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Record W2331819284 · doi:10.1021/ar200285h

Single Polymer Studies of Hydrophobic Hydration

2012· article· en· W2331819284 on OpenAlex

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.

Bibliographic record

VenueAccounts of Chemical Research · 2012
Typearticle
Languageen
FieldBiochemistry, Genetics and Molecular Biology
TopicProtein Structure and Dynamics
Canadian institutionsUniversity of Toronto
Fundersnot available
KeywordsHydrophobic effectPolymerChemical physicsFolding (DSP implementation)MacromoleculeForce spectroscopyChemistryHydrophobeMoleculeLength scaleLattice proteinSolvationInteraction energyProtein foldingOrganic chemistry

Abstract

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Hydrophobic interactions guide protein folding, multidomain protein assembly, receptor-ligand binding, membrane formation, and cellular transportation. On the macroscale, hydrophobic interactions consist of the aggregation of "oil-like" objects in water by minimizing the interfacial energy. However, studies of the hydration behavior of small hydrophobic molecules have shown that the microscopic (~1 nm) hydration mechanism differs fundamentally from its macroscopic counterpart. Theoretical studies over the last two decades have pointed to an intricate dependence of molecular hydration mechanisms on the length scale. The microscopic-to-macroscopic crossover length scale is critically important to hydrophobic interactions in polymers, proteins, and other macromolecules. Accurate experimental determination of hydration mechanisms and interaction strengths directly influence our understanding of protein folding. In this Account, we discuss our recent measurements of the hydration energies of single hydrophobic homopolymers as they unfold. We describe in detail our single molecule force spectroscopy technique, the interpretation of the single polymer force curve, and how it relates to the hydration free energy of a hydrophobic polymer. Specifically, we show how temperature, side-chain sizes and solvent conditions, affect the driving force of hydrophobic collapse. The experiments reveal that the size of the nonpolar polymer side-chains changes the thermal signatures of hydration. The sizes of the polymer side-chains bridge the length scale where theories had predicted a transition between entropically driven microscopic hydration and enthalpically driven macroscopic hydrophobic hydration. Our experimental results revealed a crossover length scale of approximately 1 nm, similar to the results from recent theoretical studies. Experiments that probe solvent dependency show that the microscopic polymer hydration is correlated with macroscopic interfacial tension. Consistent with theoretical predictions, the solvent conditions affect the microscopic and macroscopic hydrophobic strengths in similar ways. Although the extended polymers and proteins span hundreds of nanometers, the experiments show that their hydration behavior is determined by the size of a single hydrophobic monomer. As the hydrophobic particle size decreases from the macroscopic to the microscopic regime, the scaling relationship changes from a dependence on interfacial area to a dependence on volume. Therefore, under these conditions, the driving force for the aggregation of hydrophobic molecules is reduced, which has significant implications for the strength of hydrophobic interactions in molecular systems, particularly in protein folding.

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Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.007
Threshold uncertainty score0.249

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.059
GPT teacher head0.387
Teacher spread0.328 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it