Use to increase selectivity

Figure 5.31. Examples of how zeolites can be used to increase selectivity for a reaction.

Additives are often used to increase selectivity. They are paramount in chiral separations, but they are also frequently used in non-chiral separations, e.g., cyclodextrins (CDs). In our lab, BGEs with and without a cyclodextrin are part of our generic protocol. Figure 8 demonstrates that although one can more or less predict interaction with the additive from the chemical structures, it is still difficult to predict separation.Batch-to-batch variability and variability between suppliers can be a problem of (chiral) additives and a check of different batches has to be part of the robustness test (e.g., reference 56). If the additive is charged and has one or more pK s around the pH of the BGE, extra care should be taken to control the pH. Alternatively, better robustness might be obtained with another uncharged additive, even if this results in lower resolution. 

This oxidation is unique, since only silver is capable of epoxidizing ethylene, and silver is active only in the oxidation of ethylene. A low-surface-area a-alumina is usually applied to support about 10-15% silver. Organic halides (1,2-dichloro-ethane, ethyl and vinyl chloride) are added as moderators, and additives (Cs, Ba) are also used to increase selectivity. At present selectivity in industrial oxidations is about 80%. 

In general, lower reaction temperatures are used to increase selectivity and to avoid side reactions. The reaction of cyclohexanone with diethyl dicarbonate (18) led to the O-acylated product 19 at —78°C (Figure 5.7), with the C-acylated product 20 being produced at about 80°C [17]. Cooling a lipase-mediated esterification to — 40°C enriched the product ester 21 to 97% ee (Figure 5.7) [18]. Reaction rates slow with decreasing temperatures, and the rule of thumb is that increasing the reaction temperature by 10°C will usually double the reaction rate. 

Another technique that increases separating power for complex mixtures is continuous development. The top end of the plate is extended out of the chamber so that solvent evaporates and its flow is continuous. Weak solvents are used to increase selectivity, and the development distances are kept short so time does not become excessive. The method is mostly used with HPTLC plates, for which Regis markets a short bed/continuous development (SB/CD) chamber. 

The Fourier transformed interferograms provide IR spectra that can be recorded at will in normalized reflectance spectra (reflectance units R) (Fig. 17A), in quasi-absorbance units that are not proportional to concentration (-log/ ) (Fig. 17B), or in Kubelka-Munk units that are proportional to concentration (Fig. 17C). The substances can be localized on the TLC plate by using either spectral windows chosen at will (Fig. 18A and also dashed line in B) or the Gram-Schmidt technique (Fig. 18 dotted line in B). The first method can be used to increase selectivity (e.g., the spectral window can be chosen so as to detect only compounds with carbonyl groups), while the latter is universally applicable and independent of wave number. 

Electrochemical (EC) detection is particularly well suited to capillary electrophoresis. In contrast to many optical methods, EC detection can be miniaturized without a loss of sensitivity. It is very selective because there are few compounds in biological samples that are electroactive. The selectivity is tunable and dependent on the electrode material and the applied potential. Modified electrodes and multiple electrode systems can be used to increase selectivity for certain classes of analytes. Electrodes and potentiostats can also be integrated into chip-based CE systems using procedures similar to those employed for the manufacture of the analytical chips. 

At present, improved chromatographic separation can only be used to increase selectivity if the matrix is well characterized. The best hope for a selective analysis, without false positives, is by use of detectors specific for the surfactant of interest. Other compounds will still be present during chromatography, but they will not be seen. 

Additions to the PLM include monochromatic filters or a monochromator to obtain dispersion data (eg, the variation in refractive index with wavelength). By the middle of the twentieth century, ultraviolet and infrared radiation were used to increase the identification parameters. In 1995 the FTIR microscope gives a view of the sample and an infrared absorption pattern on selected 100-p.m areas (about 2—5-ng samples) (37). 

