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Ariel Fernández

Publications and source records attributed to Ariel Fernández.

At least 19 recordsLinked to original sources

Feature-similarity protein classifier as a ligand engineering tool.

Kinases have been often targeted in drug therapy aimed at blocking signaling pathways. However, the conservation of protein structure across homologs often leads to uncontrolled cross-reactivity. On the other hand, sticky packing defects in proteins are typically not conserved across homologs, making them ligand-anchoring sites potentially important to enhance selectivity. Thus, we introduce a hierarchical clustering of PDB-reported kinases according to packing differences. This kinome partitioning is highly correlated with proximity relations arising from the pharmacological profiling of kinases. A variable packing sensitivity is observed for individual drugs, with highly promiscuous ligands being the most insensitive to packing differences. Our classifier enables a strategy to design selective inhibitors.

Computer Simulation↗

Packing defects as selectivity switches for drug-based protein inhibitors.

The conservation of structure across homolog proteins often diffuses the impact of drug-based inhibition by promoting alternative protein-ligand associations that may lead to toxic side effects. However, sticky packing defects are typically not conserved across homologs, making them valuable a priori targets to enhance specificity. By introducing a homology to quantify packing differences among proteins, we enable a previously undescribed strategy for the design of highly selective drug inhibitors involving ligands that wrap nonconserved packing defects. The selectivity of these ligands is validated by performing affinity assays on a cancer-related pharmacokinome. Minor reengineering of a powerful inhibitor guided by wrapping differences across its target kinome can selectively direct its impact toward a specific kinase. Thus, nonconserved packing defects may be used as selectivity switches across homolog targets, using spatial displacements of packing defects across aligned protein structures.

Drug Design↗

What factor drives the fibrillogenic association of beta-sheets?

The identification of the driving factor for fibril formation is paramount to understand the molecular basis of amyloidogenic disease. Recently, an atomic-detail structure of a fibrillogenic aggregate was reported and revealed a tight packing of beta-sheets. However, there is not a single pair-wise interaction of significance between the beta-sheets, no hydrogen bond and no hydrophobic interaction. Instead, there is extensive burial of polar groups at the interface. These observations lead to the question: What factor drives the association of beta-sheets? This issue is addressed by combining all-atom molecular dynamics with an implicit-solvent analysis. The driving force for the association arises from the mechanical equivalent of the dehydration propensity of pre-formed intra-sheet hydrogen bonds and dipole-dipole interactions.

Amyloid↗

The integrated development of network complexity modulates the diverse evolutionary mutation rates of individual proteins.

The rate of evolution-related mutation varies widely among proteins while the unity of the organism implies an integrated evolution of its protein network. Focusing on the yeast interactome, we monitored the structural impact of amino acid substitution on yeast proteins with reported structure. The impact of mutation in creating or deleting structural markers for interactivity varies across proteins and modulates the evolutionary rates, yielding a unified kinetic law of accumulation of connectivities consistent with an integrated evolution of the interactome.

Amino Acid Substitution↗

Incomplete protein packing as a selectivity filter in drug design.

The conservation of structure across paralog proteins promotes alternative protein-ligand associations often leading to side effects in drug-based inhibition. However, sticky packing defects are typically not conserved across paralogs, making them suitable targets to reduce drug toxicity. This observation enables a strategy for the design of highly specific inhibitors involving ligands that wrap nonconserved packing defects. The selectivity of these inhibitors is evidenced in affinity assays on a cancer-related pharmacokinome: a powerful inhibitor is redesigned by using the wrapping technology to enhance its selectivity and affinity for a target kinase. In this way, the packing defects of a soluble protein may be used as selectivity filters for drug design.

Antineoplastic Agents↗

Protein promiscuity: drug resistance and native functions--HIV-1 case.

