Solvent switchable nanostructures and the function of a π-amphiphile

Abstract

This manuscript reports solvent tunable functional nano-assemblies of an unsymmetrical bola-shaped π-amphiphile (NDI-PY) which consists of a hydrophobic naphthalene-diimide (NDI) chromophore connected to a non-ionic hydrophilic wedge and a pyridine group at its two opposite arms. Importantly, it contains a hydrazide group located at the hydrophobic domain between the NDI-chromophore and the hydrophilic-wedge to drive the supramolecular assembly by directional H-bonding. NDI-PY exhibits spontaneous assembly in water as well as in a highly non-polar solvent like tetra-chloroethylene (TCE) by the synergistic effect of H-bonding and π-stacking interaction. Spectroscopy studies reveal almost identical self-assembly features in water and TCE with critical aggregation concentrations in the range of 0.3 mM, which matches the values obtained from the isothermal calorimetry (ITC) dilution experiment. Differential scanning calorimetry (DSC) experiments reveal a single endothermic peak at 31 °C (ΔH = −12.3 kJ mol⁻¹) and 40 °C (ΔH = −5.35 kJ mol⁻¹) for water and TCE, respectively, indicating marginally higher thermal stability in TCE, which is consistent with the FT-IR data, suggesting stronger H-bonding in TCE. Although the molecular assembly features appear to be similar, NDI-PY produces distinctly different mesoscopic structures in water and TCE. In water, it forms vesicles (D_h = 150–180 nm) with the pyridine groups displayed at the outer surface, while in TCE it generates a transparent gel (CGC = 8.0 mM) with a nanotubular (width ∼50 nm, wall thickness ∼10 nm) morphology. Powder X-ray diffraction studies show clearly different packing structures; in water a single sharp peak at the low angle (d = 19.3 Å, a little shorter than the extended length of the molecule) suggests the formation of a monolayer membrane, while in TCE several sharp peaks appear with the d values maintaining a ratio of 1 : 1/√3 : 1/2 : 1/√7 : 1/3 : 1/√12, indicating the formation of a 2D hexagonal lattice. Photoconductivity measurements reveal moderate electronic conduction in both cases. However, it shows a remarkable enhancement of the life time of the charge-carriers for the nanotubular structure compared to the vesicular morphology. On the other hand, the vesicles in water display antimicrobial activity against Gram-positive S. aureus with a highly promising MIC_LB value of 29.4 μg mL⁻¹. In contrast, it does not lyse human red blood cells even at as high a concentration as 2.5 mg mL⁻¹ (HC₅₀ > 2.5 mg mL⁻¹), implying high selectivity of the NDI-PY vesicles towards bacterial cells over mammalian cells. Display of the pyridine groups at the outer surface of the membrane enables molecular recognition by complementary H-bonding with a carboxylic acid group and thereby facilitates uptake of the attached pyrene chromophores in the NDI-membrane by charge-transfer interaction between the NDI acceptor and the pyrene donor. In fact a Job's plot experiment reveals maximum uptake at a 1 : 1 ratio of the NDI-PY and the pyrene guest, indicating all the pyridine groups are accessible at the vesicular surface.