Electrostatic and steric interactions determine bacteriorhodopsin single-molecule biomechanics.

Bacteriorhodopsin (bR) is a haloarchaeal membrane protein that converts the energy of single photons into large structural changes to directionally pump protons across purple membrane. This is achieved by a complex combination of local dynamic interactions controlling bR biomechanics at the submolecular level, producing efficient amplification of the retinal photoisomerization. Using single molecule force spectroscopy at different salt concentrations, we show that tryptophan (Trp) residues use steric specific interactions to create a rigid scaffold in bR extracellular region and are responsible for the main unfolding barriers. This scaffold, which encloses the retinal, controls bR local mechanical properties and anchors the protein into the membrane. Furthermore, the stable Trp-based network allows ion binding to two specific sites on the extracellular loops (BC and FG), which are involved in proton release and lateral transport. In contrast, the cytoplasmic side of bR is mainly governed by relatively weak nonspecific electrostatic interactions that provide the flexibility necessary for large cytoplasmic structural rearrangements during the photocycle. The presence of an extracellular Trp-based network tightly enclosing the retinal seems common to most haloarchaeal rhodopsins, and could be relevant to their exceptional efficiency.

[1]  J. Killian,et al.  Interfacial anchor properties of tryptophan residues in transmembrane peptides can dominate over hydrophobic matching effects in peptide-lipid interactions. , 2003, Biochemistry.

[2]  Aharon Oren,et al.  Amino acid composition of bulk protein and salt relationships of selected enzymes of Salinibacter ruber, an extremely halophilic bacterium , 2002, Extremophiles.

[3]  J. Riesle,et al.  Proton migration along the membrane surface and retarded surface to bulk transfer , 1994, Nature.

[4]  Duan Yang,et al.  Side-chain contributions to membrane protein structure and stability. , 2004, Journal of molecular biology.

[5]  Shay Bar-Haim,et al.  G protein-coupled receptors: in silico drug discovery in 3D. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[6]  Gyo«rgy Värö Analogies between halorhodopsin and bacteriorhodopsin , 2000 .

[7]  Daniel J. Muller,et al.  Locating ligand binding and activation of a single antiporter , 2005, EMBO reports.

[8]  H Luecke,et al.  Structure of bacteriorhodopsin at 1.55 A resolution. , 1999, Journal of molecular biology.

[9]  Daniel J Müller,et al.  Controlled unfolding and refolding of a single sodium-proton antiporter using atomic force microscopy. , 2004, Journal of molecular biology.

[10]  E. Querol,et al.  Contribution of Extracellular Glu Residues to the Structure and Function of Bacteriorhodopsin , 2001, The Journal of Biological Chemistry.

[11]  H. Khorana,et al.  Bacteriorhodopsin mutants containing single tyrosine to phenylalanine substitutions are all active in proton translocation. , 1987, Proceedings of the National Academy of Sciences of the United States of America.

[12]  E. Siggia,et al.  Entropic elasticity of lambda-phage DNA. , 1994, Science.

[13]  S. Misra,et al.  Mutation of a surface residue, lysine-129, reverses the order of proton release and uptake in bacteriorhodopsin; guanidine hydrochloride restores it. , 1997, Biophysical journal.

[14]  Jane Clarke,et al.  Hidden complexity in the mechanical properties of titin , 2003, Nature.

[15]  E. Evans Probing the relation between force--lifetime--and chemistry in single molecular bonds. , 2001, Annual review of biophysics and biomolecular structure.

[16]  M. Kates,et al.  [13] Lipids of purple membrane from extreme halophiles and of methanogenic bacteria , 1982 .

[17]  V. Lattanzio,et al.  Lipid-protein stoichiometries in a crystalline biological membrane: NMR quantitative analysis of the lipid extract of the purple membrane. , 2002, Journal of lipid research.

[18]  A. Lee,et al.  Lipid-protein interactions in biological membranes: a structural perspective. , 2003, Biochimica et biophysica acta.

[19]  Klaus Gerwert,et al.  Proton binding within a membrane protein by a protonated water cluster. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[20]  D. Oesterhelt,et al.  Dynamics of different functional parts of bacteriorhodopsin: H-2H labeling and neutron scattering. , 1998, Proceedings of the National Academy of Sciences of the United States of America.

[21]  H. Khorana,et al.  Structure-function studies on bacteriorhodopsin. IX. Substitutions of tryptophan residues affect protein-retinal interactions in bacteriorhodopsin. , 1989, The Journal of biological chemistry.

[22]  T. Ebrey,et al.  Light isomerizes the chromophore of bacteriorhodopsin , 1980, Nature.