The rate of side-chain cleavage of sterols is limited by the low solubiUty of substrates and products and thek low transport rates to and from cells. Cyclodextrins have been used to increase the solubiUties of these compounds and to assist in thek cellular transport. Cyclodextrins increase the rate and selectivity of side-chain cleavage of both cholesterol and P-sitosterol with no effect on cell growth. Optimal conditions have resulted in enhancement of molar yields of androsta-l,4-diene-3,17-dione (92) from 35—40% to >80% in the presence of cyclodextrins (120,145,146,155). 

Catalysts that do not contain potassium lose activity very quickly because of coke deposition on the surface of the catalyst. Chemical changes that occur when the catalyst is removed from the operating environment make it very difficult to determine the nature of most of the promoter elements during the reaction, but potassium is always found to be present as potassium carbonate in the used catalyst. The other promoters are claimed to increase selectivity and the operating stabiUty of the catalyst. 

The ultraviolet lamps used in the photochlorination process serve to dissociate the chlorine into free radicals and start the radical-chain reaction. Other radical sources, such as 2,2 -a2obisisobutyronitrile, have been used (63,64). Primary by-products of the photochlorination process include 1,1,2-trichloroethane (15—20%), tetrachloroethanes, and pentachloroethane. Selectivity to 1,1,1-trichloroethane is higher in vapor-phase chlorination. Various additives, most containing iodine or an aromatic ring in the molecule, have been used to increase the selectivity of the reaction to... 

The use of peroxyacids, including PMSA, makes it possible to improve photometric method of nickel determination - to increase selectivity, accuracy and reproducibility of measurements. Peroxyacids as oxidants ai e used for nickel determination in aluminium and copper alloys, natural waters, stomatological products. 

Modification techniques for activated carhon were used to increase the removal capacity by surface adsorption and to improve the selectivity to volatile organic compounds (VOCs). Modified activated carbons (MACs) were prepared by modifying the purified activated carbon with various acids or bases. The effects of adsorption capacity and modified contents on the textural properties of the MACs were investigated. Furthermore, VOC adsorption and desorption experiments were carried out to determine the relationship between the adsorption capacity and the chemical properties of the adsorbents. High adsorption capacity for the selected VOCs was obtained over lwt%-H3P04/AC (lwt%-PA/AC). As a result, MAC was found to be very effective for VOC removal by adsorption with the potential for repeated use through desorption by simple heat treatment. 

Several techniques for VOC removal have been investigated such as thermal incineration, catalytic oxidation, condensation, absorption, bio-filtration, adsorption, and membrane separation. VOCs are present in many types of waste gases and are often removed by adsorption [1]. Activated carbon (AC) is commonly used as an adsorbent of gases and vapors because of its developed surface area and large pore volumes [2]. Modification techniques for AC have been used to increase surface adsorption and hence removal capacity, as well as to improve selectivity to organic compounds [3]. 

A technique known as selective electron capti sensitization has been used to increase the response of the BCD weakly electron-capturing compounds [117]. In this mode a standard electron-capture detector is used with a supply of makeup gas doped with a specific sensitizing reagent such as oxygen nitrous oxide. In this way the BCD functions as an ion-aoleculSj... 

The most commonly used filter medium is woven cloth, but a great variety of other media is also used. The main types are listed in Table 10.2. A comprehensive discussion of the factors to be considered when selecting filter media is given by Purchas (1971) and Mais (1971) see also Purchas and Sutherland (2001). Filter aids are often used to increase the rate of filtration of difficult slurries. They are either applied as a precoat... 

Other poisons (modifiers) used to create such selective Pd catalysts may be metals 23 Zn, Cd, Zr, Ru, Au, Cu, Fe, Hg, Ag, Pb, Sb, and Sn or solvents (organic modifiers) 24 pyridine, quinoline, piperidine, aniline, diethylamine, other amines, chlorobenzene, and sulfur compounds. Hydroxides have also been used to increase the half-hydrogenation selectivity of Pd. 

The salting-in effect may be used to increase the solubility of a drug substance through the formation of associated ion pairs, most commonly making use of anionic countering (hydrochloride being the most popular). Detailed reviews of pharmaceutical salts have been published, which contain extensive tables of anions and cations acceptable for pharmaceutical use [44,47]. These articles also describe useful processes for the selection of the most desirable salt... 

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