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International Journal of Bioprinting                      3D-printed thermosensitive hydrogel based microrobots




































            Figure 5. (a) SEM spectra of PNAGA-100 in helix shape. (b) SEM spectra of PNAGA-100 in five-pointed star pattern. (c) SEM spectra of PNAGA-100
            hexagonal pattern.

            3.3.2. Scanning electron microscopy                by increasing the monomer NAGA amount from 50 mg
            Figure 5 shows the scanning electron microscopy (SEM)   (PNAGA-50) to 100 mg (PNAGA-100). However,
            images of PNAGA-100 microstructures prepared by 2PP   they decreased sharply when the NAGA amount was
            method. Structure design with CAD software incorporated   further increased to 200  mg (PNAGA-200) and 300 mg
            with advanced 3D printing technology makes it possible   (PNAGA-300), indicating that NAGA concentration plays
            to obtain diverse shapes of PNAGA hydrogels with high   a vital role in modulating the thermosensitive performance
            resolution, high precision, and compact morphologies   of these materials. Noticeably, the optimized growth rate
            (Figure 5a). Helix, five-pointed star (Figure 5b), and   of PNAGA-100 was 22.5% when it was incubated in DI
            hexagonal  patterns  (Figure  5c)  of  PNAGA-100-based   water at 45°C for 12 h. PNAGA-100 reached a growth rate
            microrobots were designed and successfully 3D-printed,   of 20.8% in the shortest time (6 h), which demonstrates the
            and  their  sizes  can  be  adjusted  according  to  different   best thermosensitive performance among these hydrogels.
            application situations.                            Furthermore, it is hard to evaluate the thermosensitive
                                                               performance of PNAGA-300 after it was incubated in DI
            3.4. Thermosensitive properties of 3D-printed      water at 45°C for 24 h owing to its preference for bending
            PNAGA microstructures                              because of swelling (Figure S5).
            First, we prepared PNAGA microstructures with different
            NAGA loadings via the 2PP method to estimate the      Although we lack a comprehensive theory to explain
            thermosensitive properties of materials (Table 1). As shown   why  PNAGA-100 exhibits better thermosensitive
            in Figure 6, the thermosensitive properties of these hydrogels   performance  than  others,  we  rationalized  this  by  the
            were evaluated with different duration times (6 h; 12 h;   variations of PNAGA polymer structures induced by
            24 h) at room temperature (25°C) and 45°C, respectively.   NAGA monomer concentrations. In detail, PNAGA has
            The growth rates of these hydrogels were measured for the   dual H-bonding donors (D) and dual H-bonding acceptors
            sake of evaluating their swelling performance. In detail, the   (A), which feature an ADAD hydrogen network (Figure 7).
            growth rates of these hydrogels were much higher at 45°C   Based on the NAGA concentrations, the phase diagrams
                                                                                                     [44]
            (close to body temperature) than that at 25°C, revealing   of PNAGA are mainly divided into two regions . Region
            that all these PNAGA-based microrobots exhibit better   1 has medium NAGA concentration, and swellable and
            thermosensitive performance under 45°C. In addition,   thermosensitive hydrogels are observed with a gel-like
            the growth rates of these microstructures were enhanced   behavior in this region. PNAGA-100 with higher NAGA

            Volume 9 Issue 3 (2023)                        277                         https://doi.org/10.18063/ijb.709
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