Multimaterial Shape Memory Polymer Fibers for Advanced Drug Release Applications

Abstract

Stimuli-responsive polymers offer unprecedented control over drug release in implantable delivery systems. Shape memory polymer fibers (SMPFs), with their large specific surface area and programmable properties, present promising alternatives for triggerable drug delivery. However, the existing SMPFs face limitations in resolution, architecture, scalability, and functionality. We introduce thermal drawing as a materials and processing platform to fabricate microstructured, multimaterial SMPFs that are tens of meters long, with high resolution (10 μm) and extreme aspect ratios (> 10⁵). These novel fibers achieve highly controlled, sequential drug release over tailored time periods of 6 months. Post thermal drawing photothermal coatings enable accelerated, spatially precise drug release within 4 months and facilitate light-triggered, untethered shape recovery. The fibers’ fast self-tightening capability within 40 s shows their potential as smart sutures for minimally invasive procedures that deliver drugs simultaneously. In addition, the advanced multimaterial platform facilitates the integration of optical and metallic elements within SMP systems, allowing highly integrated fibers with shape memory attributes and unprecedented functionalities. This versatile technology opens new avenues for diverse biomedical applications, including implantable drug delivery systems, smart sutures, wound dressings, stents, and functional textiles. It represents a significant advancement in precise spatio-temporal control of drug delivery and adaptive medical devices.

Keywords

Shape memory polymers / Multimaterial fibers / Drug delivery / Sequential drug release / Multifunctionality

References

[1] HeG-Q, LiH, LiuJ, HuY-L, LiuY, WangZL, JiangP. Recent progress in implantable drug delivery systems. Adv Mater, 2024, 362312530

[2] TalebianS, ForoughiJ, WadeSJ, VineKL, Dolatshahi-PirouzA, MehraliM, CondeJ, WallaceGG. Biopolymers for antitumor implantable drug delivery systems: recent advances and future outlook. Adv Mater, 2018, 301706665

[3] KutnerN, KunduruKR, RizikL, FarahS. Recent advances for improving functionality, biocompatibility, and longevity of implantable medical devices and deliverable drug delivery systems. Adv Funct Mater, 2021, 312010929

[4] StuartMAC, HuckWTS, GenzerJ, MüllerM, OberC, StammM, SukhorukovGB, SzleiferI, TsukrukVV, UrbanM, WinnikF, ZauscherS, LuzinovI, MinkoS. Emerging applications of stimuli-responsive polymer materials. Nat Mater, 2010, 9101

[5] ZhangQ, ZhangY, WanY, CarvalhoW, HuL, SerpeMJ. Stimuli-responsive polymers for sensing and reacting to environmental conditions. Prog Polym Sci, 2021, 116101386

[6] ZhangA, JungK, LiA, LiuJ, BoyerC. Recent advances in stimuli-responsive polymer systems for remotely controlled drug release. Prog Polym Sci, 2019, 99101164

[7] DelaeyJ, DubruelP, Van VlierbergheS. Shape-memory polymers for biomedical applications. Adv Funct Mater, 2020, 301909047

[8] LendleinA, GouldOEC. Reprogrammable recovery and actuation behaviour of shape-memory polymers. Nat Rev Mater, 2019, 4116

[9] XiaY, HeY, ZhangF, LiuY, LengJ. A review of shape memory polymers and composites: mechanisms, materials, and applications. Adv Mater, 2021, 332000713

[10] WanX, XiaoZ, TianY, ChenM, LiuF, WangD, LiuY, BartoloPJDS, YanC, ShiY, ZhaoRR, QiHJ, ZhouK. Recent advances in 4D printing of advanced materials and structures for functional applications. Adv Mater, 2024, 362312263

[11] ZhaoW, YueC, LiuL, LiuY, LengJ. Research progress of shape memory polymer and 4D printing in biomedical application. Adv Healthcare Mater, 2023, 122201975

[12] BilM, Kijeńska-GawrońskaE, Głodkowska-MrówkaE, Manda-HandzlikA, MrówkaP. Design and in vitro evaluation of electrospun shape memory polyurethanes for self-fitting tissue engineering grafts and drug delivery systems. Mater Sci Eng C, 2020, 110110675

