Nitrogenase structure and function relationships by density functional theory.

Area of Science:

• Computational Chemistry
• Biochemistry
• Bioinorganic Chemistry

Background:

• Density functional theory (DFT) is a powerful computational method widely used in metalloenzymology.
• DFT provides atomic and molecular insights into experimental data, explaining observed trends and differences.
• Biological nitrogen fixation presents a complex challenge regarding its structure and molecular mechanism.

Purpose of the Study:

• To review and detail the compilation and evaluation of experimental data for DFT analysis.
• To demonstrate the application of DFT in critically evaluating diverse experimental information.
• To gain new insights into the structure-function relationships of nitrogenase iron-sulfur clusters.

Main Methods:

• Systematic compilation of experimental data related to nitrogenase.
• Unbiased evaluation of compiled data using density functional theory.
• Application of DFT to analyze the structure and reactivity of iron-sulfur clusters.

Main Results:

• DFT analysis offers a unified approach to assess disparate experimental findings.
• The study provides a framework for integrating structural and reactivity data.
• New insights into the electronic structure and function of nitrogenase active sites are obtained.

Conclusions:

• DFT is invaluable for unraveling complex metalloenzyme mechanisms like nitrogen fixation.
• A rigorous DFT approach, grounded in comprehensive experimental data, yields significant understanding.
• This work highlights the potential of DFT to advance the study of iron-sulfur clusters in nitrogenase.