Low selectivity

For determining the adsorption isotherm, the equilibrium concentrations of bound and free template must be reliably measured within a large concentration interval. Since the binding sites are part of a solid, this experiment is relatively simple and can be carried out in a batch equilibrium rebinding experiment or by frontal analysis. 

The isotherms for the two enantiomers of phenylalanine anilide were measured at 40, 50, 60 and 70 C, and the data fitted to each of the models given in Equations (1-3) [42]. The isotherms obtained by fitting the data to the Langmuir equation were of a quality inferior to the other two. Fittings of the data to the Freundlich and to the bi-Langmuir equations were both good. A comparison of the residuals revealed that the different isotherms of d-PA were best fitted to a bi-Langmuir model, while the 

6 Enantiomer Separations using Designed Imprinted Chiral Phases 

For preparative or semipreparative-scale enantiomer separations, the enantiose-lectivity and column saturation capacity are the critical factors determining the throughput of pure enantiomer that can be achieved. The above-described MICSPs are stable, they can be reproducibly synthesized, and they exhibit high selectivities - all of which are attractive features for such applications. However, most MICSPs have only moderate saturation capacities, and isocratic elution leads to excessive peak tailing which precludes many preparative applications. Nevertheless, with the L-PA MICSP described above, mobile phases can be chosen leading to acceptable resolution, saturation capacities and relatively short elution times also in the isocratic mode (Fig. 6-6). 

5 Adsorption-Desorption Kinetics and Chromatographic Band Broadening 

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An arrangement is to be chosen to inhibit the side reaction, i.e., give low selectivity losses. The side reaction is suppressed by starving the reactor of either monochlorodecane or chlorine. Since the reactor is designed to produce monochlorodecane, the former option is not practical. However, it is practical to use an excess of decane. 

The selectivity of an electrophile, measured by the extent to which it discriminated either between benzene and toluene, or between the meta- and ara-positions in toluene, was considered to be related to its reactivity. Thus, powerful electrophiles, of which the species operating in Friedel-Crafts alkylation reactions were considered to be examples, would be less able to distinguish between compounds and positions than a weakly electrophilic reagent. The ultimate electrophilic species would be entirely insensitive to the differences between compounds and positions, and would bring about reaction in the statistical ratio of the various sites for substitution available to it. The idea has gained wide acceptance that the electrophiles operative in reactions which have low selectivity factors Sf) or reaction constants (p+), are intrinsically more reactive than the effective electrophiles in reactions which have higher values of these parameters. However, there are several aspects of this supposed relationship which merit discussion. 

Dehydrogenation of Propionates. Oxidative dehydrogenation of propionates to acrylates employing vapor-phase reactions at high temperatures (400—700°C) and short contact times is possible. Although selective catalysts for the oxidative dehydrogenation of isobutyric acid to methacrylic acid have been developed in recent years (see Methacrylic ACID AND DERIVATIVES) and a route to methacrylic acid from propylene to isobutyric acid is under pilot-plant development in Europe, this route to acrylates is not presentiy of commercial interest because of the combination of low selectivity, high raw material costs, and purification difficulties. 

Other Rhodium Processes. Unmodified rhodium catalysts, eg, 1 14(00)22 [19584-30-6] have high hydroformylation activity but low selectivity to normal aldehydes. 

Extraction and Extractive Distillation. The choice of an extraction or extractive distillation solvent depends upon its boiling point, polarity, thermal stabiUty, selectivity, aromatics capacity, and upon the feed aromatic content (see Extraction). Capacity, defined as the quantity of material that is extracted from the feed by a given quantity of solvent, must be balanced against selectivity, defined as the degree to which the solvent extracts the aromatics in the feed in preference to paraffins and other materials. Most high capacity solvents have low selectivity. The ultimate choice of solvent is deterrnined by economics. The most important extraction processes use either sulfolane or glycols as the polar extraction solvent. 

Erom 1955—1975, the Ziegler-Natta catalyst (91), which is titanium trichloride used in combination with diethylaluminum chloride, was the catalyst system for propylene polymerization. However, its low activity, which is less than 1000 g polymer/g catalyst in most cases, and low selectivity (ca 90% to isotactic polymer) required polypropylene manufacturers to purify the reactor product by washing out spent catalyst residues and removing unwanted atactic polymer by solvent extraction. These operations added significantly to the cost of pre-1980 polypropylene. 

MULTISENSOR SYSTEMS ELECTRONIC TONGUE BASED ON LOW-SELECTIVE SENSORS AND MULTIWAY METHODS OF RECEIVED DATA TREATMENT... 

Definition the electronic tongue is an analytical instrarment including an array of low-selective chemical sensors and appropriate pattern recognition tool, capable to recognize quantitative and qualitative compositions of simple and complex solutions . 

