Polyimides (PIs) represent a benchmark for high-performance polymers on the basis of a remarkable collection of valuable traits and accessible production pathways and therefore have incited serious attention from the ever-demanding medical field. Their characteristics make them suitable for service in hostile environments and purification or sterilization by robust methods, as requested by most biomedical applications. Even if PIs are generally regarded as “biocompatible”, proper analysis and understanding of their biocompatibility and safe use in biological systems deeply needed. This mini-review is designed to encompass some of the most robust available research on the biocompatibility of various commercial or noncommercial PIs and to comprehend their potential in the biomedical area. Therefore, it considers (i) the newest concepts in the field, (ii) the chemical, (iii) physical, or (iv) manufacturing elements of PIs that could affect the subsequent biocompatibility, and, last but not least, (v) in vitro and in vivo biocompatibility assessment and (vi) reachable clinical trials involving defined polyimide structures. The main conclusion is that various PIs have the capacity to accommodate in vivo conditions in which they are able to function for a long time and can be judiciously certified as biocompatible.

Aromatic polyimides containing side azo-naphthalene groups have been investigated regarding their capacity of generating surface relief gratings (SRGs) under pulsed UV laser irradiation through phase masks, using different fluencies and pulse numbers. The process of the material photo-fluidization and the supramolecular re-organization of the surface were investigated using atomic force microscopy (AFM). At first, an AFM nanoscale topographical analysis of the induced SRGs was performed in terms of morphology and tridimensional amplitude, spatial, hybrid, and functional parameters. Afterward, a nanomechanical characterization of SRGs using an advanced method, namely, AFM PinPoint mode, was performed, where the quantitative nanomechanical properties (i.e., modulus, adhesion, deformation) of the nanostructured azo-polyimide surfaces were acquired with a highly correlated topographic registration. This method proved to be very effective in understanding the formation mechanism of the surface modulations during pulsed UV laser irradiation. Additionally to AFM investigations, confocal Raman measurements and molecular simulations were performed to provide information about structured azo-polyimide chemical composition and macromolecular conformation induced by laser irradiation.