The review synthesizes the statistical-mechanical model of the DNA helix-coil transitionβincluding heterogeneous nearest-neighbor stacking, loop entropy, and strand dissociationβand tests it against new differential melting curves (DMCs) of seven pBR322 fragments (154-587 bp) plus eight lac fragments, measured at 268 nm in 0.105 M Na+ .
Agreement is excellent for 14/15 fragments (ΞTm β€ 0.6Β°C, comparable to the Β±0.3Β°C experimental SD); the sole outlier is the 516 bp fragment, whose three observed peaks the model cannot reproduceβrationally attributed to three inverted-repeat stem-loop structures excluded from the theory, independently corroborated by Lilley's finding that these are the only pBR322 sites induced into stem-loops by negative supercoiling .
Strengths: (1) The authors show that least-squares fits of stacking parameters (Ξ΄G_MN) are non-uniqueβtwo different parameter sets both fit 17 Tm values within Β±0.82Β°C, and the popular Gotoh-Tagashira parameters badly fail on short DNAs in 0.1 M Na+ (Tm off by ~3Β°C) . (2) It flags non-equilibrium artifacts: melting in 0.02 M Na+ (0.1 SSC) shows hysteresis, with Anshelevich et al. estimating kinetic shifts of ~0.2Β°Cβundermining interpretation of earlier long-DNA theory-experiment fits .
Weaknesses/blind spots: fitted dissociation parameters (K=5000, aβ-2.7 to -3.2) are admittedly arbitrary and not unique; the small-stacking-heterogeneity conclusion rests on only 18 DNAs; and the fluctuational-opening section concedes a 10Β²-10Β³ discrepancy between helix-coil theory and formaldehyde-exchange experiments left unresolved . A later coarse-grained model predicted Tm within ~0.6 K at 50 mM Na+ but persistence lengths off ~2Γ, showing the parameterization problem persists .
A landmark, self-critical review that set the standard for rigorous theory-experiment testing in DNA biophysics, correctly diagnosing non-equilibrium artifacts and secondary-structure confounds, and anticipating denaturing-gradient-gel mutation screening (Lerman/Fischer) . What would change this verdict: systematic fits showing large non-zero Ξ΄G_MN values reproduce short-DNA curves in high salt, or an alternative explanation of the 516 bp anomaly.
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