Bound working point

Electron and nuclear double resonance (ENDOR) studies at 5 K have led to the assignment of all protons of histidines bound to copper (248, 249) and to the factorization of the coupling constants into a dipolar and an isotropic part. This has been possible through irradiation of a frozen sample at different g values. Figure 39 shows ENDOR spectra of bovine Cu2Zn2SOD, obtained at five working points of the... 

Studies by Chan and Floss et al. [32a] with another kind of MMO, the so-called particulate form pMMO from Methylococcus capsulatus (Bath) (which is membrane bound and contains copper), confirmed that the rate controlling step of methane hydroxylation has a very high KIE, while ethane produces only a moderate KIE. The data obtained in this work point to a mechanism in which C-H bond cleavage is preceded by bond formation at the alkyl carbon, i.e., one proceeding through a pentacoordinated carbon species [32a]. 

One small movement is carried out to obtain a nonvertex working point (no degeneracy). The only requirement is that the bound constraints on each variable are fulfilled. 

The first violates its upper bound, and the second and the fifth violate their lower bound. The working point to which the KKT conditions must be applied to becomes... 

In related work a library of 1,458 peptide ligands and various metal salts was tested in hydrolysis reactions of (p-nitrophenyl)phosphates.35 An active substructure composed of polymer-bound histidine in combination with Eu3+ was identified by further dissecting the original hit structure. It needs to be pointed out that catalytically active polymer beads can also be tested for catalytic activity using IR-thermography. In a seminal paper this was demonstrated using 7,000 encoded polymer beads prepared by split-and-pool methods, specifically in the metal-free acylation of alcohols.36... 

---