[13] WangL, MaJ, GuoT, ZhangF, DongA, ZhangS, LiuY, YuanH, LengJ. Control of surface wrinkles on shape memory PLA/PPDO micro-nanofibers and their applications in drug release and anti-scarring. Adv Fiber Mater, 2023, 5632

[14] LvH, TangD, SunZ, GaoJ, YangX, JiaS, PengJ. Electrospun PCL-based polyurethane/HA microfibers as drug carrier of dexamethasone with enhanced biodegradability and shape memory performances. Colloid Polym Sci, 2020, 298103

[15] ChenW, XuY, LiuY, WangZ, LiY, JiangG, MoX, ZhouG. Three-dimensional printed electrospun fiber-based scaffold for cartilage regeneration. Mater Des, 2019, 179107886

[16] ZareM, ParvinN, PrabhakaranMP, MohandesiJA, RamakrishnaS. Highly porous 3D sponge-like shape memory polymer for tissue engineering application with remote actuation potential. Compos Sci Technol, 2019, 184107874

[17] LiuH, ZhangM, XiaoH, WangK, HuangW, WuG, YangJ, JiaY-G, ZhuX. Tunable bio-derived skin-like shape memory fibers for smart suturing. Adv Funct Mater, 2024, 20242412565

[18] BaoM, LouX, ZhouQ, DongW, YuanH, ZhangY. Electrospun biomimetic fibrous scaffold from shape memory polymer of PDLLA-co-TMC for bone tissue engineering. ACS Appl Mater Interfaces, 2014, 62611

[19] WeiW, ZhangP, CaoF, LiuJ, QianK, PanD, YaoY, LiW. Ultrathin flexible electrospun EVA nanofiber composite with electrothermally-driven shape memory effect for electromagnetic interference shielding. Chem Eng J, 2022, 446137135

[20] ParkS, BaughN, ShahHK, ParekhDP, JoshipuraID, DickeyMD. Ultrastretchable elastic shape memory fibers with electrical conductivity. Adv Sci, 2019, 61901579

[21] LiM, ChenK, ZhangD, YeZ, YangZ, WangQ, JiangZ, ZhangY, ShangY, CaoA. Wet-spinning carbon nanotube/shape memory polymer composite fibers with high actuation stress and predesigned shape change. Adv Sci, 2024, 20242404913

[22] LeeHP, GaharwarAK. Light-responsive inorganic biomaterials for biomedical applications. Adv Sci, 2020, 72000863

[23] YanW, DongC, XiangY, JiangS, LeberA, LokeG, XuW, HouC, ZhouS, ChenM, HuR, ShumPP, WeiL, JiaX, SorinF, TaoX, TaoG. Thermally drawn advanced functional fibers: new frontier of flexible electronics. Mater Today, 2020, 35168

[24] LokeG, YanW, KhudiyevT, NoelG, FinkY. Recent progress and perspectives of thermally drawn multimaterial fiber electronics. Adv Mater, 2020, 321904911

[25] ChenM, WangZ, LiK, WangX, WeiL. Elastic and stretchable functional fibers: a review of materials, fabrication methods, and applications. Adv Fiber Mater, 2021, 31

[26] ChenX, MengY, LaperrousazS, BanerjeeH, SongJ, SorinF. Thermally drawn multi-material fibers: from fundamental research to industrial applications. Natl Sci Rev, 2024, 11nwae290

[27] BayindirM, AbouraddyAF, SorinF, JoannopoulosJD, FinkY. Detectors. Opt Photon News, 2004, 1524

[28] BayindirM, SorinF, AbouraddyAF, ViensJ, HartSD, JoannopoulosJD, FinkY. Metal–insulator–semiconductor optoelectronic fibres. Nature, 2004, 431826

[29] YanW, NoelG, LokeG, MeiklejohnE, KhudiyevT, MarionJ, RuiG, LinJ, CherstonJ, SahasrabudheA, WilbertJ, WicaksonoI, HoytRW, MissakianA, ZhuL, MaC, JoannopoulosJ, FinkY. Single fibre enables acoustic fabrics via nanometre-scale vibrations. Nature, 2022, 603616

[30] QuY, Nguyen-DangT, PageAG, YanW, Das GuptaT, RotaruGM, RossiRM, FavrodVD, BartolomeiN, SorinF. Superelastic multimaterial electronic and photonic fibers and devices via thermal drawing. Adv Mater, 2018, 301707251

