BP 204 Focus Paper: Ligand Binding - Stroud:

P1) Fersht AR; Shi JP; Knill-Jones J; Lowe DM; Wilkinson AJ; Blow DM; et al. Hydrogen bonding and biological specificity analysed by protein engineering. Nature, 1985 Mar 21-27, 314(6008):235-8.

• Energetic accounting for a hydrogen bond

• Paired-to-unpaired hydrogen bonds to charged moieties

• Balancing the equation of hydrogen bonds versus solvent

______

P2) Livnah O; Stura EA; Johnson DL; Middleton SA; Mulcahy LS; Wrighton NC; Dower WJ; Jolliffe LK; Wilson IA. Functional mimicry of a protein hormone by a peptide agonist: the EPO receptor complex at 2.8 A Science, 1996 Jul 26, 273(5274):464-71.

• Biology of selection: ‘phage display’; why dimerizing ligands selected?

• Avidity. Additivity of free energy contributors

• Buried surface areas and affinity

• Transmembrane signaling by cytokine receptors depends on dimerization

______

P3) Robert C. Rizzo, De-Ping Wang, Julian Tirado-Rives, and

William L. Jorgensen Validation of a Model for the Complex of HIV-1

Reverse Transcriptase with Sustiva through Computation of Resistance Profiles

______

P4) David E. Shaw,1,2* Paul Maragakis,1† Kresten Lindorff-Larsen,1† Stefano Piana,1†Ron O. Dror,1 Michael P. Eastwood,1 Joseph A. Bank,1 John M. Jumper,1 John K. Salmon,1Yibing Shan,1 Willy Wriggers Atomic-Level Characterization of the Structural Dynamics of Proteins

______

P5) Chimera tutorial:

(

______

P6) Zhou, Y; Morals-Cabral, JH; Kaufman, A., MacKinnon, R. Chemistry of ion coordination and hydration revealed by a K+ channel-Fab complex at 2.0 Å resolution. Nature, 2001 Nov 01, (414):43-48.

• Basis for coordinating K+ ions – the pathway

• Compensation for lipids in the center

• Selectivity for K+ versus other ions

• Hydrophobic exit port

______

P7). Erlanson,DA; Braisted, AC; Raphael, DR; Randal, Mike; Stroud,RM; Gordon, EM; Wells, JA. Site-directed ligand discovery. PNAS. 2000 Aug 15, 97(17)9367-9372.

• Facing problems for Drug Discovery

• Tethering – Why? How? Reducing potential

• Additivity of energy

Jencks WP. On the attribution and additivity of binding energies. Proc Natl Acad Sci U S A. 1981;78(7):4046-50.

• The conundrum of non-additivity

• Fragmenting Biotin

• Entropy reduction

______

P8) Rasmussen SG, DeVree BT, Zou Y, Kruse AC, Chung KY, Kobilka TS, et al. Crystal structure of the beta2 adrenergic receptor-Gs protein complex. Nature. 2011;477(7366):549-55.

• The

• The

• The

Chun E, Thompson AA, Liu W, Roth CB, Griffith MT, Katritch V, et al. Fusion partner toolchest for the stabilization and crystallization of G protein-coupled receptors. Structure. 2012;20(6):967-76.

• The

• The

• The

______

Focus Papers: Enzymes and Catalysis: Miller/Gross

P9)

______

P10) Jiang L, Althoff EA, Clemente FR, Doyle L, Röthlisberger D, Zanghellini A, Gallaher JL, Betker JL, Tanaka F, Barbas III CF, Hilvert D, Houk KN, Stoddard BL, Baker D. De novo computational design of retro-aldol enzymes. Science. 2008;319:1387-91.

• initial designs for catalysis – levels of success and kinetic behaviors

Lassila JK, Baker D, Herschlag D. Origins of catalysis by computationally designed retroaldolase enzymes. PNAS. 2010;107:4937-42.

