Proton donor/acceptor

Proton donor/acceptors (amphoteric solvents) water, alcohols. 

The solvent triangle classification method of Snyder Is the most cosDBon approach to solvent characterization used by chromatographers (510,517). The solvent polarity index, P, and solvent selectivity factors, X), which characterize the relative importemce of orientation and proton donor/acceptor interactions to the total polarity, were based on Rohrscbneider s compilation of experimental gas-liquid distribution constants for a number of test solutes in 75 common, volatile solvents. Snyder chose the solutes nitromethane, ethanol and dloxane as probes for a solvent s capacity for orientation, proton acceptor and proton donor capacity, respectively. The influence of solute molecular size, solute/solvent dispersion interactions, and solute/solvent induction interactions as a result of solvent polarizability were subtracted from the experimental distribution constants first multiplying the experimental distribution constant by the solvent molar volume and thm referencing this quantity to the value calculated for a hypothetical n-alkane with a molar volume identical to the test solute. Each value was then corrected empirically to give a value of zero for the polar distribution constant of the test solutes for saturated hydrocarbon solvents. These residual, values were supposed to arise from inductive and... 

Kiefer PM, Hynes JT (2002) Nonlinear free energy relations for adiabatic proton transfer reactions in a polar environment. I. Fixed proton donor—acceptor separation. J Phys Chem A... 

Some complications arise from the presence of proton donor-acceptor interactions134 when the donor is a protic amine. The separate evaluation of the two kinds of interactions may be a difficult problem. Similarly, if the electron acceptor is also a proton donor, the overlapping of salification and complexation processes makes the separate investigation of the interactions very difficult. This is the case in the complexes between amines and picric acid or other related phenols. For complexes of 2,4,6-trinitro-3-hydroxypyridine135 and... 

Charge transfer complexes between amines and discharged substances were investigated extensively (mainly by spectroscopic methods). The choice of more simple models excludes the presence of proton donor-acceptor interactions which complicate the investigations of other interactions by overlapping different interactions. 

Various energy terms calculated for the linear water dimer molecule and for some hexamer water clusters at the HF level in both the canonical and the separated representations, using various basis sets are given in the present work. This study is twofold. First, the differences between the proton donor and proton acceptor molecules have been assessed in the linear water dimer. The EM energy contributions (obtained in the separated representation) are expected to characterize the proton donor / acceptor ability of the monomers. Secondly, a possibility of identification of a proton donor or acceptor character of the monomers in some water hexamers was tested. 

In 1923, the same year in which Bronsted and Lowry defined acids and bases in terms of their proton donor/acceptor properties, the American chemist G. N. Lewis proposed an even more general concept of acids and bases. Lewis noticed... 

The protons are dissociated away in contact with the water in the internal channels. Center. A covalent bonding of proton donor-acceptor molecules and a sufficiently dense stacking leads to a solvent free proton transport. Bottom. In the soggy sand electrolytes anions are absorbed at the surfaces of the insulating matrix (e.g., SiOJ. The respective cations (e.g., Li+) are free while far away from the matrix essentially associated in form of ions pairs if the solvent is a weak dielectric. 

Johannes Nicolaus Bronsted and Thomas Martin Lowry simultaneously developed the proton donor/acceptor theory of acids and bases in the... 

It is known that sweet-tasting compounds are quite common and their chemical structures vary widely. In order to establish a structure-taste relationship, a large number of compounds have been tested, and several molecular theories of sweet taste have been proposed by different groups. At present, the phenomenon of sweet taste seems best explained by the tripartite functioning of the postulated AH, B (proton donor-acceptor) system and hydro-phobic site X (1, 2, J3, 4 5). Sweet-tasting compounds possess the AH-B-X system in the molecules, and the receptor site seems to be also a trifunctional unit similar to the AH-B-X system of the sweet compounds. Sweet taste results from interaction between the receptor site and the sweet unit of the compounds. Space-filling properties are also important as well as the charge and hydro-phobic properties. The hydrophile-hydrophobe balance in a molecule seems to be another important factor. 

