Biocompatible three-dimensional printed artificial muscles

Abstract

Provided herein are antimicrobial liquid crystal materials for use in therapeutic and wound-healing applications. Also provided herein are devices and methods for use of the antimicrobial liquid crystal materials, for example in artificial muscle, soft- engineering, and wound healing methods.

Description

BIOCOMPATIBLE THREE-DIMENSIONAL PRINTED ARTIFICIAL MUSCLESCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to United States Provisional Patent Application No. 63 / 595,952 filed November 3, 2023, the disclosure of which is hereby incorporated by reference in its entirety.STATEMENT REGARDING FEDERAL FUNDING

[0002] This invention was made with government support under 1921842 awarded by the National Science Foundation. The government has certain rights in the invention.

[0003] The advancement of new materials with multifunctional properties has gained interest in the scientific field and industry. There are a wide variety of materials that have been reported in the literature. Among those materials, elastomers have gained lots of interest due to their interesting properties such as elasticity, tear resistance, impermeability, soft texture, etc. These elastic soft materials exhibit tissue-like assent, stretchability, and bio-compatibility which are essential for the future generation of skin-interfaced materials. However, their thermo-mechanical properties are less tunable. Liquid crystal elastomers (LCEs) have anisotropic thermomechanical properties that can be precisely controlled. Elastomers have more fixed mechanical properties, which may limit their adaptability in situations when particular mechanical qualities are necessary. Hence, LCEs have emerged as a class of smart elastomer materials, with remarkable thermal, mechanical, and optical properties. The unique property of LCEs is that they undergo reversible shape change in response to external stimuli like light, mechanical stress, and temperature. Due to this, LCEs have a remarkable and wide variety of applications in the field of soft robotics, optical devices, and biomimetic systems. However, most of the LCEs have a nematic-isotropic transition temperature (TNI) higher than the human body temperature of 37°C. This issue has received little attention, further limiting their biological applications. The issue has been resolved in recent years by many of the reports published in the literature to decrease the TNI by the introduction of chain extenders, and modulating the length of the aliphatic chains connected to liquid crystalline diacrylate mesogenic monomers, and controlling the core structure of the liquid crystalline diacrylate (C6BAPE) (see e.g., McCracken et al. “Molecular engineering of mesogenic constituents within liquid crystalline elastomers to sharpen thermotropic actuation”,Advanced Functional Materials, 2021 , 31 (16): 2100564 and Bauman et al. “Actuation of liquid crystalline elastomers at or below ambient temperature”, Angewandte Chemie International Edition, 2022, 61 (28): e202202577). Reducing the TNI slightly above body temperature has also been reported, using the GDMP chain extender compared with other chains (Martinez et al. “Thermomechanically active electrodes power work- dense soft actuators”, Soft Matter, 2021 , 17(6): 1521 -1529).

[0004] Alongside interest in the development of body or ambient temperature LCEs, the demand has led to the exploration of healthcare materials with effective antibacterial properties for multiple industries including healthcare products and textiles. Antibacterial liquid crystal elastomers are promising materials for wound healing and in active implantable devices. Yaoyao Jiang et al. reported a breathable and waterproof porous PHG-mLCE / hydrogel patch designed to increase skin adhesion (Jiang et al. “Skin-friendly and antibacterial monodomain liquid crystal elastomer actuator”, Colloids and Surfaces B: Biointerfaces, 2023, 222: 113110). Jun Wu et al. reported the LCE metamaterials integrated with medical dressing skin repair with both round and cross-shaped wounds demonstrating the advantages of the hemostatic patch over conventional strategies. But the actuation temperature of these materials was 46 °C; still above body temperature (Wu et al. “Liquid crystal elastomer metamaterials with giant biaxial thermal shrinkage for enhancing skin regeneration”, Advanced Materials, 2021 , 33(45): 2106175).

[0005] Antimicrobial LCE (ALCE) polymer materials and devices or implants comprising those materials, with an actuation temperature at or close to human physiological temperatures are desirable, e.g., in the range of from 30eC-45eC, are desired.SUMMARY OF THE INVENTION

[0006] Provided herein are antibacterial liquid crystal elastomers, artificial muscles including antibacterial liquid crystal elastomers, and methods of making liquid crystal elastomers. Also provided herein are devices including antibacterial liquid crystal elastomers.