•Testing designed catalytic “features” for actual contribution

• model & enzyme rate-pH profile and Bronsted analysis of rate vs pKa

• teasing out source of unexpected kinetics and how to work around

______

P11) Neal SE, Eccleston JF, Hall A, Webb MR. Kinetic Analysis of the hydrolysis of GTP by p21N-ras. J. Biol. Chem. 1988;263:19718-22.

• Ras GTPase activity is extremely low – what is rate limiting?

• single turnover methods to measure association, dissociation, hydrolysis rate constants

• pulse-chase methods to measure partitioning of intermediates

______

P12) Scheffzek K, Ahmadian MR, Kabsch W, Wiesmüller L, Lautwein A, Schmitz F, Wittinghofer A. The Ras-RasGAP complex structural basis for GTPase activation and its loss in oncogenic Ras mutants. Science. 1997;277:333-38.

• protein-protein interaction provides key residue for TS activation

Gideon P, John J, Frech M, Lautwein A, Clark R, Scheffler JE, Wittinghofer A. Mutational and kinetic analyses of the GTPase-activating protein (GAP)-p21 interaction: the C-terminal domain of GAP is not sufficient for full activity. Mol.Cell.Biol. 1992;12:2050-56.

• novel method to measure kinetics of activation of hydrolysis

• role for additional protein-protein interaction domains

______

P13) Milburn MV, Tong L, deVos AM, Brunger A, Yamaizumi Z, Nishimura S, et al. Molecular switch for signal transduction: structural differences between active and inactive forms of protooncogenic ras proteins. Science. 1990;247

Kraulis PJ, Domaille PJ, Campbell-Burk SL, Van Aken T, Laue ED. Solution structure and dynamics of ras p21.GDP determined by heteronuclear three- and four-dimensional NMR spectroscopy. Biochemistry. 1994

• GTPases are moleculer switches controlled by nucleotide state

• Conformational changes of “Switch” regions detected by crystallography provides insights into interactions of RAS with effectors

• Mobility of individual residues can be measured by NMR and provides insights into regulation of enzymes by interaction with ligands or other proteins

______

P14) Worthylake DK, Rossman KL, Sondek J. Crystal structure of Rac1 in complex with the guanine nucleotide exchange region of Tiam1. Nature. 2000;408

Aghazadeh B, Lowry WE, Huang XY, Rosen MK. Structural basis for relief of autoinhibition of the Dbl homology domain of proto-oncogene Vav by tyrosine phosphorylation. Cell. 2000;102(5):625-33.

• GEF proteins activate GTPases by promoting exchange of GDP for GTP

• The exchange reaction requires alleviation of GEF autoinhibition

• The mechanism of activation requires an order-to-disorder transition that can be followed by NMR

______

P15) Li P, Martins IR, Amarasinghe GK, Rosen MK. Internal dynamics control activation and activity of the autoinhibited Vav DH domain. Nat Struct Mol Biol. 2008;15(6):613-8.

• Proteins conformational transitions in GEF can limit rates of activation

• Transitions from major to minor populated allow post-translational modification to consolidate activated state

• NMR can be used to measure conformational excursions on pathway to activation

______

END OF COHERENT

Interaction: The C-Terminal Domain of GAP IS Not Sufficient for Full Activity

1) Kraut, J. [1988] How do enzymes work?Science242, 533-540.

• Transition state theory

• Basic kinetics

• Catalysis

• Enzyme kinetics

______

2) Fastrez, J. & Fersht, A.R. [1973] Demonstration of the acyl-enzyme mechanism for the hydrolysis of peptides and anilides by chymotrypsin. Biochemistry12, 2025-2034.

• Serine proteases

• Covalent intermediates

• Multistep processing

• Free energy vs. reaction coordinate

______

3) Abrahmsen, L., et al. [1991] Engineering subtilisin and its substrates for efficient ligation of peptide bonds in aqueous solution. Biochemistry30, 4151-4159.

• Changing the properties of enzymes

• Microscopic reversibility

• Chemical reactivity of active site groups

• Additional examples of tailored enzymes

______

4) Raines, R.T., et al. [1986] Reaction energetics of a mutant triosephosphate isomerase in which the active-site glutamate has been changed to an aspartate. Biochemistry25, 7142-7154.

