Solvents proton-containing, acceptors

Selectivity effects are determined by mobile phase interactions between the stationary phase and the solute. Those mobile phases containing proton donors will interact with basic solutes. Conversely, mobile phases containing proton donor acceptors will interact strongly with acidic solvents. Where excessive interactions occur between the solute and the mobile phase, peak tailing can result. However, the inclusion of a basic modifier (triethylamine) can overcome such strong interactions and thereby improve peak shape. 

Halide donor-acceptor reactions (of XX ) are generally those in which X is donated to or accepted from an interhalogen. They include self-ionization reactions such as that of BrF3 shown in Equation (18.53). This property makes bromine trifluoride a common aprotic (without protons) self-ionizing solvent. In addition to its self-ionization, BrF3 readily accepts fluoride ions from other sources, such as alkali-metal fluorides, to produce salts containing the bromine tetrafluoride ion, as shown in Equation (18.54). Conversely, it can donate fluoride ions to produce salts containing the bromine difluoride cation, as shown in Equation (18.55). 

Since free protons cannot exist, acidic properties can only be shown when the solvent can act as a proton acceptor, i.e. as a base. Thus aqueous solutions of acids contain the hydroxonium ion,... 

Reactions with succinic anhydride or acetic anhydride to block dendrimer amines can be done in aqueous or methanolic solution. If organic solvent is used for the reaction, then it is typical to include triethylamine as a proton acceptor, which helps drive the reaction. Such reactions, however, can t be done to dendrimer amines once a protein containing amines also has been conjugated, as the protein too will get modified. 

Recently, a rhodium-catalyzed tandem cyclization has been reported with an arylboronic ester bearing a pendant Michael-type acceptor olefin and acetylenic65 or olefinic66 derivatives. This transformation proceeds in a water-containing medium as solvent and proton source. This catalyst system is optimized with electron-rich and bulky ligands to stabilize the rhodium intermediate and decrease the protonolysis of boron derivatives in a protic solvent. 

Besides the effect of solvent polarity, the C=C rotation in many push-pull ethylenes is sensitive to acid catalysis (143). This is probably explained by protonation of the acceptor groups, for example, the oxygen atoms in C=0 groups (16), which increases their acceptor capacity. Small amounts of acids in halogenated solvents, or acidic impurities, may have drastic effects on the barriers, and it is advisable to add a small quantity of a base such as 2,4-lutidine to obtain reliable rate constants (81). Basic catalysis is also possible, but it has only been observed in compounds containing secondary amino groups (38). 

Tyrosine fluorescence emission in proteins and polypeptides usually has a maximum between 303 and 305 nm, the same as that for tyrosine in solution. Compared to the Stokes shift for tryptophan fluorescence, that for tyrosine appears to be relatively insensitive to the local environment, although neighboring residues do have a strong effect on the emission intensity. While it is possible for a tyrosine residue in a protein to have a higher quantum yield than that of model compounds in water, for example, if the phenol side chain is shielded from solvent and the local environment contains no proton acceptors, many intra- and intermolecular interactions result in a reduction of the quantum yield. As discussed below, this is evident from metal- and ionbinding data, from pH titration data, and from comparisons of the spectral characteristics of tyrosine in native and denatured proteins. 

It has been observed in several instances29,64,121 that C=C rotations in Case 1 systems are strongly catalyzed by traces of acid. This can often be explained by protonation of the acceptor groups, which increases their acceptor capacity. Since halogenohydrocarbon solvents often contain traces of acid, it is advisable to add a small amount of a sterically hindered base like 2,6-lutidine in order to obtain reproducible results. 

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