[0007] According to a first aspect or embodiment, an antibacterial liquid crystal elastomer is provided. The antibacterial liquid crystal elastomer includes a liquid crystal polymer network of cross-linked liquid crystal oligomers including a pendant antibiotic moiety, wherein the liquid crystal oligomers include a liquid crystalcomponent, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, wherein the antibacterial liquid crystal elastomer includes a nominal nematic-isotropic transition temperature (TNI) in a range of from 30 °C to 45 °C

[0008] According to a second aspect or embodiment, a method of making an antibacterial liquid crystal elastomer is provided. The method includes forming liquid crystal oligomers including a pendant antibiotic moiety, wherein the liquid crystal oligomers include a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, wherein forming the liquid crystal oligomers includes: preparing a mixture of liquid crystal monomers, chain extender monomers, optionally, monomers including an antibiotic moiety, and optionally, non-liquid crystalline monomers, and heating the mixture to form the liquid crystal oligomers; depositing the liquid crystal oligomers onto the surface of a substrate; aligning the liquid crystal components of the liquid crystal oligomers; and cross-linking the liquid crystal oligomers to form a liquid crystal polymer network, wherein the antibacterial liquid crystal elastomer includes a nominal nematic- isotropic transition temperature (TNI) in a range of from 30 °C to 45 °C.

[0009] According to a further aspect or embodiment, a device is provided. The device includes a first component including a first antibacterial liquid crystal elastomer, wherein the first antibacterial liquid crystal elastomer includes a liquid crystal polymer network of cross-linked liquid crystal oligomers including a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non- liquid crystalline component, and wherein the first antibacterial liquid crystal elastomer of the first component includes a nominal nematic-isotropic transition temperature (TNI) in a range of from 30°C to 45°C; a second component including a second antibacterial liquid crystal elastomer including an ionic component, an electronic conductive material, or combinations thereof, wherein the second component is in direct contact with the first component, wherein the second antibacterial liquid crystal elastomer includes a liquid crystal polymer network of cross-linked liquid crystal oligomers including a pendant antibiotic moiety, wherein the liquid crystal oligomers include a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, and wherein the second antibacterial liquid crystal elastomer of the second component includes anominal nematic-isotropic transition temperature (TNI) in a range of from about 30 °C to about 45 °C; and a resistive heating component in electrical contact with the second component, wherein the first component and the second component undergo a reversible change in shape in response to activation of the resistive heating component.

[0010] The following numbered clauses outline various embodiments of the present invention.

[0011] Clause 1. An antibacterial liquid crystal elastomer comprising: a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, wherein the antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 30 °C to about 45 °C.

[0012] Clause 2. The antibacterial liquid crystal elastomer of clause 1 , comprising a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

[0013] Clause 3. The antibacterial liquid crystal elastomer of clause 1 or 2, wherein the liquid crystal component is formed from a liquid crystal monomer comprising: a first terminal acrylate functional group; a second terminal acrylate functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the first terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the second terminal acrylate functional group to the second end of the mesogenic core.

[0014] Clause 4. The antibacterial liquid crystal elastomer of any of clauses 1 -3, wherein the mesogenic core comprises from one to three aromatic rings, wherein one or more of the aromatic rings are optionally substituted with an alkyl group, an ether group, an ester group, a halogen, a hydroxyl group, or combinations thereof.

[0015] Clause 5. The antibacterial liquid crystal elastomer of any of clauses 1 -4, wherein the first flexible linker and the second flexible linker comprise an aliphatic carbon chain optionally substituted with an oxygen atom.

[0016] Clause 6. The antibacterial liquid crystal elastomer of any of clauses 1 -5, wherein the first flexible linker and the second flexible linker comprise a C3 - C10 aliphatic carbon chain.

[0017] Clause 7. The antibacterial liquid crystal elastomer of any of clauses 1 -6, wherein the liquid crystal monomer comprises 1 ,4-bis-[4-(6- acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene) (RM82), 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2- Methyl-1 ,4-phenylene-bis[4[3(acryloyloxy) propyloxy]benzoate] (RM257), or combinations thereof.

