ENHANCED SELECTIVITY

Depressants are reagents that selectively prevent the reaction between a coUector and a mineral, thus preventing its flotation. For example, sodium cyanide [143-33-9] depresses sphalerite [12169-28-7] (zinc sulfide) and pyrite [1309-36-0] (iron sulfide) but not galena. It thus enhances selective flotation of the galena. 

Acid catalysis using strong acid catalysts, especially 2eohtes which enhance selectivity because of pore si2e restrictions, has been used for a variety of alkenes and dienes (9—11). /-Butyltoluenediamine [106398-83-8] (/-BTDA) (C H gN2) is available on a semicommercial basis (12). 

The main advantages of the ms/ms systems are related to the sensitivity and selectivity they provide. Two mass analyzers in tandem significantly enhance selectivity. Thus samples in very complex matrices can be characterized quickly with Htde or no sample clean-up. Direct introduction of samples such as coca leaves or urine into an ms or even a gc/lc/ms system requires a clean-up step that is not needed in tandem mass spectrometry (28,29). Adding the sensitivity of the electron multiplier to this type of selectivity makes ms/ms a powerhil analytical tool, indeed. It should be noted that introduction of very complex materials increases the frequency of ion source cleaning compared to single-stage instmments where sample clean-up is done first. 

Nowadays all over the world considerable attention is focused on development of chemical sensors for the detection of various organic compounds in solutions and gas phase. One of the possible sensor types for organic compounds in solutions detection is optochemotronic sensor - device of liquid-phase optoelectronics that utilize effect of electrogenerated chemiluminescence. In order to enhance selectivity and broaden the range of detected substances the modification of working electrode of optochemotronic cell with organic films is used. Composition and deposition technique of modifying films considerably influence on electrochemical and physical processes in the sensor. 

This is an oversimplified treatment of the concentration effect that can occur on a thin layer plate when using mixed solvents. Nevertheless, despite the complex nature of the surface that is considered, the treatment is sufficiently representative to disclose that a concentration effect does, indeed, take place. The concentration effect arises from the frontal analysis of the mobile phase which not only provides unique and complex modes of solute interaction and, thus, enhanced selectivity, but also causes the solutes to be concentrated as they pass along the TLC plate. This concentration process will oppose the dilution that results from band dispersion and thus, provides greater sensitivity to the spots close to the solvent front. This concealed concentration process, often not recognized, is another property of TLC development that helps make it so practical and generally useful and often provides unexpected sensitivities. 

Fig. 12A, has a 10° libration. This gives a channel size which would be optimal for an ionic radius between that of Rb+ and Cs+. Therefore enhanced discrimination is not expected between Rb+ and Cs+, but the energy required to librate further inward to make contact with smaller ions in the series can be expected to enhance selectivity between these ions. Work is currently in progress to calculate the change in channel energy as a function of libration angle or of the equivalent, the effective channel radius S6). The implications of a peptide libration mechanism for enhancing ion selectivity can also be pursued experimentally as outlined below. 

The enhanced selectivity of alkane bromination over chlorination can be explained by turning once again to the Hammond postulate. In comparing the abstractions of an alkane hydrogen by Cl- and Br- radicals, reaction with Br- is less exergonic. As a result, the transition state for bromination resembles the alkyl radical more closely than does the transition state for chlorination, and the stability of that radical is therefore more important for bromination than for chlorination. 

Addilion of benzophenone to the lithium derivative 2 (M = Li) proceeds in a stereorandom fashion, which is attributed to the participation of radicals, detected by ESR and produced by single-electron transfer (SET)12. The magnesium derivative reacts with 90% diastereoselectivity with no SET being recorded. Benzaldehyde as the carbonyl compound affords the [1/, 1(1S)]-and [15,1(1/ )]-diastereomers in a 70 30 mixture, with 40% de12. Enhanced selectivities are achieved with camphor-derived 2-(2-oxazolyl)isoquinolines12a. 

The Lewis acid, boron trifluoride, enhances selectivity, but not reactivity. 

A further improvement utilizes the compatibility of hindered lithium dialkylamides with TMSC1 at —78 °C. Deprotonation of ketones and esters with lithium dialkylamides in the presence of TMSC1 leads to enhanced selectivity (3) for the kinetically generated enolate. Lithium t-octyl-t-butyl-amide (4) appears to be superior to LDA for the regioselective generation of enolates and in the stereoselective formation of (E) enolates. 

Alcohols can be selectively bound to the same host type if they are combined with an amine and vice versa, considering that a cation and an anion will be formed through a proton transfer. The so-formed alkoxide anion will bind to the boron atom, while the ammonium ion will be complexed by the crown ether (147, Fig. 39). Competition experiments involving benzyl-amine have shown enhanced selectivity for the complexation of alcohols with... 

Many chemical reactions, especially those involving the combination of two molecules, pass through bulky transition states on their way from reactants to products. Carrying out such reactions in the confines of the small tubular pores of zeolites can markedly influence their reaction pathways. This is called transition-state selectivity. Transition-state selectivity is the critical phenomenon in the enhanced selectivity observed for ZSM-5 catalysts in xylene isomerization, a process practiced commercially on a large scale. 

In this chapter, the main aspects of mass spectrometry that are necessary for the application of LC-MS have been described. In particular, the use of selected-ion monitoring (SIM) for the development of sensitive and specific assays, and the use of MS-MS for generating structural information from species generated by soft ionization techniques, have been highlighted. Some important aspects of both qualitative and quantitative data analysis have been described and the power of using mass profiles to enhance selectivity and sensitivity has been demonstrated. 

A dipolarophile bearing an ionic group and an associated counterion provides enhanced selectivity as has been recently demonstrated by Raposo and Wilcox [14]. Cycloaddition of benzonitrile 4 and the uncharged amine 5 a (a chiral phenylmaleimide derivative) in THE or chloroform provides a mixture of cycloadducts 6-9a in 1 4 4 4 diastereomeric ratio (i.e., 8 5 in favor of the methyl face approach of the dipolarophile. The ortho-substituents of the... 

It was eoncluded that the enhanced selectivity and yield for TFE over Cu-Mixed catalyst may be attributed to the surface modifications by the attack of HF produced during the pyrolysis of R22. The results suggest that R23 is formed by the secondary reaction between intermediate CF2 and HF. 

Selective polarization transfer A polarization transfer experiment in which only one signal is enhanced selectively. 

Reactive distillation is one of the classic techniques of process intensification. This combination of reaction and distillation was first developed by Eastman Kodak under the 1984 patent in which methyl acetate was produced from methanol and acetic acid. One of the key elements of the design is to use the acetic acid as both a reactant and an extraction solvent within the system, thereby breaking the azeotrope that exists within the system. Likewise, the addition of the catalyst to the system allowed sufficient residence time such that high yields could be obtained, making the process commercially viable. Other examples in which reactive distillation may enhance selectivity include those of serial reactions, in which the intermediate is the desired product, and the reaction and separation rates can be systematically controlled to optimize the yield of the desired intermediate. ... 

Because of this lack of resolving power, much electroanalytical research is aimed at providing increased selectivity. This can be accomplished in two ways. First, electrochemistry can be combined with another technique which provides the selectivity. Examples of this approach are liquid chromatography with electrochemical detection (LCEC) and electrochemical enzyme immunoassay (EEIA). The other approach is to modify the electrochemical reaction at the electrode to enhance selectivity. This... 

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