A database of transitional direct numerical simulation (DNS) realizations of a supercritical mixing layer is analysed for understanding small-scale behaviour and examining subgrid-scale (SGS) models duplicating that behaviour. Initially, the mixing layer contains a single chemical species in each of the two streams, and a perturbation promotes roll-up and a double pairing of the four spanwise vortices initially present. The database encompasses three combinations of chemical species, several perturbation wavelengths and amplitudes, and several initial Reynolds numbers specifically chosen for the sole purpose of achieving transition. The DNS equations are the Navier-Stokes, total energy and species equations coupled to a real-gas equation of state; the fluxes of species and heat include the Soret and Dufour effects. The large-eddy simulation (LES) equations are derived from the DNS ones through filtering. Compared to the DNS equations, two types of additional terms are identified in the LES equations: SGS fluxes and other terms for which either assumptions or models are necessary. The magnitude of all terms in the LES conservation equations is analysed on the DNS database, with special attention to terms that could possibly be neglected. It is shown that in contrast to atmospheric-pressure gaseous flows, there are two new terms that must be modelled: one in each of the momentum and the energy equations. These new terms can be thought to result from the filtering of the nonlinear equation of state, and are associated with regions of high density-gradient magnitude both found in DNS and observed experimentally in fully turbulent high-pressure flows. A model is derived for the momentum-equation additional term that performs well at small filter size but deteriorates as the filter size increases, highlighting the necessity of ensuring appropriate grid resolution in LES. Modelling approaches for the energy-equation additional term are proposed, all of which may be too computationally intensive in LES. Several SGS flux models are tested on an a priori basis. The Smagorinsky (SM) model has a poor correlation with the data, while the gradient (GR) and scale-similarity (SS) models have high correlations. Calibrated model coefficients for the GR and SS models yield good agreement with the SGS fluxes, although statistically, the coefficients are not valid over all realizations. The GR model is also tested for the variances entering the calculation of the new terms in the momentum and energy equations; high correlations are obtained, although the calibrated coefficients are not statistically significant over the entire database at fixed filter size. As a manifestation of the small-scale supercritical mixing peculiarities, both scalar-dissipation visualizations and the scalar-dissipation probability density functions (PDF) are examined. The PDF is shown to exhibit minor peaks, with particular significance for those at larger scalar dissipation values than the mean, thus significantly departing from the Gaussian behaviour.