• Evolutionary perfection of enzyme catalysis

• Concerted reactions

• Diffusion control

• Isotope effects

______

5) Wells, T.N.C. & Fersht, A.R. [1986] Use of binding energy in catalysis analyzed by mutagenesis of the tyrosyl-tRNA synthetase. Biochemistry25, 1881-1886.

• Specificity

• Limits of fidelity

• Proofreading mechanisms

• Binding energy in catalysis

______

1) Kraut, J. [1988] How do enzymes work?Science242, 533-540.

• Transition state theory

• Basic kinetics

• Catalysis

• Enzyme kinetics

______

2) Fastrez, J. & Fersht, A.R. [1973] Demonstration of the acyl-enzyme mechanism for the hydrolysis of peptides and anilides by chymotrypsin. Biochemistry12, 2025-2034.

• Serine proteases

• Covalent intermediates

• Multistep processing

• Free energy vs. reaction coordinate

______

3) Abrahmsen, L., et al. [1991] Engineering subtilisin and its substrates for efficient ligation of peptide bonds in aqueous solution. Biochemistry30, 4151-4159.

• Changing the properties of enzymes

• Microscopic reversibility

• Chemical reactivity of active site groups

• Additional examples of tailored enzymes

______

4) Raines, R.T., et al. [1986] Reaction energetics of a mutant triosephosphate isomerase in which the active-site glutamate has been changed to an aspartate. Biochemistry25, 7142-7154.

• Evolutionary perfection of enzyme catalysis

• Concerted reactions

• Diffusion control

• Isotope effects

______

5) Wells, T.N.C. & Fersht, A.R. [1986] Use of binding energy in catalysis analyzed by mutagenesis of the tyrosyl-tRNA synthetase. Biochemistry25, 1881-1886.

• Specificity

• Limits of fidelity

• Proofreading mechanisms

• Binding energy in catalysis

______

Focus Papers for Protein Folding: Agard

1) Eriksson AE; Baase WA; Zhang XJ; Heinz DW; Blaber M; Baldwin EP; Matthews BW. Response of a protein structure to cavity-creating mutations and its relation to the hydrophobic effect. Science 255:178-183. (1992)

• Quantitative measurement of contribution of hydrophobic effect to protein stability

• Deletions result in cavities within the protein that compact to differing degrees

• Energetics of cavity formation comparable to hydrophobic effect

• Rationalizes energetic consequences of side chain mutations-after contradictions

______

2) Riddle DS, Santiago JV, Bray-Hall ST, Doshi N, Grantcharova VP, Yi Q, Baker D Functional rapidly folding proteins from simplified amino acid sequences Nature Struct Biol 4:805-809 (1997)

• How complex a sequence “alphabet” is required to code a stable protein fold?

• Is the folding rate of small protein domains optimized through evolution?

• Use of phage display for simplifying proteins

______

3) Hughson,F.M., Wright, P.E., Baldwin, R.L. Structural characterization of a partly folded apomyoglobin intermediate Science 249:1544-1548 (1990).

• Molten globules are thought to be critical intermediates along folding pathways

• Structure of a molten globule

• Use of hydrogen exchange to study properties of folding reactions

______

4)Chamberlain AK; Handel TM; Marqusee S. Detection of rare partially folded molecules in equilibrium with the native conformation of RNaseH Nature Structure Biology 3:782-7 (1996).

• Rare conformational states are accessible from the native state

• Correlation between relative stability and folding pathways

• Domains in a structure have different stabilities

______

5)Netzer WJ, Hartl FU. Recombination of protein domains facilitated by co-translational folding in eukaryotes Nature 388:343-349 (1997)

• Comparison; protein folding machinery in prokaryotes and eukaryotes

• Fundamental differences may be adapted for folding of different kinds of proteins

______

Focus Papers: Protein-Protein Interactions: Fletterick

1) Schuster SC; Swanson RV; Alex LA; Bourret RB; Simon MI. Assembly and function of a quaternary signal transduction complex monitored by surface plasmon resonance. 1993 Nature, 365(6444):343-7.

