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keysbackpackphoto.Experimental and computational approaches to cofactor-assisted catalysis. The research presented in this review is focused on three types of biological catalysts, all of which require molecular oxygen or nitrogen to accomplish their catalytic activity. The first is an enzyme system, where a catalytic group is cofactor bound to an enzyme. The second is a naturally occurring system, in which an enzyme performs the reaction via a ligand bound to the enzyme. The third is a synthetic metalloenzyme, which we have termed a metal-directed enzyme, in which a transition metal is bound to the active site of an enzyme. The review emphasizes a variety of experimental approaches to study enzyme systems and metalloenzymes. We discuss the concepts and methods of fluorescence quenching, electron paramagnetic resonance, and electron transfer to define the relationship between cofactors and the active site of enzymes and metalloenzymes. On the basis of the synthetic metalloenzymes that we have synthesized, we have concluded that the design of synthetic metal-binding sites in proteins requires the following features: an accessible amino acid (aspartic acid), a group capable of donating electrons, and an imidazole or similar nitrogen-based ligand to which the metal ion can bind. We also have been able to define the ligand-metal distance as a function of metal and ligand and have established the importance of this distance in determining the selectivity of the reaction. We have compared computational results with experimental data and conclude that quantum mechanical calculations of the energies of multiple transition states and intermediates are required to establish the reaction mechanisms of enzyme systems and metalloenzymes. The computational chemistry approach to the design of metal-binding sites is demonstrated with a homology model of the active site of pyridoxal 5'-phosphate (PLP) dependent enzymes.MR-guided focused ultrasound for pain relief in patients with bone metastases: a case report. Bone metastases are a common complication of advanced cancer, and bone metastases may be the cause of significant pain and immobility. In cases where pain is more severe than the possible consequences of bone metastases, alternative treatments, including external beam radiotherapy, must be considered. However, if the disease has already progressed to a point where the patient's life expectancy is limited, then the use of non-radiotherapy techniques, including radiotherapy and surgery, are more appropriate. Here, we present a case of successful treatment




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