[23]  J. Lanyi,et al.  Steric interaction between the 9-methyl group of the retinal and tryptophan 182 controls 13-cis to all-trans reisomerization and proton uptake in the bacteriorhodopsin photocycle. , 1996, Biochemistry.

[24]  H Li,et al.  Atomic force microscopy reveals the mechanical design of a modular protein. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[25]  J. Lanyi,et al.  Structural clues to the mechanism of ion pumping in bacteriorhodopsin. , 2003, Advances in protein chemistry.

[26]  John E. Sader,et al.  Parallel beam approximation for V‐shaped atomic force microscope cantilevers , 1995 .

[27]  G. Zaccaı̈,et al.  Thermal motions and function of bacteriorhodopsin in purple membranes: effects of temperature and hydration studied by neutron scattering. , 1993, Proceedings of the National Academy of Sciences of the United States of America.

[28]  E. Pebay-Peyroula,et al.  X-ray structure of bacteriorhodopsin at 2.5 angstroms from microcrystals grown in lipidic cubic phases. , 1997, Science.

[29]  D. Oesterhelt,et al.  Rhodopsin-like protein from the purple membrane of Halobacterium halobium. , 1971, Nature: New biology.

[30]  H. Gaub,et al.  Unfolding pathways of individual bacteriorhodopsins. , 2000, Science.

[31]  Daniel J Müller,et al.  Stability of bacteriorhodopsin alpha-helices and loops analyzed by single-molecule force spectroscopy. , 2002, Biophysical journal.

[32]  Andres F. Oberhauser,et al.  The molecular elasticity of the extracellular matrix protein tenascin , 1998, Nature.

[33]  J. Bišćan,et al.  Determination of iso-electric point of silicon nitride by adhesion method , 2000 .

[34]  D. Oesterhelt,et al.  Localization of glycolipids in membranes by in vivo labeling and neutron diffraction. , 1998, Molecular cell.

[35]  A. Kidera,et al.  The structure of bacteriorhodopsin at 3.0 A resolution based on electron crystallography: implication of the charge distribution. , 1999, Journal of molecular biology.

[36]  R Henderson,et al.  Specific labelling of the protein and lipid on the extracellular surface of purple membrane. , 1978, Journal of molecular biology.

[37]  J. Klafter,et al.  Beyond the conventional description of dynamic force spectroscopy of adhesion bonds , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[38]  N. Dencher,et al.  Protonation dynamics of the extracellular and cytoplasmic surface of bacteriorhodopsin in the purple membrane. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[39]  D. Oesterhelt,et al.  Probing origins of molecular interactions stabilizing the membrane proteins halorhodopsin and bacteriorhodopsin. , 2005, Structure.

[40]  S. Taneva,et al.  Bacteriorhodopsin Thermal Stability: Influence of Bound Cations and Lipids on the Intrinsic Protein Fluorescence , 2000, Zeitschrift fur Naturforschung. C, Journal of biosciences.

[41]  J. Lanyi,et al.  Bacteriorhodopsin as a model for proton pumps , 1995, Nature.

[42]  Marek Cieplak,et al.  Mechanical unfolding of ubiquitin molecules. , 2005, The Journal of chemical physics.

[43]  Jens Struckmeier,et al.  Probing the energy landscape of the membrane protein bacteriorhodopsin. , 2004, Structure.

[44]  A. Engel,et al.  Adsorption of biological molecules to a solid support for scanning probe microscopy. , 1997, Journal of structural biology.

[45]  R. Becker,et al.  A comprehensive investigation of the mechanism and photophysics of isomerization of a protonated and unprotonated Schiff base of 11-cis-retinal , 1985 .

[46]  J. Killian,et al.  Protein–lipid interactions studied with designed transmembrane peptides: role of hydrophobic matching and interfacial anchoring (Review) , 2003, Molecular membrane biology.

[47]  D. Madern,et al.  Halophilic adaptation of enzymes , 2000, Extremophiles.

[48]  H. Hansma,et al.  The backbone conformational entropy of protein folding: experimental measures from atomic force microscopy. , 2002, Journal of molecular biology.

[49]  H. Gaub,et al.  Unfolding pathways of native bacteriorhodopsin depend on temperature , 2003, The EMBO journal.

[50]  Sadashiva S. Karnik,et al.  Structure-Function Studies on Bacteriorhodopsin , 1987 .

[51]  J. Killian,et al.  The effects of hydrophobic mismatch between phosphatidylcholine bilayers and transmembrane alpha-helical peptides depend on the nature of interfacially exposed aromatic and charged residues. , 2002, Biochemistry.

[52]  A. Engel,et al.  Determining molecular forces that stabilize human aquaporin-1. , 2003, Journal of structural biology.

