title: An expanded genetic code for probing the role of electrostatics in enzyme catalysis by vibrational Stark spectroscopy.
abstract: To find experimental validation for electrostatic interactions essential for catalytic reactions represents a challenge due to practical limitations in assessing electric fields within protein structures.
  
  
  
  This review examines the applications of non-canonical amino acids (ncAAs) as genetically encoded probes for studying the role of electrostatic interactions in enzyme catalysis.
  
  
  
  ncAAs constitute sensitive spectroscopic probes to detect local electric fields by exploiting the vibrational Stark effect (VSE) and thus have the potential to map the protein electrostatics.
  
  
  
  Mapping the electrostatics in proteins will improve our understanding of natural catalytic processes and, in beyond, will be helpful for biocatalyst engineering. This article is part of a Special Issue entitled "Biochemistry of Synthetic Biology - Recent Developments" Guest Editor: Dr. Ilka Heinemann and Dr. Patrick O'Donoghue.
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Müller-Breslau-Strasse 10, D-10623 Berlin, Germany. Electronic address: jan.voeller@85mail.com.
authors.forename: Jan-Stefan
authors.initials: JS
authors.lastname: Völler
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Müller-Breslau-Strasse 10, D-10623 Berlin, Germany; Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, D-10623 Berlin, Germany.
authors.forename: Hernan
authors.initials: H
authors.lastname: Biava
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, D-10623 Berlin, Germany. Electronic address: hildebrandt@chem.tu-berlin.de.
authors.forename: Peter
authors.initials: P
authors.lastname: Hildebrandt
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Müller-Breslau-Strasse 10, D-10623 Berlin, Germany. Electronic address: budisa@chem.tu-berlin.de.
authors.forename: Nediljko
authors.initials: N
authors.lastname: Budisa
mesh_terms: D002384:Catalysis; D005815:Genetic Code; D056004:Molecular Dynamics Simulation; D015202:Protein Engineering / Q000379:methods; D011506:Proteins / Q000737:chemistry* / Q000235:genetics / Q000378:metabolism; D013057:Spectrum Analysis / Q000379:methods*; D055672:Static Electricity; D014732:Vibration
chemical_list: D011506:Proteins
keywords: Electric fields; Enzyme catalysis; Enzyme electrostatics; Non-canonical amino acids; Vibrational Stark spectroscopy