-methyl-pyrrole) 2 > or poly(A-methylpyrrole in a p-type silicon wafer solid-state field-effect transistor By modifying the transistor switching, these electronic devices can also be employed as pH-sensitive chemical sensors or as hydrogen or oxygen sensors 221) in aqueous solutions. Recently a PPy alcohol sensor has also been reported 222). 

Fig. 16-4 pH sensitivity to SO4- and NH4. Model calculations of expected pH of cloud water or rainwater for cloud liquid water content of 0.5 g/m. 100 pptv SO2, 330 ppmv CO2, and NO3. The abscissa shows the assumed input of aerosol sulfate in fig/m and the ordinate shows the calculated equilibrium pH. Each line corresponds to the indicated amoimt of total NH3 + NH4 in imits of fig/m of cloudy air. Solid lines are at 278 K, dashed ones are at 298 K. The familiar shape of titration curves is evident, with a steep drop in pH as the anion concentration increases due to increased input of H2SO4. (From Charlson, R. J., C. H. Twohy and P. K. Quinn, Physical Influences of Altitude on the Chemical Properties of Clouds and of Water Deposited from the Atmosphere." NATO Advanced Research Workshop Acid Deposition Processes at High Elevation Sites, Sept. 1986. Edinburgh, Scotland.)... 

An alternative approach is the use of pH-sensitive fluorophores (Lichtenberg and Barenholz, lOSS). These probes are located at the lipid-water interface and their fluorescence behavior reflects the local surface pH, which is a function of the surface potential at the interface. This indirect approach allows the use of vesicles independent of their particle size. Recently, techniques to measure the C potential of Liposome dispersions on the basis of dynamic light scattering became commercially available (Muller et al., 1986). 

Wang, C., and Huang, L. (1987). pH-sensitive immunoliposomes mediate target-cell-specific delivery and controlled expression of a foreign gene in mouse, Proc. Natl. Acad. Sci. USA, 84, 7851-7855. 

Carminic acid is a water-solnble componnd, stable nnder conditions of light and heat. It shows a maximnm absorption at 518 mn in aqneous ammonia solutions and at 494 mn in dilnted hydrochloric acid. ° The cochineal color is-pH sensitive. In... 

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