Heterogeneous growth in a myriad of biological systems can lead to the formation of distinct morphologies during the maturation processes of different species. We demonstrate that the distinct circumferential buckling observed in pumpkins can be reproduced by a core-shell barrel structure using four-dimensional (4D) printing, taking advantage of digital light processing (DLP)-based three-dimensional (3D) printing and stimulus-responsive hydrogels. The mechanical mismatch between the stiff core and compliant shell results in buckling instability on the surface. The initiation and development of the buckling are governed by the ratio of core/shell radius, the ratio of core/shell swelling ratios, and the mismatch between the core and shell in stiffness. Furthermore, the rigid core not only acts as a source of circumferential confinement but also sets a boundary at the poles of the entire structure. The heterogeneous structures with controllable buckling geometrically and structurally behave much like plants' fruits. This replicates the biological morphologic change and elucidates the general mechanism and dynamics of the complex instability formation of heterogeneous 3D objects.

Metal patterning via additive manufacturing has been phasing-in to broad applications in many medical, electronics, aerospace, and automotive industries. While previous efforts have produced various promising metal-patterning strategies, their complexity and high cost have limited their practical application in rapid production and prototyping. Herein, a one-step gold printing technique based on anion-assisted photochemical deposition (APD), which can directly print highly conductive gold patterns (1.08 × 10⁷ S m^-1 ) under ambient conditions without post-annealing treatment, is introduced. Uniquely, the APD uses specific ion effects with projection lithography to pattern Au nanoparticles and simultaneously sinter them into tunable porous gold structures. The significant influence of kosmotropic or chaotropic anions in the precursor ink on tuning the morphologies and conductivities of the printed patterns by employing a series of different ions, including Cl^- ions, in the printing process is presented. Additionally, the resistance stabilities and the electrochemical properties of the APD-printed gold patterns are carefully investigated. The high conductivity and excellent conformability of the printed Au electrodes are demonstrated with reliable performance in electrophysiological signal delivery and acquisition for biomedical applications. This work exploits the potential of photochemical-deposition-based metal patterning in flexible electronic manufacturing.