[0018] Clause 8. The antibacterial liquid crystal elastomer of any of clauses 1 -7, wherein the liquid crystal component is further formed from an additional liquid crystal monomer comprising: a terminal acrylate functional group; a terminal reactive functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the terminal reactive functional group to the second end of the mesogenic core.

[0019] Clause 9. The antibacterial liquid crystal elastomer of any of clauses 1 -8, wherein the additional liquid crystal monomer comprises 4-cyanophenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (RM23).

[0020] Clause 10. The antibacterial liquid crystal elastomer of any of clauses 1 -9, wherein the chain extending component is formed from one or more chain extending monomers comprising a C2-C6 aliphatic carbon chain or one or more ether groups and from two or four terminal thiol groups, a C2-C6 aliphatic carbon chain and from one to two amine groups, or combinations thereof.

[0021] Clause 1 1. The antibacterial liquid crystal elastomer of any of clauses1 -10, wherein the one or more chain extending monomers are selected from the group consisting of ethane-1 ,2-dial bis(3-mercapto propanoate) (GDMP), 2,2’- (ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), 1 ,4-benzenedimethanethiol (BDMT), mixtures thereof, and combinations thereof.

[0022] Clause 12. The antibacterial liquid crystal elastomer of any of clauses 1 -1 1 , wherein the pendant antibiotic moiety comprises norfloxacin, acyclovir, afloxacin, ampicillin, amphotericin B, atovaquone, azithromycin, ciprofloxacin, clarithromycin, clindamycin, clofazimine, dapsone, diclazaril, doxycycline, erythromycin, ethambutol, fluconazole, fluoroquinolones, foscarnet, ganciclovir, gentamicin, iatroconazole, isoniazid, ketoconazole, levofloxacin, lincomycin, miconazole, neomycin, ofloxacin, paromomycin, penicillin, pentamidine, polymixin B, pyrazinamide, pyrimethamine,rifabutin, rifampin, sparfloxacin, streptomycin, sulfadiazine, tetracycline, tobramycin, trifluorouridine, trimethoprim sulphate, Zn-pyrithione, or vancomycin.

[0023] Clause 13. The antibacterial liquid crystal elastomer of any of clauses 1 -12, wherein the pendant antibiotic moiety comprises norfloxacin.

[0024] Clause 14. The antibacterial liquid crystal elastomer of any of clauses 1 -13, wherein the pendant antibiotic moiety comprises an antibacterial peptide.

[0025] Clause 15. The antibacterial liquid crystal elastomer of any of clauses 1 -14, wherein the pendant antibiotic moiety component is covalently bonded to a surface of the cross-linked liquid crystal oligomers.

[0026] Clause 16. The antibacterial liquid crystal elastomer of any of clauses 1 -15, wherein the pendant antibiotic moiety component is formed from a monomer comprising the antibiotic moiety, wherein the monomer comprising the antibiotic moiety comprises the following structure:wherein: Ri is the antibiotic moiety; X is -NH-, -S-, -O-, or -OC(O)-; and Y is a bond or a linker, and wherein the monomer comprising the antibiotic moiety is cross-linked with the liquid crystal component, the chain extender component, and optionally, the non-liquid crystalline component.

[0027] Clause 17. The antibacterial liquid crystal elastomer of any of clauses 1 -16, wherein the liquid crystal oligomers further comprise a non-liquid crystalline component, wherein the non-liquid crystalline component is formed from a non-liquid crystalline monomer.

[0028] Clause 18. The antibacterial liquid crystal elastomer of any of clauses 1 -17, wherein the non-liquid crystalline monomer is glyoxal bis(diallyl acetal) (GBDA).

[0029] Clause 19. The antibacterial liquid crystal elastomer of any of clauses 1 -18, wherein the liquid crystal oligomers comprising the liquid crystal component, the chain extender component, and the pendant antibiotic moiety component are cross-linked using a cross-linker in the presence of one or more catalysts, one or more inhibitors of thermal polymerization (e.g., 2,6-Di-tert-butyl-4-methylphenol (BHT)), and / or one or more photoinitiators.