Based on chemical considerations alone, ribozymes should be able to catalyze many different types of reactions. Ribozymes can maintain defined secondary and tertiary structures, just as protein enzymes do. Ribozymes can interact with substrates specifically via hydrogen bond networks, just as protein enzymes do. Finally, ribozymes have available to them a chemistry that, while more limited than of proteins, is substantial. RNA contains proton donors and acceptors with pK, values that cluster at 4 and 9.71 The critical lack of a good donor/acceptor with a pKt near 7 can be rectified by any of several simple expedients, such as modification of guanosine to 7-methylguanosine, protonation of triple base-paired cysto-sine,72 or inclusion of a proton donor/acceptor in an environment with a different polarity than water (in this respect, it is interesting to note that Dahm and Uhlenbeck have found that the cleavage reaction catalyzed by the hammerhead ribozyme is dependent on some dissociable proton with a pKa of 8.0).73... 

It should be noted that the effect does not require the addition of an extra proton donor-acceptor system. In fact, the proton exchange may take place between a zwitterion and a non-zwitterion state of different orientation as indicated by the reaction scheme... 

Once the gas phase Hamiltonian is parametrized as a function of the inner-sphere reaetion coordinate(s), the free energy is calculated as a function of the proton coordinate(s), the scalar solvent coordinates, and the inner-sphere reaction coordinate(s). Note that this approaeh assumes that the optimized geometries of the VB states are not significantly affected by the solvent. For proton transfer reactions, the proton donor-acceptor distance may be treated as an additional solute reaction coordinate that ean be incorporated into the molecular mechanical terms describing the diagonal matrix elements hf- and, in some cases, the off-diagonal matrix elements (/io)y. If the inner-sphere reaction coordinate represents a slow mode, it is treated in the same way as the solvent coordinates. As discussed throughout the literature, however, often the inner-sphere reaction coordinate must be treated quantum mechanically [27, 28]. In this case, the inner-sphere reaction coordinate is treated in the same way as the proton coordinate(s), and the vibrational wave functions depend explicitly on both the proton coordinate(s) and the inner-sphere reaction coordinate(s). 

Solvents may be classifiedf broadly according to their proton donor-acceptor properties as either amphiprotic, that is, both acidic and basic, or aprotic, neither acidic nor basic. 

Adsorption TLC selection of the mobile phase is conditioned by sample and stationary-phase polarities. The following polarity scale is valid for various compound classes in NPTLC in decreasing order of K values carboxylic acids>amides>amines>alcohols>aldehydes > ketones > esthers > nitro compounds > ethers > hal-ogenated compounds > aromatics >olefins > saturated hydrocarbons > fluorocarbons. For example, retention on silica gel is controlled by the number and functional groups present in the sample and their spatial locations. Proton donor/acceptor functional groups show the greatest retention, followed by dipolar molecules, and, finally, nonpolar groups. 

Replacement of hydrogen by alkali-metal disrupts the hydrogen bonding necessary for the concerted mechanism, but the relatively high activity of -SOali was attributed to failure to remove all the water of hydration under the conditions used for drying the catalyst. Hence -SOali could act as a proton-donor acceptor of sufficient strength to act in the concerted mechanism, but was unable to catalyse the carbonium ion mechanism. The soluble toluene-p-sulphonic acid was less active at high concentration because it could not act in a concerted mechanism. 

The system 2-naphthylamine/triethylamine forms proton donor/acceptor interaction, which was investigated in the excited state by measuring time-resolved fluorescence spectra. While the similar 2-naphthol/triethylamine system affords the ion pair interaction, via the hydrogen bond complex, the 2-naphthylamine/triethylamine system presents hydrogen bond interaction which shows a low-temperature absorption with 7max = 370 nm, and Amax = 370 nm in the fluorescence spectrum148. 

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