Symmetrical hydrogen bond

Structural data from in situ high pressure ND studies are analyzed in [163], they show that the O-H and H- - -O distances follow the same correlations as have been established at ambient conditions on different compounds. Another pressure effect is the evolution of the double-welled, hydrogen bond potential into a single-well potential. According to ab initio calculations, the bulk modulus must have a discontinuity at this point and this can be an indication for hydrogen bond symmetrization it means that the hydrogen bond symmetrization is a second-order phase transition. 

Aoki K, Katoh E, Yamawaki H et al (1999) Hydrogen-bond symmetrization and molecular dissociation in hydrogen halids. Physica B 265 83—86... 

E. Katoh, H. Yamawaki, H. Fujihisa, M. Sakashita, K Aoki, Raman study of phase transition and hydrogen bond symmetrization in solid DQ at high pressure. Phys. Rev. B 61(1), 119... 

Table 1 Hsts some of the physical properties of duoroboric acid. It is a strong acid in water, equal to most mineral acids in strength and has a p p o of —4.9 as compared to —4.3 for nitric acid (9). The duoroborate ion contains a neady tetrahedral boron atom with almost equidistant B—F bonds in the sohd state. Although lattice effects and hydrogen bonding distort the ion, the average B—F distance is 0.138 nm the F—B—F angles are neady the theoretical 109° (10,11). Raman spectra on molten, ie, Hquid NaBF agree with the symmetrical tetrahedral stmcture (12).

Like Thr 124 and Thr 215, the Asn 69 and Asn 159 residues occupy equivalent positions in the two homologous motifs of TBP. By analogy with the symmetric binding of a dimeric repressor molecule to a palindromic sequence described in Chapter 8, the two motifs of TBP form symmetric sequence-specific hydrogen bonds to the quasi-palindromic DNA sequence at the center of the TATA box. The consensus TATA-box sequence has an A-T base pair at position 4, but either a T-A or an A-T base pair at the symmetry-related position 5, and the sequence is, therefore, not strictly palindromic. However, the hydrogen bonds in the minor groove can be formed equally well to an A-T base pair or to a T-A base pair, because 02 of thymine and N3 of adenine occupy nearly stereochemically equivalent positions, and it is sufficient, therefore, for the consensus sequence of the TATA box to be quasi-palindromic. 

The two peptides form a symmetrical dimer stabilized by four hydrogen bonds (red dashes) and hydrophobic contacts. The two monomers form a four-stranded, anti-parallel pleated sheet. 

Chain extenders are usually low molecular weight symmetrical diols or diamines. Chain extenders react with isocyanates in the same way as polyols do, but because they are low molecular weight, a high concentration of hydrogen-bonded molecules can associate and phase out of the polyol to form plastic-like domains called hard segments . Hard segments will be discussed in Section 4. Some of the more common diol and diamine chain extenders are shown in Table 3. 

While crystal structures of rubredoxins have been known since 1970 (for a full review on rubredoxins in the crystalline state, see Ref. (15)), only recently have both crystal and solution structures of Dx been reported (16, 17) (Fig. 3). The protein can be described as a 2-fold symmetric dimer, firmly hydrogen-bonded and folded as an incomplete /3-barrel with the two iron centers placed on opposite poles of the molecule, 16 A apart. Superimposition of Dx and Rd structures reveal that while some structural features are shared between these two proteins, significant differences in the metal environment and water structure exist. They can account for the spectroscopic differences described earlier. 

---