Recycle reactors at that time were called Backmix Reactors. They were correctly considered the worst choice for the production of a reactive intermediate, yet the best for kinetic studies. The aim of the kinetic study for ethylene oxidation was to maximize the quality of the information, leaving the optimization of production units for a later stage in engineering studies. The recycle reactors could provide the most precise results at well defined conditions even if at somewhat low selectivity to the desired product. 

Important differences are seen when the reactions of the other halogens are compared to bromination. In the case of chlorination, although the same chain mechanism is operative as for bromination, there is a key difference in the greatly diminished selectivity of the chlorination. For example, the pri sec selectivity in 2,3-dimethylbutane for chlorination is 1 3.6 in typical solvents. Because of the greater reactivity of the chlorine atom, abstractions of primary, secondary, and tertiary hydrogens are all exothermic. As a result of this exothermicity, the stability of the product radical has less influence on the activation energy. In terms of Hammond s postulate (Section 4.4.2), the transition state would be expected to be more reactant-like. As an example of the low selectivity, ethylbenzene is chlorinated at both the methyl and the methylene positions, despite the much greater stability of the benzyl radical ... 

The comparison among these techniques is tabulated in Table 22.1. In summary, HdC is a separation technique with low selectivity however, the efficiency can be very high. Especially in PCHdC, high analysis speed can be achieved over a wide MW range. ThFFF performs best for the separation of high MW samples. SEC has an intermediate selectivity between FldC and ThFFF. Practicality makes SEC the most suitable method for the common MW range of synthetic polymers. SEC is by far the most commonly used technique for molecular weight distribution determinations. However, HdC is better for the fast analysis purpose. 

Free-radical arylation of heterocyclic compounds is a relatively inefficient process in which yields of particular products greater than 50% are rare. This is the inevitable result of the high reactivity and low selectivity of aryl radicals not only is it usual for the heterocyclic compound to be attacked at each of its available positions, but, as shown in preceding sections, other by-products are numerous. Nevertheless, the method often presents the only short route to a given compound and it has been widely applied. Preparative uses are grouped in this section under the heading of the heterocyclic system concerned. 

When a first column of a very short length (and therefore a low selectivity) is used (this is especially suitable for multiresidue methods), we talk about an on-line precolumn (PC) switching technique coupled to LC (PC-LC or solid-phase extraction (SPE)-LC). This is particulary useful for the enrichment of analytes, and enables a higher sample volume to be injected into the analytical column and a higher sensitivity to be reached. The sample is passed through the precolumn and analytes are retained, while water is eliminated then, by switching the valve, the analytes retained in the precolumn are transferred to the analytical column by the mobile phase, and with not just a fraction, as in the previous cases. 

One problem with SPE-LC is the low selectivity of the precolumn. Immunosorbents, which have been developed for a few compounds (72), can considerably improve selectivity. The selectivity was high for different pollutants (73, 74). Figure 13.14 shows that selectivity is higher with an anti-isoproturon cartridge than with aPLRP-S precolumn. 

The low selectivity of the SPE columns currently in use can be increased with more selective sorbents such as the immunosorbents, which have been quite extensively used in SPE-LC (72). Immunoaffinity-based solid-phase extraction (lASPE) sorbents have also been used in coupled gas chromatography for determining... 

A better solution for preparative columns is the development of separation media with substantially increased selectivities. This approach allows the use of shorter columns with smaller number of theoretical plates. Ultimately, it may even lead to a batch process in which one enantiomer is adsorbed selectively by the sorbent while the other remains in the solution and can be removed by filtration (single plate separation). Higher selectivities also allow overloading of the column. Therefore, much larger quantities of racemic mixtures can be separated in a single run, thus increasing the throughput of the separation unit. Operation under these overload conditions would not be possible on low selectivity columns without total loss of resolution. 

Through the use of a tin(iv) enolate with benzaldehyde it was possible to generate the anti A diastereomer 47 with high selectivity (Entry 5). With tin(n) etiolates a highly substituent-dependent outcome was observed. Low selectivities resulted with para-substituted aromatic aldehydes, but good selectivities were observed for ortho-substituted aromatic aldehydes (Entries 7-9). Simultaneous re-... 

The addition of titanated 2-methylpropenamides to 2-(ter/-butoxycarbonylamino)a]dehydes was investigated during the synthesis of dipeptide isosteres and was shown to exhibit low selectivity only93,94. 

Finally, it should be mentioned that the allylation of 2,4-disubstituted pyrrolidine derivatives proceeds with reasonable diastereosclectivity for the trans-compound 2,4-rra .v-l, but with low selectivity for the m-isomer 2,4-m-l131. 

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