[0030] Clause 20. The antibacterial liquid crystal elastomer of any of clauses 1 -19, wherein the cross-linker is selected from the group consisting of 1 ,3,5-triallyl- 1 ,3,5- triazine-2,4,6(1 H,3H,5H)-trione (TATATO), 2,4,6,8-tetramethyl-2,4,6,8- tetravinylcyclotetrasiloxane, mixtures thereof, and combinations thereof.

[0031] Clause 21 . The antibacterial liquid crystal elastomer of any of clauses 1 -20, wherein the liquid crystal oligomers comprising the liquid crystal component, the chain extender component, the pendant antibiotic moiety component, and the non-liquid crystalline component are cross-linked in the presence of one or more catalysts, one or more radical one or more inhibitors of thermal polymerization, and / or one or more photoinitiators.

[0032] Clause 22. The antibacterial liquid crystal elastomer of any clauses 1 -21 , wherein the liquid crystal components of the liquid crystal oligomers are aligned.

[0033] Clause 23. The antibacterial liquid crystal elastomer of any of clauses 1 -22, wherein the liquid crystal oligomers are formed from 4-(6- (acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2,2’- (ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), glyoxal bis(diallyl acetal) (GBDA), and

[0034] Clause 24. The antibacterial liquid crystal elastomer of any of clauses 1 -23, further comprising an ionic component, an electronic conductive material, or combinations thereof.

[0035] Clause 25. The antibacterial liquid crystal elastomer of any of clauses 1 -24, wherein the ionic component is formed by doping with an ionic liquid, an imidazolium- functionalized cross-linker comprising the following formula:wherein X’ isor combinations thereof.

[0036] Clause 26. The antibacterial liquid crystal elastomer of any of clauses 1 -25, wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

[0037] Clause 27. An artificial muscle comprising the antibacterial liquid crystal elastomer of any of clauses 1 -26.

[0038] Clause 28. The artificial muscle of clause 27, wherein the antibacterial liquid crystal elastomer undergoes a reversible change in shape in response to an external stimuli.

[0039] Clause 29. The artificial muscle of clause 27 or clause 28, wherein the antibacterial liquid crystal elastomer comprises an ionic component, an electronic conductive material, or combinations thereof and the external stimuli is heat generated by resistive heating.

[0040] Clause 30. A method of making an antibacterial liquid crystal elastomer, the method comprising: forming liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, wherein forming the liquid crystal oligomers comprises: preparing a mixture of liquid crystal monomers, chain extender monomers, optionally, monomers comprising an antibiotic moiety, and optionally, non-liquid crystalline monomers, and heating the mixture to form the liquid crystal oligomers; depositing the liquid crystal oligomers onto the surface of a substrate; aligning the liquid crystal components of the liquid crystal oligomers; and cross-linking the liquid crystal oligomers to form a liquid crystal polymer network, wherein the antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 30 °C to about 45 °C.

[0041] Clause 31 . The method of clause 30, wherein cross-linking the liquid crystal oligomers is completed after aligning the liquid crystal components of the liquid crystal oligomers.

[0042] Clause 32. The method of clause 30 or clause 31 , wherein cross-linking the liquid crystal oligomers is completed before aligning the liquid crystal components of the liquid crystal oligomers.

[0043] Clause 33. The method of any of clauses 30-32, wherein aligning the liquid crystal components of the oligomers is completed through stretching.

[0044] Clause 34. The method of any of clauses 30-33, wherein the liquid crystal oligomers are deposited in an extrusion printing process, wherein the extrusion printing process aligns the liquid crystal components of the liquid crystal oligomers.

[0045] Clause 35. The method of any of clauses 30-34, further comprising adding an ionic liquid, an imidazolium-functionalized cross-linker, an electronic conductive material, or combinations thereof to the mixture of the liquid crystal monomers, the chain extender monomers, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers.

