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Site reactive 190 structure

Some of these heterocycles can also be suicide inhibitors if a new reactive structure is unmasked during acylation and this reactive species can further react with an active site nucleophile. For example, the presence of a 7-amino substituent (compounds 14, Fig. 11.9) makes the formation of a QIM possible. [Pg.372]

The overall trend is explainable, at least qualitatively, with simple unimolecular decay theory. When a correction term is incorporated into the theoretical collision limit to account for the intrinsic surface site reactivity in the bulk, excellent agreement is obtained with the overall reactivity. In considering the overall trends, certain clusters, namely Cu+, Cuj, and Cu in particular, displayed somewhat anomalous reactivities which might be associated with structural and/or electronic effects. [Pg.230]

While there is at present no full understanding as to why plastocyanin should require two sites for reaction, there is now much evidence detailing this two-site reactivity. Moreover, the recent X-ray crystal structure of ascorbate oxidase (which has 4 Cu atoms per molecule) has indicated a plastocyanin-like domain, with the two type 3 Cu s (in close proximity with the type 2 Cu) located at the remote site. Fig. 2 [5]. Since electrons are transferred, from the type 1 Cu to O2 bound at the type 3 center this structure defines two very similar through-bond routes for biological electron transfer. [Pg.179]

Figure 10 The global structures of Bowman-Birk inhibitors are diverse, but the reactive sites are structurally highly conserved. Reactive sites are oriented to the bottom right corner. The double-stranded /3-sheets neighboring the reactive sites are clearly visible, (a) 1 mvz, (b) 1 bbi, and (c) 1 h34. (d) The overlay of the backbone traces of the three BBIs ((a)-(c), colors as before) reveals their structural similarity. Additionally SFTI-1 (green, Ijbl) adopts the same fold in its active site. The residues (Arg in 1 mvz, Lys for other peptides) are also shown N and C denote the N- and C-termini of the truncated loops. Figure 10 The global structures of Bowman-Birk inhibitors are diverse, but the reactive sites are structurally highly conserved. Reactive sites are oriented to the bottom right corner. The double-stranded /3-sheets neighboring the reactive sites are clearly visible, (a) 1 mvz, (b) 1 bbi, and (c) 1 h34. (d) The overlay of the backbone traces of the three BBIs ((a)-(c), colors as before) reveals their structural similarity. Additionally SFTI-1 (green, Ijbl) adopts the same fold in its active site. The residues (Arg in 1 mvz, Lys for other peptides) are also shown N and C denote the N- and C-termini of the truncated loops.
LIF receptor also uses its Ig domain (D3) to receive site III epitopes of GNTF, LIF, GT-1, OSM, and others. So the Ig domain of LIF receptor is, in fact, more cross-reactive than gplSO. The site III structures of all gp 130-cytokines maintain a conserved aromatic residue at the tip of the D helix (Fig. 7) that is certainly the structural analog to the Trp residues we see in the center of the gplSO site III interface. Therefore we predict that the LIFR site III interface cross-reactivity is achieved by using similar structural features at the gplSO IgD. [Pg.135]

Once the hexameric structure of the yeast FAS was established, the number of functional active sites still remained to be determined. Earlier studies had shown that the functional complex contains approximately six equivalents each of two prosthetic groups 4 -phosphopantetheine [60,63], necessary for the AGP functionality, and flavin mononucleotide [64], an essential component of the enoyl reductase activity. These studies provided an early indication that each of the six active sites in the complex has a full set of the chemical groups necessary for fatty acid synthesis. Nevertheless, conflicting reports appeared in the literature as to the competence of six active sites. Whereas some reports suggested the possibility of half-sites reactivity (only three of the six sites are catalytically competent) [65, 66], others proposed that all six active sites could synthesize fatty acids [62]. Subsequent active site titration experiments were performed which quantitated the amount of fatty acyl products formed in the absence of turnover [67]. Single-turnover conditions were achieved through the use of... [Pg.94]

Hennig M, Griimn B, Contestabile R, John RA, Jansonius JN. Crystal structure of glutamate-1-semialdehyde aminomutase an alpha 2-dimeric vitamin B6-dependent enzyme with asymmetry in structure and active site reactivity. 1997 94 4866-4871. [Pg.680]

It has been concluded from a study of the optical and e.p.r. spectra of Co —Cu bovine superoxide dismutase, in which zinc has been replaced by cobalt, that the cobalt site reactivity should be described in terms of reaction of the Co-imidazolate-Cu system as a whole the crystal structure reported last year indicated that the metals were linked by a common histidine residue. There is an exchange interaction between the cobalt and copper however, this is abolished when the linking imidazole is protonated. Further evidence for the close proximity and interactive dependence of the zinc and copper binding sites was obtained from a study of the 4 Cu protein a two-fold enhancement of the activity of 2 Cu dismutase was observed upon occupation of the zinc sites by the Cu ". On the basis of C1 n.m.r. studies, Fee and Ward have suggested that one co-ordination position of Cu in superoxide dismutase is normally occupied by water they further suggest that superoxide can displace the solvent to form a cupric peroxide complex. [Pg.427]

On the basis of the crystal structure of a Bacillus stearothermophilus pyruvate dehydrogenase subcomplex formed between the heterotetrameric El and the peripheral subunit binding domain of E2 with an evident stmctural dissymmetry of the two active sites, a direct active center communication via an acidic proton tunnel has been proposed (Frank et ak, 2004). According to this, one active site is in a closed state with an activated cofactor even before a substrate molecule is engaged, whereas the activation of the second active site is coupled to decarboxylation in the first site. Our own kinetic NMR studies on human PDH El (unpublished) support the model suggested, but similar studies on related thiamin enzymes, such as pyruvate decarboxylase, transketolase or pyruvate oxidase reveal that half-of-the-sites reactivity is a unique feature of ketoacid dehydrogenases. In line with this. X-ray crystallography studies on intermediates in transketolase catalysis indicated an active site occupancy close to unity in both active sites (Fiedler et al., 2002 and G. Schneider, personal communication). [Pg.1425]

Our formalism shall include three types of OSC. We will explore electronic OSC. Here, we will consider OSC where the electronics of a ligand are influenced by some species not directly bound to a metal these perturbations manifest in altered spectroscopic and thermodynamic properties. Electronic OSC will also be considered where nonligating atoms participate in active site reactivity, as with hydrogen bonds that define electron transfer (ET) pathways. Structural OSC will be... [Pg.120]

Some detailed x-ray studies in this field have appeared the structures investigated are summarized in Figure 8. In the partially reduced [l,3,4]thiadiazolo[2,3-i][l,3]thiazinium salt (65) the C(7)—S(8) bond proved to be longer (1.846 A) than expected (1.82 A) which might account for the enhanced chemical reactivity of this compound towards nucleophiles at this site <89JOC2024>. Structure elucidation of the isomers (66a R = Ph, R = H) and (66b R = H, R = Ph) revealed that both compounds are planar and the phenyl group in each derivative is coplanar <89MI 816-01 >. X-ray analysis... [Pg.423]


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See also in sourсe #XX -- [ Pg.314 ]




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Active Site Electronic Structure ontributions to Reactivity

Dinuclear site structure reactivity

Quaternary Structure and Half-Site Reactivity

Reactive sites

Site Structure

Site structural

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