The association of a drug with its target protein has the effect of blocking the protein activity and is termed a promiscuous function to distinguish from the protein's native function (Tawfik and associates, Nat. Genet. 37, 73-6, 2005). Obviously, a protein has not evolved naturally for drug association or drug resistance. Promiscuous protein functions exhibit unique traits of evolutionary adaptability, or evolvability, which is dependent on the induction of novel phenotypic traits by a small number of mutations. These mutations might have small effects on native functions, but large effects on promiscuous function; for example, an evolving protein could become increasingly drug resistant while maintaining its original function. Ariel Fernandez, in his opinion piece, notes that drug-binding "promiscuity" can hardly be dissociated from native functions; a dominant approach to drug discovery is the protein-native-substrate transition-state mimetic strategy. Thus, man-made ligands (e.g. drugs) have been successfully crafted to restrain enzymatic activity by focusing on the very same structural features that determine the native function. Using the successful inhibition of HIV-1 protease as an example, Fernandez illustrates how drug designers have employed naturally evolved features of the protein to suppress its activity. Based on these arguments, he dismisses the notion that drug binding is quintessentially promiscuous, even though in principle, proteins did not evolve to associate with man made ligands. In short, Fernandez argues that there may not be separate protein domains that one could term promiscuous domains. While acknowledging that drugs may bind promiscuously or in a native-like manner a la Fernandez, Tawfik maintains the role of evolutionary adaptation, even when a drug binds native-like. In the case of HIV-1 protease, drugs bind natively, and the initial onset of mutations results in drug resistance in addition to a dramatic decline in enzymatic activity and fitness of the virus. A chain of compensatory mutations follows this, and then the virus becomes fully fit and drug resistant. Ben Berkhout and Rogier Sanders subscribe to the evolution of new protein functions through gene duplication. With two identical protein domains, one domain can be released from a constraint imposed by the original function and it is thus free to move in sequence space toward a new function without loss of the original function. They emphasize that the forced evolution of drug-resistance differs significantly from the spontaneous evolution of an additional protein function. For instance, the latter process could proceed gradually on an evolutionary time scale, whereas the acquisition of drug-resistance is an all or nothing process for a virus, leading to the failure or success of therapy. They find no evidence to the thesis that resistance-mutations appear more rapidly in promiscuous domains than native domains. Berkhout and Sanders illustrate the genetic plasticity of HIV-1 by citing examples in which well-conserved amino acid residues of catalytic domains are forced to mutate under drug-pressure. HIV drug resistance biology is very complex. Instead of a viral protein, a drug can be targeted at a cellular protein. For example, Berkhout and Sanders claim, a drug targeted at the cellular protein CCR5 inhibits the binding of the viral envelope glycoprotein (Env) to CCR5. However, Env mutates so that it binds to the CCR5-drug complex and develops drug resistance. Interestingly, CCR5 has not evolved to bind to Env, but to a series of chemokines. Andrzej Kloczkowski, Taner Sen, and Bob Jernigan point out the importance of protein motions for binding. They believe it is likely that different ligands can bind to the diverse protein conformations sampled in the course of normal protein conformational fluctuations. They have been applying simple elastic network models to extract the motions as normal modes, which yield relatively small numbers of conformations that are useful for developing protein mechanisms; while these are typically small motions, for some proteins they can be quite large in scale. One of the major advantages of the approach is that only relatively small numbers of modes are important contributors to the overall motion -- so the approach provides a way to systematically map out a protein's motions. These models successfully represent the conformational fluctuations manifested in the crystallographic B-factors, and often suggest motions related to protein functional behaviors, such as those observed for reverse transcriptase, where two dominant hinges clearly relate to the processing steps -- one showing anti-correlation between the polymerase and ribonuclease H sites related to the translation and positioning of the nucleic acid chain, and another for opening and closing the polymerase site. Disordered proteins represent a more extreme case where the set of accessible conformations is much larger; thus they could offer up a broader range of possible binding forms. Whether evolution controls the functional motions for proteins remains little studied. Intriguingly, buried in the existing databases of protein-protein interactions may be information that can shed light on the extent of promiscuous binding among proteins themselves. Within these data there are cases where large numbers of diverse proteins have been shown to interact with a single protein; some of these could represent promiscuous protein-protein binding. Uncovering these promiscuous behaviors could be important for comprehending the details of how proteins can bind promiscuously to one another, and can exhibit even greater promiscuity in their binding to small molecules. The evolutionary routes, the dynamics of the target protein, and the many other aspects that need to be addressed while designing a drug that may dodge drug resistance, indicate the complexity and multi-disciplinary nature of the issue of drug resistance.

Adaptation, Physiological↗

Buffering the entropic cost of hydrophobic collapse in protein chains.

Direct inspection of high-resolution protein structures reveals that backbone dehydration promotes extra conformational freedom in the peptide bond, especially when the residue is not involved in secondary structure. The results imply a buffering effect that lowers the entropic cost of hydrophobic collapse. (c) 2004 American Institute of Physics.

Biophysics↗

Dielectric modulation of biological water.

We show that water constrained by vicinal hydrophobes undergoes a librational dynamics that lowers the dielectric susceptibility and induces a "redshift" of the relaxation frequency in the hydration shell. The results shed light on the way proteins enhance their intramolecular interactions as they fold or associate.

