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However, the topic of short or ��strong�� hydrogen bonds involving amongst others the carboxyl(ate) groups found in proteins has received great attention especially since they were associated with enzymatic catalytic mechanisms (Perrin & Nielson, 1997 ?; Katz et al., 2002 ?; Gilli & Gilli, 2009 ?; Perrin, 2010 ?; Hosur et al., 2013 ?) involving either the syn or anti lone pairs (Zimmerman et al., 1991 ?). The carboxyl�Ccarboxyl hydrogen bonds are generally considered as ��-cooperative bonds or bonds belonging to the class of ��resonance-assisted hydrogen bonds�� (RAHB; Vishweshwar et al., 2004 ?; Bertolasi et al., 2006 ?; Gilli & Gilli, 2009 ?). In these motifs, the COOH donor is activated by ��-cooperative hydrogen bonding (O��H?O=C). The carboxyl�Ccarboxylate hydrogen bonds that involve a bond between an acid and its conjugate base fall clearly in a different pool where the stabilizing effect is induced by the presence of the negative charge. PRDX4 These bonds are also called ionic hydrogen bonds (Steiner, 1999 ?; Meot-Ner, 2012 ?) or negatively ��charge-assisted hydrogen bonds�� (CAHB; Vishweshwar et al., 2004 ?; Gilli & Gilli, 2009 ?). They are on average ??0.1?? shorter than the RAHB hydrogen bonds (Fig. 6 ?). This is particularly obvious when both groups have similar pK a values as in protein structures where they play important structural and sometimes catalytic functions (Cleland & Kreevoy, 1994 ?; Hosur et al., 2013 ?). A third category of hydrogen bonds find more is found in mono-anion dicarboxylic compounds (Fig. 3 ?). These intramolecular hydrogen bonds can be regarded as very short CAHBs given their average 2.43?? distance (Fig. 6 ? d). Consequently, they also belong to the strongest class of hydrogen bonds among those involving carboxyl(ate) groups. The shortening of the hydrogen bond is attributed to the presence of the electronegative O acceptor atom. They are probably further stabilized by some synergism due to increased ��-delocalization facilitated by their intramolecular character (Perrin & Nielson, Duvelisib research buy 1997 ?). These dimers involve both the anti conformer and a carbonyl lone pair, supporting the view that the lone pair basicity scale might be essentially contextual. Further, these mono-anion dicarboxylic compounds are involved in the formation of at least two types of hetero-catemeric chains: (i) the SA-A��AS-S (Fig. 7 ? d) and (ii) SA-A��AA-S types (Fig. 13d). Rather counterintuitively, the shortest carboxyl(ate)�Cwater hydrogen bonds involve the neutral carboxyl and not the charged carboxylate group (Fig. 11 ?). Such short hydrogen bonds were analysed by density functional theory (?miechowski et al., 2011 ?; Brown et al., 2012 ?) and extensively discussed in a small-molecule neutron diffraction study where the authors were able to demonstrate the associated chain of polarization events (Vishweshwar et al., 2004 ?).