Hydrogen bond stabilization

As Figure 25 8 shows the glucose units of cellulose are turned with respect to each other The overall shape of the chain however is close to linear Consequently neigh boring chains can pack together m bundles where networks of hydrogen bonds stabilize the structure and impart strength to cellulose fibers... 

Hydrogen bonding stabilizes some protein molecules in helical forms, and disulfide cross-links stabilize some protein molecules in globular forms. We shall consider helical structures in Sec. 1.11 and shall learn more about ellipsoidal globular proteins in the chapters concerned with the solution properties of polymers, especially Chap. 9. Both secondary and tertiary levels of structure are also influenced by the distribution of polar and nonpolar amino acid molecules relative to the aqueous environment of the protein molecules. Nonpolar amino acids are designated in Table 1.3. 

A similar effect is produced by cocrystallization with protic solvents capable of forming a hydrogen bond-stabilized environment. Thus, dihydropyrimidine 47 (R = R = aryl,R = R = COOR, R = H) cocrystallizes with water (1 1) exclusively as the 1,6 tautomer (98T9837). 2,4,6,6-Tetraphenyldihydropyrimidine 47 (R = R = R = R = Ph, R = H) exists as the 1,6 tautomer in its solvate with... 

More recently, Stepanov et al. (1989) investigated the acid-base properties of the zwitterion 3.22 which is obtained in the diazotization of 5-amino-3-nitro-l,2,4-triazole. Under alkaline conditions the (Z)-diazoate dianion 3.23 is formed. It can be isomerized thermally to give the (E)-diazoate dianion 3.24. If the solution of this compound is acidified, the primary addition of a proton takes place at the anionic ring nitrogen yielding 3.25, and subsequently the hydrogen-bond-stabilized (Z)-iso-mer (3.26). Further acidification gives the nitrosoamine (3.27). 

Fig. 9. — Antiparallel packing arrangement of the 3-fold helices of (1— 4)-(3-D-xylan (7). (a) Stereo view of two unit cells roughly normal to the helix axis and along the short diagonal of the ab-plane. The two helices, distinguished by filled and open bonds, are connected via water (crossed circles) bridges. Cellulose type 3-0H-0-5 hydrogen bonds stabilize each helix, (b) A view of the unit cell projected along the r-axis highlights that the closeness of the water molecules to the helix axis enables them to link adjacent helices.

Fig. 16.—Antiparallel packing arrangement of 3-fold sodium pectate (13) helices, (a) Stereo view of two unit cells roughly normal to the fcc-plane. The helix at the center (open bonds) is antiparallel to the two in the front (tilled bonds). Intrachain hydrogen bonds stabilize each helix. Sodium ions (crossed circles) and water molecules (open circles) connect adjacent helices, (b) A view of the unitcell contents down the t -axis highlights the ions and water molecules located between the helices.

Fig. 35.—(a) Stereo view of about a turn of the 3-fold double helix of potassium gellan (41). The two chains are drawn in open and filled bonds for distinction. Both intra- and inter-chain hydrogen bonds stabilize the helix. The vertical line is the helix axis. Octahedrally coordinated potassium ions (crossed circles) and triply hydrogen-bonded water molecules (open circles) located above the ions are integral components of the structure of 41. 

In some molecules, the twist conformation is actually preferred. In all cis-2,5-di-fert-butyl-l,4-cyclohexanediol, hydrogen bonding stabilizes the otherwise high-energy form and 1,3-dioxane 89 exists largely as the twist conformation shown. Of course, in certain bicyclic compounds, the six-membered ring is forced to maintain a boat or twist conformation, as in norbornane or twistane. 

Density functional theory study of aqueous-phase rate acceleration and endo/exo selectivity of the butadiene and acrolein Diels-Alder reaction72 shows that approximately 50% of the rate acceleration and endo/exo selectivity is attributed to hydrogen bonding and the remainder to bulk-phase effects, including enforced hydrophobic interactions and cosolvent effects. This appears to be supported by the experimental results of Engberts where a pseudothermodynamic analysis of the rate acceleration in water relative to 1-propanol and 1-propanol-water mixtures indicates that hydrogen-bond stabilization of the polarized activated complex and the decrease of the hydrophobic surface area of the reactants during the activation process are the two main causes of the rate enhancement in water.13... 

The former structure contains an intramolecular H-bond within the host, which stabilizes its planar conformation, and an N-H. ..N link to the guest species. The other structure with acetic acid contains hydrogen-bond stabilized clusters of two hosts and two guests around the crystallographic inversion centers. A distortion of... 

Oxaziridines, the products of photochemical isomerization of polymeric nitrones, are characterized by high stability. The formation of an intramolecular hydrogen bond stabilizes the nitrone group with respect to UV-irradiation... 

However, another study concluded that the changes of the hydrogen-bond stability may be important in biological processes. For these, the influence of local electric fields created by Li+, Na+, and Mg2+ ions on the properties and reactivity of hydrogen bonds in HF and HC1 dimer has been carried out by means of ab initio self-consistent field (SCF) method [33]. A few years later, the effect of intensity and vector direction of the external electric field on activation barriers of unimole-cular reactions were studied using the semiempirical MINDO/3 method [34]. However, both semiempirical and ab initio calculations were performed to study the multiplicity change for carbene-like systems in external electric fields of different configurations (carbene and silylene) and the factor that determines the multiplicity and hence the reactivity of carbene-like structures is the nonuniformity of the field [35]. 

The next question is which of the two possible cis rotamers, i. e. Cs and Ce, is the stable conformation Clearly, pi nonbonded attraction favors Cs more than Ce while sigma nonbonded attraction, L e. hydrogen bonding, stabilizes the Ce rotamer... 

Microwave spectroscopy is probably the ultimate tool to study small alcohol clusters in vacuum isolation. With the help of isotope substitution and auxiliary quantum chemical calculations, it provides structural insights and quantitative bond parameters for alcohol clusters [117, 143], The methyl rotors that are omnipresent in organic alcohols complicate the analysis, so that not many alcohol clusters have been studied with this technique and its higher-frequency variants. The studied systems include methanol dimer [143], ethanol dimer [91], butan-2-ol dimer [117], and mixed dimers such as propylene oxide with ethanol [144]. The study of alcohol monomers with intramolecular hydrogen-bond-like interactions [102, 110, 129, 145 147] must be mentioned in this context. In a broader sense, this also applies to isolated ra-alkanols, where a weak Cy H O hydrogen bond stabilizes certain conformations [69,102]. Microwave techniques can also be used to unravel the information contained in the IR spectrum of clusters with high sensitivity [148], Furthermore, high-resolution UV spectroscopy can provide accurate structural information in suitable systems [149, 150] and thus complement microwave spectroscopy. 

Fig. 53. The main chain hydrogen bonds of basic pancreatic trypsin inhibitor, plus two of the side chains whose hydrogen bonds stabilize the ends of pieces of secondary structure Ser-47 at the beginning of an a-helix and Asn-43 at the end of a fi strand.

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