Body Water↗

Molecular dimension explored in evolution to promote proteomic complexity.

The architecture of present-day protein interaction networks depends on how protein associations evolved. Here, we explore how and why evolution-related mutations influence protein structure to promote protein associations, and thereby network development. We specifically address two questions: (i) How can protein folds remain conserved while proteins accommodate new binding partnerships as genes duplicate? (ii) What is the structural/molecular basis for hub proteins being the most likely to acquire new connections? The answers stem from the examination of the structure wrapping, or protection from water attack. Wrapping is shown to be a crucial consideration in the exploration and evolution of proteomic interactivity.

Evolution, Molecular↗

Inhibitor design by wrapping packing defects in HIV-1 proteins.

Two viral proteins, HIV-1 protease and HIV-1 integrase, have been targeted for inhibitor design to prevent assembly and maturation of HIV-1 virions. The enzymatic mechanism of these proteins involves side-chain groups that serve as general acids or bases. Furthermore, catalytic activity requires that water be removed from the microenvironment surrounding the chemical reaction site or be constrained to serve as an activated nucleophile. Here, we identify previously unrecognized structural features that promote water removal from polar catalytic regions. Packing defects in the form of hydrogen bonds that are insufficiently dehydrated intramolecularly, named "dehydrons," are strategically placed in the structure to induce an anhydrous enzymatic pathway. Dehydrons become electrostatically enhanced and stabilized upon further desolvation. Thus, packing defects act synergistically with the polar active groups to enhance the enzymatic electrostatics. However, because dehydrons are sticky, they constitute targets for inhibitor design. We noticed that inhibitors attach to polar surfaces by further desolvating dehydrons, thus blocking the active sites or the sites involved in harnessing the substrate. The dehydrons are thus required for functional reasons, making them suitable targets. The differences in success when targeting HIV-1 protease, feline immunodeficiency virus protease, and HIV-1 integrase are rationalized in terms of the dehydron distribution, revealing possible improvements in the targeting strategy. Principles of design optimization are proposed to create an inhibitor that can be neutralized only at the expense of the loss of catalytic function. The possibility of using drugs that wrap dehydrons to block protein-protein associations is also discussed.

Catalytic Domain↗

Functionality of wrapping defects in soluble proteins: what cannot be kept dry must be conserved.

Soluble proteins preserve their structure only if a sufficient number of non-polar groups are clustered around the backbone hydrogen bonds, protecting them from water attack. When these bonds are not properly wrapped or dehydrated intramolecularly, structural integrity can be preserved through binding partnerships. This is because insufficiently wrapped hydrogen bonds are inherently adhesive and become better shielded upon protein-ligand association. Thus, we postulate that deficiently wrapped hydrogen bonds are functionally relevant. Two findings that support this conjecture are: (a) there is a statistically relevant linear correlation between the number of defects in a folding domain and its proteomic connectivity, obtained from large-scale two-hybrid experiments; (b) the residues paired by under-wrapped hydrogen bonds are highly conserved. The high mutational sensitivity of under-wrapped regions can be rationalized, since their structural integrity relies on their propensity to behave as binding sites, in turn, a consequence of their adhesiveness. Thus, the regions in soluble protein structure that cannot be kept dry in water tend to be conserved.

Acyl Carrier Protein↗

The nonconserved wrapping of conserved protein folds reveals a trend toward increasing connectivity in proteomic networks.

Although protein folding domains are generally conserved for function across distant homologous sequences, one crucial structural feature is not conserved: the wrapping of backbone hydrogen bonds, that is, the extent to which they are intramolecularly desolvated and thereby protected from water attack. Extensive data on protein complex interfaces led us to postulate that insufficiently wrapped backbone hydrogen bonds in monomeric domains must be adhesive, and therefore determinants of interactivity, a result that has been experimentally confirmed. Here, we show that the wrapping of certain conserved folds becomes progressively poorer as species diverge in some lineages. This trend is thus concurrent with a progressive enhancement of the interactivity of individual domains sharing the conserved fold. Such increase in interactivity is predicted to impose an "evolutionary brake" on the overall speed of sequence divergence. This phenomenon follows when more and more residues become engaged in protein associations and thus become functionally indispensable. For complete proteomes for which statistically significant structural data are available, scale-free network statistics based solely on the distribution of folding domains, catalogued by their number of wrapping defects, best describe the proteomic connectivity. Thus, the intermolecular connectivity may be effectively used as a measure of species complexity. Our results might contribute to explaining how interactome complexity may be achieved without a dramatic increase in genome size.