[0046] Clause 36. The method of any of clauses 30-35, wherein the imidazolium- functionalized cross-linker comprises the following formula: wherein X’ is

[0047] Clause 37. The method of any of clauses 30-36, wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

[0048] Clause 38. The method of any of clauses 30-37, further comprising adding cross-linkers, one or more catalysts, one or more inhibitors of thermal polymerization(e.g., 2,6-Di-tert-butyl-4-methylphenol (BHT)), and / or one or more photoinitiators to the mixture of the liquid crystal monomers, the chain extender monomers, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers.

[0049] Clause 39. The method of any of clauses 30-38, wherein the cross-linker is selected from the group consisting of 1 ,3,5-triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)- trione (TATATO), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, mixtures thereof, and combinations thereof.

[0050] Clause 40. The method of any of clauses 30-39, wherein the liquid crystal monomers comprise: a first terminal acrylate functional group; a second terminal acrylate functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the first terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the second terminal acrylate functional group to the second end of the mesogenic core.

[0051] Clause 41 . The method of any of clauses 30-40, wherein the mesogenic core comprises from one to three aromatic rings, wherein one or more of the aromatic rings are optionally substituted with an alkyl group, an ether group, an ester group, a halogen, a hydroxyl group, or combinations thereof.

[0052] Clause 42. The method of any of clauses 30-41 , wherein the first flexible linker and the second flexible linker comprise an aliphatic carbon chain optionally substituted with an oxygen atom.

[0053] Clause 43. The method of any of clauses 30-42, wherein the first flexible linker and the second flexible linker comprise a C3 - C10 aliphatic carbon chain.

[0054] Clause 44. The method of any of clauses 30-43, wherein the liquid crystal monomers comprise 1 ,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene) (RM82), 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2-methyl-1 ,4-phenylene-bis[4[3(acryloyloxy) propyloxy]benzoate] (RM257), or combinations thereof.

[0055] Clause 45. The method of any of clauses 30-44, further comprising adding an additional liquid crystal monomer to the mixture of the liquid crystal monomers, the chain extender monomers, optionally, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers, wherein the additional liquid crystal monomer comprises: a terminal acrylate functional group; a terminal reactive functional group; a mesogenic core comprising a first end and a second end; a firstflexible linker connecting the terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the terminal reactive functional group to the second end of the mesogenic core.

[0056] Clause 46. The method of any of clauses 30-45, wherein the additional liquid crystal monomer comprises 4-cyanophenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (RM23).

[0057] Clause 47. The method of any of clauses 30-46, wherein the chain extending monomers comprise a C2-C6 aliphatic carbon chain or one or more ether groups and from two or four terminal thiol groups, a C2-C6 aliphatic carbon chain and from one to two amine groups, or combinations thereof.

[0058] Clause 48. The method of any of clauses 30-47, wherein the chain extending monomers are selected from the group consisting of ethane-1 ,2-dial bis(3-mercapto propanoate) (GDMP), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), 1 ,4-benzenedimethanethiol (BDMT), mixtures thereof, and combinations thereof.

[0059] Clause 49. The method of any of clauses 30-48, wherein the pendant antibiotic moiety comprises norfloxacin, acyclovir, afloxacin, ampicillin, amphotericin B, atovaquone, azithromycin, ciprofloxacin, clarithromycin, clindamycin, clofazimine, dapsone, diclazaril, doxycycline, erythromycin, ethambutol, fluconazole, fluoroquinolones, foscarnet, ganciclovir, gentamicin, iatroconazole, isoniazid, ketoconazole, levofloxacin, lincomycin, miconazole, neomycin, ofloxacin, paromomycin, penicillin, pentamidine, polymixin B, pyrazinamide, pyrimethamine, rifabutin, rifampin, sparfloxacin, streptomycin, sulfadiazine, tetracycline, tobramycin, trifluorouridine, trimethoprim sulphate, Zn-pyrithione, or vancomycin.

[0060] Clause 50. The method of any of clauses 30-49, wherein the pendant antibiotic moiety comprises norfloxacin.

[0061] Clause 51 . The method of any of clauses 30-48, wherein the pendant antibiotic moiety comprises an antibiotic peptide

[0062] Clause 52. The method of any of clause 30-51 , further comprising reacting the pendant antibiotic moiety component with a surface of the cross-linked liquid crystal oligomers to covalently bond the pendant antibiotic moiety component to the surface of the cross-linked liquid crystal oligomers.

