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Compares experimental branching data against theoretical predictions from different branching models to identify the most likely architecture.

Usage

measure_branching_model_comparison(
  g,
  mw,
  g_prime = NULL,
  models = c("random", "star", "comb", "hyperbranched"),
  branch_frequency = NULL
)

Arguments

g

Numeric vector of experimental g ratios (Rg^2 branched / Rg^2 linear).

mw

Numeric vector of molecular weights (same length as g).

g_prime

Optional numeric vector of g' ratios (IV branched / IV linear).

models

Character vector of models to compare. Default compares all:

  • "random": Random trifunctional branching (Zimm-Stockmayer)

  • "star": Star polymers (variable arms)

  • "comb": Comb architecture

  • "hyperbranched": Hyperbranched/dendritic

branch_frequency

For fitting: assumed constant branching frequency (branches per 1000 Da). If NULL, estimated from data.

Value

A list of class branching_model_comparison containing:

model_fits

Data frame with fit statistics for each model

best_model

Name of the best-fitting model

predictions

Data frame with predicted g for each model

experimental

Input experimental data

Details

Model Equations:

Random trifunctional (Zimm-Stockmayer): $$g = \left[\left(1 + \frac{n_b}{7}\right)^{1/2} + \frac{4n_b}{9\pi}\right]^{-1/2}$$

Star polymer (f arms): $$g = \frac{3f - 2}{f^2}$$

Comb polymer (n_b branches): $$g \approx \frac{1}{1 + 2n_b/3}$$

Hyperbranched (degree of branching DB): $$g \approx \left(\frac{1}{1 + DB \cdot n/2}\right)^{0.5}$$

Model selection uses residual sum of squares and AIC-like criteria.

References

Zimm, B.H. and Stockmayer, W.H. (1949). J. Chem. Phys., 17, 1301-1314.

Burchard, W. (1999). "Solution Properties of Branched Macromolecules." Adv. Polym. Sci., 143, 113-194.

Examples

# Compare models for branched polymer data
mw <- c(50000, 100000, 200000, 500000)
g_exp <- c(0.85, 0.72, 0.58, 0.42)

comparison <- measure_branching_model_comparison(g_exp, mw)
print(comparison)
#> Branching Model Comparison
#> ============================================================ 
#> 
#> Model Fit Summary:
#> ------------------------------------------------------------ 
#>          model  parameter r_squared       rmse       aic
#>         random 0.04648146 0.9887283 0.01699313 -17.24806
#>           star 1.11325520 0.9470407 0.03683411 -11.05914
#>           comb 0.00502421 0.9670907 0.02903611 -12.96221
#>  hyperbranched 0.09231394 0.9932768 0.01312403 -19.31498
#> ------------------------------------------------------------ 
#> 
#> Best Model: hyperbranched (lowest AIC)
#>   R-squared: 0.9933
#>   RMSE: 0.0131
#>   Parameter: 0.0923
#> 
#> Note: Lower AIC indicates better fit with penalty for complexity.
#> Consider physical plausibility when selecting the final model.