Highly Elastic, Bioresorbable Polymeric Materials for Stretchable, Transient Electronic Systems

doi:10.1007/s40820-023-01268-2

Abstract

Abstract:

Substrates or encapsulants in soft and stretchable formats are key components for transient, bioresorbable electronic systems; however, elastomeric polymers with desired mechanical and biochemical properties are very limited compared to non-transient counterparts. Here, we introduce a bioresorbable elastomer, poly(glycolide-co-ε-caprolactone) (PGCL), that contains excellent material properties including high elongation-at-break (< 1300%), resilience and toughness, and tunable dissolution behaviors. Exploitation of PGCLs as polymer matrices, in combination with conducing polymers, yields stretchable, conductive composites for degradable interconnects, sensors, and actuators, which can reliably function under external strains. Integration of device components with wireless modules demonstrates elastic, transient electronic suture system with on-demand drug delivery for rapid recovery of post-surgical wounds in soft, time-dynamic tissues.

Key words: Biodegradable elastomer, Conductive polymer composites, Biomedical device, Transient electronics

Jeong-Woong Shin, Dong-Je Kim, Tae-Min Jang, Won Bae Han, Joong Hoon Lee, Gwan-Jin Ko, Seung Min Yang, Kaveti Rajaram, Sungkeun Han, Heeseok Kang, Jun Hyeon Lim, Chan-Hwi Eom, Amay J. Bandodkar, Hanul Min, Suk-Won Hwang. Highly Elastic, Bioresorbable Polymeric Materials for Stretchable, Transient Electronic Systems[J]. Nano-Micro Letters, 2024, 16(1): 102-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-023-01268-2

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/102

Figures/Tables 4

Fig. 1 Stretchable, biodegradable elastomeric polymer. a Chemical structure of stretchable and biodegradable elastomer, poly (glycolide-co-ε-caprolactone) (PGCL). The copolymer consists of glycolide as a hard, cross-linker segment and ε-caprolactone as a soft, elastic domain (top). Extreme stretchability up to ~800% of a PGCL film (150 μm thick), with an image at the initial state (bottom). b A set of images showing superior elasticity through a wide range of areal strains (~2500%) using inflation of PGCL balloons combined with light-emitting diodes (LEDs). c Time-sequential degradation images of a PGCL substrate (thickness: 250 μm) in phosphate buffer saline (PBS, pH 7) solution at body temperature (37 °C) during 12 weeks

Fig. 2 Comprehensive characteristics of PGCL polymers with different compositions. a Measured wettability of different PGCL polymers using deionized (DI) water droplets (2 μL). b Dissolution behaviors via hydrolysis and c changes in tensile strength with immersion time of the polymers in PBS solution (pH 7) at 37 °C. d Resistance profiles of Mg electrodes (thickness: 1 μm) encapsulated with a layer of stretchable PGCL (~ 400 μm), layers of and PGCL/Si₃N₄ (Si₃N₄ thickness, 300 nm), upon contact with PBS solution at room temperature (RT). e Stress-strain curves of PGCL films (150 μm) with different compositions (black, 70:30; red, 55:45; and blue, 15:85). f Mechanical properties of the copolymers depending on the ratio of glycolide (GA) and caprolactone (CL). g Changes in a mechanical behavior of PGCL films (thickness: 150 μm) under cyclic stretching tests at 40% strain. h Comparison of mechanical performances with previously reported biodegradable elastomeric materials [33,34,35,36,54,56,57]

Fig. 3 Degradable conductive elastomer. a Schematic illustration of an elastomeric conductive composite with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a conductor and D-sorbitol as an additive, with mechanisms of the modified structure in the inset. b Measurements of electrical and mechanical properties in various mixture ratios of PGCL and PEDOT:PSS at a constant concentration of D-sorbitol (2 w/w% of PEDOT:PSS). c Stable operation of the conductive composite connected with a blue LED, under external deformation modes, bending (top right), stretching (bottom left), and twisting (bottom right). d Measured light intensity of the blue LEDs during cyclic tests at a tensile strain of 50%, with the result of the first attempt in the inset. e Thread-like elastomeric heater, with infrared (IR) image of the device at an applied voltage of 1.5 V. f Temperature profiles of the heater at an applied voltage of 1-2 V. g Steady Joule heating performances of the elastic heater with stretching up to 50%

Fig. 4 Transient electronic suture system. a Illustration of a medical, electronic, and degradable suture (MED-suture) system with a wireless circuit for surgical wound healing of post-operation sites on soft, time-dynamic tissues in the body. The electronic suture includes layers of on-demand drug vehicle (PGCL 15:85), conductive composite-based resistive heater (PGCL 55:45 composite), passivation layer (SiO₂, 300 nm), electrical interconnects (W/Mg, 100-nm/1-μm thick), and temperature meter (W/Mg, 10-nm/100-nm thick). The wireless circuit includes microcontroller and bluetooth modules, amplifier, diodes, capacitors, and inductive coil (Mg, 20-μm thick). b Photograph of fabricated wireless system for MED-suture with multiple functions of temperature measurements and heating actuation. c Elastic performance of MED-suture with 50% of uniaxial tensile strain and cross-sectional view of its overall structure observed with scanning electron microscope (SEM). d In vitro drug delivery demonstration of MED-suture immersed in PBS solution at room temperature: (1) initial state (left), (2) thermal actuation (middle), and (3) drug elution (right). e On-demand drug release behaviors with ON/OFF cyclic thermal actuations and temperature monitoring profile for 24 h. f Ex vivo experiment setup for MED-suture using porcine skin with surgical incisions and IR images of heat-induced drug release via thermal actuation. g Experimental result after drug release on porcine tissues with four cyclic actuations

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