[0063] Clause 53. The method of any of clauses 30-48, wherein the mixture comprises liquid crystal monomers, chain extender monomers, monomers comprising an antibiotic moiety, and optionally, non-liquid crystalline monomers.

[0064] Clause 54. The method of clause 53, wherein the monomers comprising the antibiotic moiety comprise the following structure:wherein: Ri is the antibiotic moiety; X is -NH-, -S-, -O-, or -OC(O)-; and Y is a bond or a linker.

[0065] Clause 55. The method of clause 53 or clause 54, wherein the mixture comprises a molar ratio of the liquid crystal monomers to the monomers comprising the antibiotic moiety to the chain extending monomers to the non-crystalline monomers of 0.1 -1 .5: 0.05-0.65 : 0.01 -1 .5 : 0-0.5.

[0066] Clause 56. The method of any of clauses 30-55, wherein the liquid crystal oligomers further comprise non-liquid crystalline components.

[0067] Clause 57. The method of any of clauses 30-56, wherein the non-liquid crystalline monomer is glyoxal bis(diallyl acetal) (GBDA).

[0068] Clause 58. The method of any of clauses 30-57, wherein the antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

[0069] Clause 59. A device, comprising: a first component comprising a first antibacterial liquid crystal elastomer, wherein the first antibacterial liquid crystal elastomer comprises a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, and wherein the first antibacterial liquid crystal elastomer of the first component comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 30 °C to about 45 °C; a second component comprising a second antibacterial liquid crystal elastomer comprising an ionic component, an electronic conductive material, or combinations thereof, wherein the second component is in direct contact with the first component, wherein the second antibacterial liquid crystal elastomer comprises aliquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, and wherein the second antibacterial liquid crystal elastomer of the second component comprises a nominal nematic- isotropic transition temperature (T NI) in a range of from about 30 °C to about 45 °C; and a resistive heating component in electrical contact with the second component, wherein the first component and the second component undergo a reversible change in shape in response to activation of the resistive heating component.

[0070] Clause 60. The device of clause 59, wherein the device further comprises an inductive coupling receiver configured to produce a current through the resistive heating component by inductive coupling with an inductive coupling transmitter.

[0071] Clause 61 . The device of clause 59 or clause 60, wherein the inductive coupling receiver is fabricated from conductive soft polymers, metals, or combinations thereof.

[0072] Clause 62. The device of any of clauses 59-61 , wherein the inductive coupling transmitter is activated by a wireless actuator.

[0073] Clause 63. The device of any of clauses 59-62, wherein the resistive heating component is electrically and / or mechanically connected to the second component.

[0074] Clause 64. The device of any of clauses 59-63, wherein the resistive heating component is electrically connected to the second component through one or more wires.

[0075] Clause 65. The device of any of clauses 59-64, wherein the first antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

[0076] Clause 66. The device of any of clauses 59-65, wherein the second antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

[0077] Clause 67. The device of any of clauses 59-66, wherein the liquid crystal component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is formed from a liquid crystal monomer comprising: a first terminal acrylate functional group; a second terminal acrylate functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the first terminal acrylate functional groupto the first end of the mesogenic core; and a second flexible linker connecting the second terminal acrylate functional group to the second end of the mesogenic core.

[0078] Clause 68. The device of any of clauses 59-67, wherein the mesogenic core comprises from one to three aromatic rings, wherein one or more of the aromatic rings are optionally substituted with an alkyl group, an ether group, an ester group, a halogen, a hydroxyl group, or combinations thereof.

[0079] Clause 69. The device of any of clauses 59-68, wherein the first flexible linker and the second flexible linker comprise an aliphatic carbon chain optionally substituted with an oxygen atom.

[0080] Clause 70. The device of any of clauses 59-69, wherein the first flexible linker and the second flexible linker comprise a C3 - C10 aliphatic carbon chain.

[0081] Clause 71 . The device of any of clauses 67 to 70, wherein the liquid crystal monomer comprises 1 ,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene) (RM82), 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2-methyl-1 ,4-phenylene-bis[4[3(acryloyloxy) propyloxy]benzoate] (RM257), or combinations thereof.

