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For better understanding of soot formation and oxidation processes in diesel spray flame, the nanostructure of primary soot particles directly sampled in a diesel spray flame was investigated via High-Resolution Transmission Electron Microscopy (HRTEM). A single-shot diesel spray flame was achieved in a constant volume combustion vessel under diesel-like conditions (Ta=1000K, Pa=2.7 MPa) and a micro-grid for HRTEM observation was directly exposed to the spray flame to thermophoretically sample soot particles onto the grid surface. A preliminary nanostructure investigation was conducted for x500k magnification HRTEM images of soot particles directly sampled in diesel spray flames of Fischer-Tropsch Diesel (FTD) fuel seeded with naphthalene as a representative aromatic substance. A MATLAB code for HRTEM image processing and analysis of lattice fringes within primary soot particles was developed and used to characterize the length, tortuosity and separation of lattice fringes.