A comparative analysis of a series of DFT models of [NiFe]-hydrogenases, ranging from minimal NiFe clusters to very large systems including both the first and second coordination sphere of the bimetallic cofactor, was carried out with the aim of unraveling which stereoelectronic properties of the active site of [NiFe]-hydrogenases are crucial for efficient H2 binding and cleavage. H2 binding to the Ni-SIa redox state is energetically favored (by 4.0 kcal mol(-1)) only when H2 binds to Ni, the NiFe metal cluster is in a low spin state, and the Ni cysteine ligands have a peculiar seesaw coordination geometry, which in the enzyme is stabilized by the protein environment. The influence of the Ni coordination geometry on the H2 binding affinity was then quantitatively evaluated and rationalized analyzing frontier molecular orbitals and populations. Several plausible reaction pathways leading to H2 cleavage were also studied. It turned out that a two-step pathway, where H2 cleavage takes place on the Ni-SIa redox state of the enzyme, is characterized by very low reaction barriers and favorable reaction energies. More importantly, the seesaw coordination geometry of Ni was found to be a key feature for facile H2 cleavage. The discovery of the crucial influence of the Ni coordination geometry on H2 binding and activation in the active site of [NiFe]-hydrogenases could be exploited in the design of novel biomimetic synthetic catalysts.

Large displacement compliant joints can substitute traditional kinematic pairs in robotic articulated structures for increasing ease-of-assembly, robustness, and safety. Nonetheless, besides their limited motion capabilities, compliant joints might be subjected to undesired spatial deformations which can deteriorate the system stability and performance whenever a low number of control inputs is available. In all these cases, it is convenient to select/design joint morphologies which enable a selectively compliant behavior, i.e., a low stiffness along a single desired direction. Within this context, this paper outlines an engineering method for quantifying the joint's selective compliance by means of local and global performance indices. The approach is validated by comparing two beam-like flexures whose analytic solution is known from the literature. Finally, two joint morphologies, previously employed in the fabrication of robotic/prosthetic hands, are critically compared on the basis of the proposed criteria

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