Animals↗

Adherence of packing defects in soluble proteins.

For protein structure to prevail in water, its backbone hydrogen bonds must be shielded from water attack, requiring a cluster of "wrapping" nonpolar groups. Thus, underwrapped regions are adhesive, as exogenous removal of surrounding water becomes thermodynamically favorable. Here we measure the average adhesive force exerted by an underwrapped hydrogen bond on a test hydrophobe and thus define a new interactivity constant.

Apoproteins↗

Structural defects and the diagnosis of amyloidogenic propensity.

Disease-related amyloidogenic propensity has been unexpectedly found in proteins driven to adopt a monomeric uncomplexed state at high concentrations under near-physiological conditions. This situation occasionally arises in new health treatments, such as kidney dialysis. Assuming that under such conditions a partial retention of native structure takes place, this work identifies a structural characteristic indicating amyloidogenic propensity: a high density of backbone hydrogen bonds exposed to water attack in monomeric structure. On this basis, we propose a diagnostic tool based on the identification of hydrogen bonds with a paucity of intramolecular dehydration or "wrapping." We use this predictor to identify potentially pathogenic mutations that foster amyloidogenic propensity in human prions. Such mutations either enhance the intramolecular dehydration of beta-sheet hydrogen bonds, thus stabilizing the nucleus for rearrangement into the scrapie fold, or contribute to the destabilization of the cellular form by introducing additional underwrapped hydrogen bonds. Our predictions are consistent with known disease-related mutations and lead to a cogent explanation of the pathogenic nature of specific mutations affecting the cellular prion protein structural wrapping. On the other hand, a different wrapping of a very similar fold, mouse doppel, induces a dramatically different level of amyloidogenic propensity, suggesting that the packing within the fold, and not the fold itself, contains the signal for aggregation.

Amyloid↗

Proteins with H-bond packing defects are highly interactive with lipid bilayers: Implications for amyloidogenesis.

We noticed that disease-related amyloidogenic proteins and especially cellular prion proteins have the highest proportion of incompletely desolvated backbone H bonds among soluble proteins. Such bonds are vulnerable to water attack and thus represent structural weaknesses. We have measured the adsorption of proteins onto phospholipid bilayers and found a strong correlation between the extent of underwrapping of backbone H bonds in the native structure of a protein and its extent of deposition on the bilayer: the less the H bond wrapping, the higher the propensity for protein-bilayer binding. These observations support the proposition that soluble proteins with amyloidogenic propensity and membrane proteins share a pervasive building motif: the underwrapped H bonds. Whereas in membrane proteins, this motif does not signal a structural vulnerability, in soluble proteins, it is responsible for their reactivity.

Adsorption↗

Protein folding: could hydrophobic collapse be coupled with hydrogen-bond formation?

A judicious examination of an exhaustive PDB sample of soluble globular proteins of moderate size (N<102) reveals a commensurable relationship between hydrophobic surface burial and number of backbone hydrogen bonds. An analysis of 50,000 conformations along the longest all-atom MD trajectory allows us to infer that not only the hydrophobic collapse is concurrent with the formation of backbone amide-carbonyl hydrogen bonds, they are also dynamically coupled processes. In statistical terms, hydrophobic clustering of the side chains is inevitably conducive to backbone burial and the latter process becomes thermodynamically too costly and kinetically unfeasible without amide-carbonyl hydrogen-bond formation. Furthermore, the desolvation of most hydrogen bonds is exhaustive along the pathway, implying that such bonds guide the collapse process.

Animals↗

Large-scale context in protein folding: villin headpiece.

The villin headpiece folds autonomously in vitro forming three alpha-helical regions. Local propensities, however, strongly disfavor the formation of the C-terminal helix because most native residue pairs in that helix are hydrophobic/polar mismatches. Even the N-terminal helix is unfavored according to the AGADIR criterion. Our coarse-grained ab initio simulations reveal three-body correlations in which hydrophobic residues position to protect amide-carbonyl hydrogen bonds from attack by water, thus inducing the growth of the C-terminal helix and guiding the folding process. Similar correlations are also found in all-atom simulations with an implicit solvent model that accurately reproduces the results of simulations with explicit solvent molecules. The correlations establish a large-scale, many-body context that may be probed experimentally by introducing mutations of certain nonobvious residues that reside outside the native hydrophobic core but that are predicted to affect the folding rates and dynamics dramatically.

Alanine↗