• Measuring association and dissociation of proteins

• Role of ATP driven phosphorylation and covalent modification in complex stability

• Role of ligand binding to receptor in promoting assembly

• SPR to derive binding constants

• Quaternary signal transduction complex controls chemotaxis

______

2) Horton N; Lewis M. Calculation of the free energy of association for protein complexes. (1992) Protein Science 1(1):169-81.

• Thermodynamics of Protein Assembly

• Structural Change on complexation

• Empirical fitting of Atomic Interactions with Free Energy of Association

• Estimate of free energy of H bonds and charge interactions in protein complexes and role of hydrophobic effect

______

3) Chothia C; Lesk AM; Tramontano A; Levitt M; Smith-Gill SJ; Air G; Sheriff S; Padlan EA; Davies D; Tulip WR; et al. Conformations of immunoglobulin hypervariable regions. Nature, 1989 Dec 21-28, 342(6252):877-83.

• Definition of IgG fold

• Definition of CDR’s and their conformations

• Target sites on antigens and Fab’s

• Structural changes, characterization of interfaces

______

4) Clackson T; Ultsch MH; Wells JA; de Vos AM. Structural and functional analysis of the 1:1 growth hormone:receptor complex reveals the molecular basis for receptor affinity. Journal of Molecular Biology, 1998 Apr 17, 277(5):1111-28.

• Structure of Growth hormone with its receptor

• Mutagenesis and Affinity define important interfaces

______

5)Russo AA; Jeffrey PD; Patten AK; Massague J; Pavletich NP. Crystal structure of the p27Kip1 cyclin-dependent-kinase inhibitor bound to the cyclin A-Cdk2 complex. Nature, 1996 Jul 25, 382(6589):325-31.

• Multiple interactions build a three-protein complex

• Protein mimic of ATP

• Changes in protein structure on complex formation

______

Focus Papers: Nucleic acid-Protein Interactions: Frankel

1) Weeks, K. M. and Crothers, D. M. Major groove accessibility of RNA. 1993 Science261, 1574-1577.

• The major groove provides a prime recognition surface in nucleic acids

• RNA and DNA structures are very different

• Discontinuities in RNA helices make virtually all base pairs available for recognition

______

2) Murray, J. B., Terwey, D. P., Maloney, L., Karpeisky, A., Usman, N., Beigelman, L., and Scott, W. G. The structural basis of hammerhead ribozyme self-cleavage. 1998 Cell92, 665-673.

• RNAs adopt complex folds

• RNAs can perform chemical reactions

• Metal ions are important for structure and catalysis

• RNAs can undergo major conformational change

______

3) Sclavi, B., Sullivan, M., Chance, M. R., Brenowitz, M., and Woodson, S. A. RNA folding at millisecond intervals by synchrotron hydroxyl radical footprinting. 1998 Science279, 1940-1943.

• RNA folding is ordered but does not necessarily follow a single pathway

• Secondary structures (helices) assemble into higher order structures

• Kinetic traps are possible

• Folding time scales are similar to proteins

______

4) Rastinejad, F., Perlmann, T., Evans, R.M., and Sigler, P.B. Structural determinants of nuclear receptor assembly on DNA direct repeats. 1995 Nature375, 203-211.

• DNA-binding proteins often share common structural motifs

• The major groove, minor groove, and backbone provide specific recognition points

• Water molecules often are located at protein-nucleic acid interfaces

• Oligomeric arrangements can generate different specificities

______

5) Price, S. R., Evans, P. E., and Nagai, K. Crystal structure of the spliceosomal U2B"-U2A' protein complex bound to a fragment of U2 small nuclear RNA. 1998 Nature394, 645-650.

• RNA loops provide important recognition features

• Both RNA and protein often show induced fit upon binding

• Recognition surfaces can be remodeled to generate different specificities

______

1.

Epub 2000/09/28. PubMed PMID: 11007481.