[31] ShadmanS, Nguyen-DangT, Das GuptaT, PageAG, RichardI, LeberA, RuzaJ, KrishnamaniG, SorinF. Microstructured biodegradable fibers for advanced control delivery. Adv Funct Mater, 2020, 301910283

[32] KoppesRA, ParkS, HoodT, JiaX, Abdolrahim PoorheraviN, AchyutaAH, FinkY, AnikeevaP. Thermally drawn fibers as nerve guidance scaffolds. Biomaterials, 2016, 8127

[33] LeberA, DongC, ChandranR, Das GuptaT, BartolomeiN, SorinF. Soft and stretchable liquid metal transmission lines as distributed probes of multimodal deformations. Nat Electron, 2020, 3316

[34] DongC, LeberA, YanD, BanerjeeH, LaperrousazS, Das GuptaT, ShadmanS, ReisPM, SorinF. 3D stretchable and self-encapsulated multimaterial triboelectric fibers. Sci Adv, 2022, 8wabo0869

[35] DongC, PageAG, YanW, Nguyen-DangT, SorinF. Microstructured multimaterial fibers for microfluidic sensing. Adv Mater Technol, 2019, 41900417

[36] ZhangY, LiX, KimJ, TongY, ThompsonEG, JiangS, FengZ, YuL, WangJ, HaDS, SontheimerH, JohnsonBN, JiaX. Thermally drawn stretchable electrical and optical fiber sensors for multimodal extreme deformation sensing. Adv Opt Mater, 2021, 92001815

[37] YanW, Nguyen-DangT, CayronC, Das GuptaT, PageAG, QuY, SorinF. Microstructure tailoring of selenium-core multimaterial optoelectronic fibers. Opt Mater Express, 2017, 71388

[38] BanerjeeH, LeberA, LaperrousazS, La PollaR, DongC, MansourS, WanX, SorinF. Soft multimaterial magnetic fibers and textiles. Adv Mater, 2023, 352212202

[39] LeberA, DongC, LaperrousazS, BanerjeeH, AbdelazizMEMK, BartolomeiN, SchyrrB, TemelkuranB, SorinF. Highly integrated multi-material fibers for soft robotics. Adv Sci, 2023, 102204016

[40] StrutynskiC, EvrardM, DésévédavyF, GadretG, JulesJ-C, BrachaisC-H, KiblerB, SmektalaF. 4D optical fibers based on shape-memory polymers. Nat Commun, 2023, 146561

[41] DologR, WeissRA. Shape memory behavior of a polyethylene-based carboxylate ionomer. Macromolecules, 2013, 467845

[42] XieT. Tunable polymer multi-shape memory effect. Nature, 2010, 464267

[43] ZengX, LuoM, LiuG, WangX, TaoW, LinY, JiX, NieL, MeiL. Polydopamine-modified black phosphorous nanocapsule with enhanced stability and photothermal performance for tumor multimodal treatments. Adv Sci, 2018, 51800510

[44] DallavalleS, DobričićV, LazzaratoL, GazzanoE, MachuqueiroM, PajevaI, TsakovskaI, ZidarN, FrutteroR. Improvement of conventional anti-cancer drugs as new tools against multidrug resistant tumors. Drug Resist Updates, 2020, 50100682

[45] XieZ, Buschle-DillerG. Electrospun poly(d,l-lactide) fibers for drug delivery: the influence of cosolvent and the mechanism of drug release. J Appl Polym Sci, 2009, 1151

[46] ZilbermanM, SchwadeND, EberhartRC. Protein-loaded bioresorbable fibers and expandable stents: mechanical properties and protein release. J Biomed Mater Res B Appl Biomater, 2004, 691

[47] LavinDM, StefaniRM, ZhangL, FurtadoS, HopkinsRA, MathiowitzE. Multifunctional polymeric microfibers with prolonged drug delivery and structural support capabilities. Acta Biomater, 1891, 20128

[48] SiegelSJ, KahnJB, MetzgerK, WineyKI, WernerK, DanN. Effect of drug type on the degradation rate of PLGA matrices. Eur J Pharm Biopharm, 2006, 64287

[49] NiG, YangG, HeY, LiX, DuT, XuL, ZhouS. Uniformly sized hollow microspheres loaded with polydopamine nanoparticles and doxorubicin for local chemo-photothermal combination therapy. Chem Eng J, 2020, 379122317