[53]  Daniel J. Muller,et al.  Characterizing molecular interactions in different bacteriorhodopsin assemblies by single-molecule force spectroscopy. , 2006, Journal of molecular biology.

[54]  David Eisenberg,et al.  The discovery of the α-helix and β-sheet, the principal structural features of proteins , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[55]  A. Ikai,et al.  Mechanical unfolding of a2‐macroglobulin molecules with atomic force microscope , 1996 .

[56]  A. Oberhauser,et al.  Atomic force microscopy captures length phenotypes in single proteins. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[57]  J. Lanyi,et al.  Changes in hydrogen bonding and environment of tryptophan residues on helix F of bacteriorhodopsin during the photocycle: a time-resolved ultraviolet resonance Raman study. , 2002, Biochemistry.

[58]  S Haacke,et al.  Probing the Ultrafast Charge Translocation of Photoexcited Retinal in Bacteriorhodopsin , 2005, Science.

[59]  H. R. Catchpole,et al.  A microprobe analysis of inorganic elements in Halobacterium salinarum , 2005, Cell biology international.

[60]  H. Gaub,et al.  Unfolding barriers in bacteriorhodopsin probed from the cytoplasmic and the extracellular side by AFM. , 2006, Structure.

[61]  H. Luecke,et al.  X-ray crystallographic analysis of lipid-protein interactions in the bacteriorhodopsin purple membrane. , 2003, Annual review of biophysics and biomolecular structure.

[62]  J. Otomo,et al.  Bacteriorhodopsin mutants of Halobacterium sp. GRB. II. Characterization of mutants. , 1989, The Journal of biological chemistry.

[63]  Hans-Jürgen Butt,et al.  Calculation of thermal noise in atomic force microscopy , 1995 .

[64]  Glutamate-194 to cysteine mutation inhibits fast light-induced proton release in bacteriorhodopsin. , 1997, Biochemistry.

[65]  M. Rief,et al.  Reversible unfolding of individual titin immunoglobulin domains by AFM. , 1997, Science.

[66]  S. Smith,et al.  Folding-unfolding transitions in single titin molecules characterized with laser tweezers. , 1997, Science.

[67]  D. Oesterhelt,et al.  The halo‐opsin gene. II. Sequence, primary structure of halorhodopsin and comparison with bacteriorhodopsin , 1987, The EMBO journal.

[68]  G Büldt,et al.  Atomic force microscopy of native purple membrane. , 2000, Biochimica et biophysica acta.

[69]  Anthony Watts,et al.  Differential stiffness and lipid mobility in the leaflets of purple membranes. , 2006, Biophysical journal.

[70]  Stefan Haacke,et al.  Ultrafast excited state dynamics of the protonated Schiff base of all-trans retinal in solvents. , 2005, Biophysical journal.

[71]  A. Oberhauser,et al.  The study of protein mechanics with the atomic force microscope. , 1999, Trends in biochemical sciences.

[72]  A. Naito,et al.  Regio-selective detection of dynamic structure of transmembrane alpha-helices as revealed from (13)C NMR spectra of [3-13C]Ala-labeled bacteriorhodopsin in the presence of Mn2+ ion. , 2001, Biophysical journal.

[73]  J. Vonck A three-dimensional difference map of the N intermediate in the bacteriorhodopsin photocycle: part of the F helix tilts in the M to N transition. , 1996, Biochemistry.

[74]  Karl Edman,et al.  Bacteriorhodopsin: a high-resolution structural view of vectorial proton transport. , 2002, Biochimica et biophysica acta.

[75]  V. Lemaître,et al.  Unfolding and extraction of a transmembrane alpha-helical peptide: dynamic force spectroscopy and molecular dynamics simulations. , 2005, Biophysical journal.

[76]  H. Khorana,et al.  Effects of tryptophan mutation on the deprotonation and reprotonation kinetics of the Schiff base during the photocycle of bacteriorhodopsin. , 1992, Biophysical journal.

[77]  H. Khorana,et al.  Vibrational spectroscopy of bacteriorhodopsin mutants: chromophore isomerization perturbs tryptophan-86. , 1989, Biochemistry.

[78]  Daniel J. Muller,et al.  Bacteriorhodopsin folds into the membrane against an external force. , 2006, Journal of molecular biology.

[79]  M. Krebs,et al.  Role of helix-helix interactions in assembly of the bacteriorhodopsin lattice. , 1999, Biochemistry.

[80]  A. Caflisch,et al.  Sequential unfolding of individual helices of bacterioopsin observed in molecular dynamics simulations of extraction from the purple membrane. , 2006, Biophysical journal.