Electronic Structure and Solvation Effects from Core and Valence Photoelectron Spectroscopy of Serum Albumin

X-ray photoelectron spectroscopy of bovine serum albumin (BSA) in a liquid jet is used to investigate the electronic structure of a solvated protein, yielding insight into charge transfer mechanisms in biological systems in their natural environment. No structural damage was observed in BSA following X-ray photoelectron spectroscopy in a liquid jet sample environment. Carbon and nitrogen atoms in different chemical environments were resolved in the X-ray photoelectron spectra of both solid and solvated BSA. The calculations of charge distributions demonstrate the difficulty of assigning chemical contributions in complex systems in an aqueous environment. The high-resolution X-ray core electron spectra recorded are unchanged upon solvation. A comparison of the valence bands of BSA in both phases is also presented. These bands display a higher sensitivity to solvation effects. The ionization energy of the solvated BSA is determined at 5.7 ± 0.3 eV. Experimental results are compared with theoretical calculations to distinguish the contributions of various molecular components to the electronic structure. This comparison points towards the role of water in hole delocalization in proteins.

[1]  Neal Fairley,et al.  Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy , 2021 .

[2]  U. Diebold,et al.  Polarons in materials , 2021, Nature Reviews Materials.

[3]  Nitai Sylvetsky.  Toward Simple, Predictive Understanding of Protein-Ligand Interactions: Electronic Structure Calculations on Torpedo Californica Acetylcholinesterase Join Forces with the Chemist’s Intuition , 2020, Scientific Reports.

[4]  Christian Plessl,et al.  CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations. , 2020, The Journal of chemical physics.

[5]  V. Grassian,et al.  Salting Up of Proteins at the Air/Water Interface. , 2019, Langmuir : the ACS journal of surfaces and colloids.

[6]  J. Toufaily,et al.  A facile preparation of CuS-BSA nanocomposite as enzyme mimics: Application for selective and sensitive sensing of Cr(VI) ions , 2019, Sensors and Actuators B: Chemical.

[7]  M. Linford,et al.  Bovine serum albumin, aqueous solution, by near-ambient pressure XPS , 2019, Surface Science Spectra.

[8]  B. Wallace,et al.  CDtoolX, a downloadable software package for processing and analyses of circular dichroism spectroscopic data , 2018, Protein science : a publication of the Protein Society.

[9]  Frank Wien,et al.  BeStSel: a web server for accurate protein secondary structure prediction and fold recognition from the circular dichroism spectra , 2018, Nucleic Acids Res..

[10]  B. Halle,et al.  The geometry of protein hydration. , 2018, The Journal of chemical physics.

[11]  A. Voityuk,et al.  Reliable charge assessment on encapsulated fragment for endohedral systems , 2018, Scientific Reports.

[12]  Marcin Płodzień,et al.  Simulating polaron biophysics with Rydberg atoms , 2017, Scientific Reports.

[13]  Jiahui Chen,et al.  Improvements to the APBS biomolecular solvation software suite , 2017, Protein science : a publication of the Protein Society.

[14]  Hirohito Hayashi,et al.  Site-Specific Dual Functionalization of Cysteine Residue in Peptides and Proteins with 2-Azidoacrylates. , 2017, Bioconjugate chemistry.

[15]  Wei-Ren Chen,et al.  Molecular Basis of the Antioxidant Capability of Glutathione Unraveled via Aerosol VUV Photoelectron Spectroscopy. , 2016, The journal of physical chemistry. B.

[16]  David T. Limmer,et al.  Water at Interfaces. , 2016, Chemical reviews.

[17]  Randima P. Galhenage,et al.  Liquid-Jet X-ray Photoelectron Spectra of TiO(2) Nanoparticles in an Aqueous Electrolyte Solution. , 2016, The journal of physical chemistry letters.

[18]  M. Silly,et al.  The Electronic Structure of Saturated NaCl and NaI Solutions in Contact with a Gold Substrate , 2016, Topics in Catalysis.

[19]  A. I. Muñoz,et al.  Electrochemical Quartz Crystal Microbalance and X-Ray Photoelectron Spectroscopy study of cathodic reactions in Bovine Serum Albumin containing solutions on a Physical Vapour Deposition-CoCrMo biomedical alloy , 2015 .

[20]  G. Whitesides,et al.  Charge Tunneling along Short Oligoglycine Chains. , 2015, Angewandte Chemie.

[21]  N. Ueno,et al.  Photoelectron spectroscopy on the charge reorganization energy and small polaron binding energy of molecular film , 2015 .

[22]  L. Kronik,et al.  Electronic Transport via Homopeptides: The Role of Side Chains and Secondary Structure. , 2015, Journal of the American Chemical Society.

[23]  Frank Wien,et al.  Accurate secondary structure prediction and fold recognition for circular dichroism spectroscopy , 2015, Proceedings of the National Academy of Sciences.

[24]  H. Stanley,et al.  The influence of water on protein properties. , 2014, The Journal of chemical physics.

[25]  K. Fears.  Measuring the pK/pI of biomolecules using X-ray photoelectron spectroscopy. , 2014, Analytical chemistry.

[26]  B. Winter,et al.  Photoemission spectra and density functional theory calculations of 3d transition metal-aqua complexes (Ti-Cu) in aqueous solution. , 2014, The journal of physical chemistry. B.

[27]  P. Cristiani,et al.  Effect of protein adsorption on the corrosion behavior of 70Cu-30Ni alloy in artificial seawater. , 2014, Bioelectrochemistry.

