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The breath figure (BF) method is a handy strategy to prepare porous films. Linear shape memory polyurethanes (SMPUs) are among the most promising polymers for bone repair or regeneration. However, little attention has been paid to the fabrication of SMPU films by using the BF method. In this work, an amorphous SMPU containing isosorbide (ISO) in the long‐chain hard segments (ISO2‐PU) is fabricated into honeycomb porous films. Strikingly, a peculiar crystalline structure with a "Z" configuration and highly regional orientation is formed on the hexagonal holes of the porous films, which results in significantly enhanced mechanical properties. Moreover, the ISO2‐PU honeycomb porous films can markedly accelerate the osteogenic differentiation of rat mesenchymal stem cells, indicating that the porous films have great potentials as bone repair materials. It is further speculated that the Marangoni effect in the condensed water droplets and the molecular assembly of ISO2‐PU due to the strong hydrogen bonds and the chiral center effect of ISO are key contributors. This work, to the best of authors' knowledge, is the first time that this special crystalline structure on BF‐based porous films is observed and also the first speculation that combines Marangoni effect with the microstructure of BF‐based porous films. [ABSTRACT FROM AUTHOR]

Linear shape memory polyurethanes based on poly(dl‐lactic acid) (PDLLA) macrodiol (PDLLA‐SMPUs) have various advantages such as good processability, biodegradability, shape memory effect, and biocompatibility, yet the insufficient mechanical properties prevent their effective applications in bone repair. 2‐Ureido‐4[1H]‐pyrimidone (UPy) can form strong quadruple hydrogen bonding. Here, a new linear PDLLA‐SMPU containing pendant UPy units (UPy‐p‐PDLLA‐SMPU) is designed and synthesized. The pendant UPy units may dimerize to form physical crosslinking among UPy‐p‐PDLLA‐SMPU chains. As a result, UPy‐p‐PDLLA‐SMPU demonstrates both good processability and significantly higher mechanical properties than the corresponding linear PDLLA‐SMPU without pendant UPys. In addition, UPy‐p‐PDLLA‐SMPU shows excellent shape memory effect near body temperature, with a shape fixity ratio of up to 98.6% and a recovery ratio of up to 92.9%. This work provides a new strategy to design SMPUs integrating the merits of linear and crosslinked polyurethanes, and the obtained UPy‐p‐PDLLA‐SMPU is a promising material for bone tissue repair in view of the mechanical, thermal, and shape memory properties. [ABSTRACT FROM AUTHOR]

Linear polyurethanes based on poly(dl‐lactic acid) (PDLLA) macrodiol are promising materials in tissue engineering, yet their synthesis requires rigorous control on various parameters. A facile way to prepare linear polyurethanes by capping the PDLLA macrodiol (Mn = 4536) with 2‐ureido‐4[1H]‐pyrimidone (UPy) is reported. The obtained low‐molecular‐weight UPy‐capped polyurethane can form flexible, stretchable, and hydrophobic supramolecular films due to the strong and unidirectional quadruple hydrogen bonding of UPy dimers. Tensile tests, shape recovery, and self‐healing observations indicate that, compared with conventional PDLLA macrodiol‐based linear polyurethane (Mn = 48840 and PDI = 1.8), the UPy‐capped polyurethane films have comparable mechanical properties (tensile modulus: 900 ± 38 MPa; ultimate strength: 9.6 ± 0.8 MPa) yet significantly better shape memory and self‐healing properties. These results suggest that the UPy‐capped polyurethane might become an alternative for conventional linear polyurethane as a new biomedical material. A facile way to prepare linear polyurethanes is introduced by capping macrodiol with UPy units. The obtained low‐molecular‐weight polyurethane can form flexible and hydrophobic supramolecular films and demonstrates comparable mechanical properties yet significantly better shape memory and self‐healing properties than the conventional high‐molecular‐weight linear polyurethane. [ABSTRACT FROM AUTHOR]