[50] XiaS, LiuD, JiangK, CaoM, LouZ, ChengR, YiJ, YinA, JiangY, ChengK, WengW, ShiB, TangB. Photothermal driven BMSCs osteogenesis and M2 macrophage polarization on polydopamine-coated Ti(3)C(2) nanosheets/poly(vinylidene fluoride trifluoroethylene) nanocomposite coatings. Mater Today Bio, 2024, 27101156

[51] DaiY, YangD, YuD, CaoC, WangQ, XieS, ShenL, FengW, LiF. Mussel-inspired polydopamine-coated lanthanide nanoparticles for NIR-II/CT dual imaging and photothermal therapy. ACS Appl Mater Interfaces, 2017, 926674

[52] RichardI, MauryaAK, ShadmanS, MasquelierE, MartheyLS, NeelsA, SorinF. Unraveling the influence of thermal drawing parameters on the microstructure and thermo-mechanical properties of multimaterial fibers. Small, 2022, 182101392

[53] WanX, WeiH, ZhangF, LiuY, LengJ. 3D printing of shape memory poly(d,l-lactide-co-trimethylene carbonate) by direct ink writing for shape-changing structures. J Appl Polym Sci, 2019, 13648177

[54] ChanM-H, PanY-T, LeeIJ, ChenC-W, ChanY-C, HsiaoM, WangF, SunL, ChenX, LiuR-S. Minimizing the heat effect of photodynamic therapy based on inorganic nanocomposites mediated by 808 nm near-infrared light. Small, 2017, 131700038

[55] YangG, YangD, YangP, LvR, LiC, ZhongC, HeF, GaiS, LinJ. A single 808 nm near-infrared light-mediated multiple imaging and photodynamic therapy based on titania coupled upconversion nanoparticles. Chem Mater, 2015, 277957

[56] ReinM, FavrodVD, HouC, KhudiyevT, StolyarovA, CoxJ, ChungC-C, ChhavC, EllisM, JoannopoulosJ, FinkY. Diode fibres for fabric-based optical communications. Nature, 2018, 560214

[57] JiF, ZhuY, HuJ, LiuY, YeungL-Y, YeG. Smart polymer fibers with shape memory effect. Smart Mater Struct, 2006, 151547

[58] LiG, ZhangP. A self-healing particulate composite reinforced with strain hardened short shape memory polymer fibers. Polymer, 2013, 545075

[59] AslanS, KaplanS. Thermomechanical and shape memory performances of thermo-sensitive polyurethane fibers. Fibers Polym, 2018, 19272

[60] GonzálezJ, ArdanuyM, GonzálezM, RodriguezR, JovančićP. Polyurethane shape memory filament yarns: melt spinning, carbon-based reinforcement, and characterization. Text Res J, 2022, 93957

[61] ZhuX, FengW, ChangJ, TanY-W, LiJ, ChenM, SunY, LiF. Temperature-feedback upconversion nanocomposite for accurate photothermal therapy at facile temperature. Nat Commun, 2016, 710437

[62] Kok-MengL, ZhiyongW, ZhiZ, Siu-PingH. Computational thermal fluid models for design of a modern fiber draw process. IEEE Trans Autom Sci Eng, 2006, 3108

[63] ZhanL, DengJ, KeQ, LiX, OuyangY, HuangC, LiuX, QianY. Grooved fibers: preparation principles through electrospinning and potential applications. Adv Fiber Mater, 2022, 4203

[64] GuM, YuW, StefanelloST, WangJ, ZhangX, ZhangY, ZhangW, GuanY, ShahinV, QianY, YuanW-E. Synergistic in vivo anticancer effects of 1,7-heptanediol and doxorubicin co-loadedliposomes in highly aggressive breast cancer. J Control Rel, 2025, 377174

[65] QianY, YaoZ, WangX, ChengY, FangZ, YuanW-E, FanC, OuyangY. (-)-Epigallocatechin gallate-loaded polycaprolactone scaffolds fabricated using a 3D integrated moulding method alleviate immune stress and induce neurogenesis. Cell Prolif, 2020, 53e12730

Funding

Swiss National Science Foundation(SNSF project 200021_204579)

EPFL Lausanne

RIGHTS & PERMISSIONS

The Author(s)