[28]  H. Gray,et al.  Long-Range Electron Tunneling , 2014, Journal of the American Chemical Society.

[29]  D. Laage,et al.  Water Dynamics in Protein Hydration Shells: The Molecular Origins of the Dynamical Perturbation , 2014, The journal of physical chemistry. B.

[30]  S. Mischler,et al.  Adsorption of BSA on Passivated CoCrMo PVD Alloy: An EQCM and XPS Investigation , 2014 .

[31]  J. Bokhoven,et al.  In situ photoelectron spectroscopy at the liquid/nanoparticle interface , 2013 .

[32]  Nicholas D M Hine,et al.  Electrostatic considerations affecting the calculated HOMO–LUMO gap in protein molecules , 2013, Journal of physics. Condensed matter : an Institute of Physics journal.

[33]  O. Björneholm,et al.  Molecular sinkers: X-ray photoemission and atomistic simulations of benzoic acid and benzoate at the aqueous solution/vapor interface. , 2012, The journal of physical chemistry. B.

[34]  C. Miron,et al.  Lifetime broadening of core-excited and -ionized states , 2012 .

[35]  J. Rehr,et al.  Electronic Structures of Formic Acid (HCOOH) and Formate (HCOO(-)) in Aqueous Solutions. , 2012, The journal of physical chemistry letters.

[36]  D. Beratan,et al.  Electronic Structure of Self-Assembled Peptide Nucleic Acid Thin Films , 2011 .

[37]  Daniel Spångberg,et al.  On the origins of core-electron chemical shifts of small biomolecules in aqueous solution: insights from photoemission and ab initio calculations of glycine(aq). , 2011, Journal of the American Chemical Society.

[38]  A. Yencha,et al.  Threshold photoelectron spectroscopy of H2O and D2O over the photon energy range 12-40 eV , 2009 .

[39]  C. Leggio,et al.  About the albumin structure in solution: cigar Expanded form versus heart Normal shape. , 2008, Physical chemistry chemical physics : PCCP.

[40]  Joost VandeVondele,et al.  Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. , 2007, The Journal of chemical physics.

[41]  H. Cachet,et al.  Study by XPS of the chlorination of proteins aggregated onto tin dioxide during electrochemical production of hypochlorous acid , 2007 .

[42]  I. Hertel,et al.  Hydrogen bonds in liquid water studied by photoelectron spectroscopy. , 2007, The Journal of chemical physics.

[43]  J. Weiss,et al.  Structural and functional changes in ultrasonicated bovine serum albumin solutions. , 2007, Ultrasonics sonochemistry.

[44]  Valentin Gogonea,et al.  Electronic structure, ionization potential, and electron affinity of the enzyme cofactor (6R)-5,6,7,8-tetrahydrobiopterin in the gas phase, solution, and protein environments. , 2006, The journal of physical chemistry. B.

[45]  L. Lartundo-Rojas,et al.  Influence of bovine serum albumin in sulphuric acid aqueous solution on the corrosion and the passivation of an iron-chromium alloy , 2006 .

[46]  P. Decleva,et al.  Photoionization cross-sections: a guide to electronic structure , 2005 .

[47]  R. Paynter,et al.  A time- and angle-resolved X-ray photoelectron spectroscopy study of polystyrene exposed to a nitrogen plasma , 2004 .

[48]  I. Hertel,et al.  Full Valence Band Photoemission from Liquid Water Using EUV Synchrotron Radiation , 2004 .

[49]  P. Marcus,et al.  Adsorption of bovine serum albumin on chromium and molybdenum surfaces investigated by Fourier-transform infrared reflection-absorption spectroscopy (FT-IRRAS) and X-ray photoelectron spectroscopy , 2003 .

[50]  M. Faubel,et al.  Photoelectron spectroscopy of liquid water, some alcohols, and pure nonane in free micro jets , 1997 .

[51]  S. Kapoor,et al.  Evidence for possible positive hole transport in the biological protein bovine serum albumin , 1993 .

[52]  V. Lakhno,et al.  A polaron model for electron transfer in globular proteins. , 1993, Journal of theoretical biology.

[53]  M. Miles,et al.  Scanning probe microscopy of collagen I and pN-collagen I. Assemblies and the relevance to scanning tunnelling microscopy contrast generation in proteins , 1993 .

[54]  Shen Panwen,et al.  Structural studies on metal-serum albumin. IV. The interaction of Zn(II), Cd(II) and Hg(II) with HSA and BSA , 1992 .

[55]  Sven Tougaard,et al.  Quantitative analysis of the inelastic background in surface electron spectroscopy , 1988 .

[56]  J. Butler,et al.  The reaction between the superoxide anion radical and cytochrome c. , 1975, Biochimica et biophysica acta.

[57]  T. Peters,et al.  Fragments of bovine serum albumin produced by limited proteolysis. Isolation and characterization of peptic fragments. , 1975, Biochemistry.

[58]  H. Siegbahn,et al.  ESCA applied to liquids , 1973 .

[59]  H. Siegbahn,et al.  ESCA studies of CO2, CS2 and COS , 1972 .

[60]  K. Siegbahn,et al.  ESCA studies of molecular core and valence levels in the gas phase , 1972 .

[61]  R. Grigorovici,et al.  Optical Properties and Electronic Structure of Amorphous Germanium , 1966, 1966.

[62]  BARNETT ROSENBERG,et al.  Electrical Conductivity of Proteins , 1962, Nature.