[0082] Clause 72. The device of any of clauses 59-71 , wherein the liquid crystal component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is further formed from an additional liquid crystal monomer comprising: a terminal acrylate functional group; a terminal reactive functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the terminal reactive functional group to the second end of the mesogenic core.

[0083] Clause 73. The device of any of clauses 59-72, wherein the additional liquid crystal monomer comprises 4-cyanophenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (RM23).

[0084] Clause 74. The device of any of clauses 59-73, wherein the chain extending component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is formed from one or more chain extending monomers comprising a C2-C6 aliphatic carbon chain or one or more ether groups and from two or four terminal thiol groups, a C2-C6 aliphatic carbon chain and from one to two amine groups, or combinations thereof.

[0085] Clause 75. The device of any of clauses 59-74, wherein the one or more chain extending monomers are selected from the group consisting of ethane-1 ,2-dial bis(3- mercapto propanoate) (GDMP), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), 1 ,4-benzenedimethanethiol (BDMT), mixtures thereof, and combinations thereof.

[0086] Clause 76. The device of any of clauses 59-75, wherein the pendant antibiotic moiety of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprises norfloxacin, acyclovir, afloxacin, ampicillin, amphotericin B, atovaquone, azithromycin, ciprofloxacin, clarithromycin, clindamycin, clofazimine, dapsone, diclazaril, doxycycline, erythromycin, ethambutol, fluconazole, fluoroquinolones, foscarnet, ganciclovir, gentamicin, iatroconazole, isoniazid, ketoconazole, levofloxacin, lincomycin, miconazole, neomycin, ofloxacin, paromomycin, penicillin, pentamidine, polymixin B, pyrazinamide, pyrimethamine, rifabutin, rifampin, sparfloxacin, streptomycin, sulfadiazine, tetracycline, tobramycin, trifluorouridine, trimethoprim sulphate, Zn-pyrithione, or vancomycin.

[0087] Clause 77. The device of any of clauses 59-76, wherein the pendant antibiotic moiety of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprises norfloxacin.

[0088] Clause 78. The device of any of clauses 59 to 75, wherein the pendant antibiotic moiety of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprises an antibacterial peptide.

[0089] Clause 79. The device of any of clauses 59 to 78, wherein the pendant antibiotic moiety component of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is covalently bonded to a surface of the cross-linked liquid crystal oligomers.

[0090] Clause 80. The device of any of clauses 59-78, wherein the pendant antibiotic moiety component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is formed from a monomer comprising the antibiotic moiety, wherein the monomer comprising the antibiotic moiety comprises the following structure:wherein: Ri is the antibiotic moiety; X is -NH-, -S-, -O-, or -OC(O)-; and Y is a bond or a linker, wherein the monomer comprising the antibiotic moiety is cross-linked with the liquid crystal component, the chain extender component, and optionally, the nonliquid crystalline componen.

[0091] Clause 81. The device of any of clauses 59-80, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer further comprise a non-liquid crystalline component, wherein the non-liquid crystalline component is formed from a non-liquid crystalline monomer.

[0092] Clause 82. The device of any of clauses 59-81 , wherein the non-liquid crystalline monomers is glyoxal bis(diallyl acetal) (GBDA).

[0093] Clause 83. The device of any of clauses 59-80, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprising the liquid crystal component, the chain extender component, and optionally, the pendant antibiotic moiety component are cross-linked using a cross-linker in the presence of one or more catalysts, one or more inhibitors of thermal polymerization (e.g., 2,6-Di-tert-butyl-4-methylphenol (BHT)), and / or one or more photoinitiators.

[0094] Clause 84. The device of any of clauses 59-83, wherein the cross-linker is selected from the group consisting of 1 ,3,5-triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)- trione (TATATO), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, mixtures thereof, and combinations thereof.

[0095] Clause 85. The device of any of clauses 59-84, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprising the liquid crystal component, the chain extender component, optionally, the pendant antibiotic moiety component, and the non-liquid crystalline component are cross-linked in the presence of one or more catalysts, one or more one or more inhibitors of thermal polymerization (e.g., 2,6-Di-tert-butyl-4- methylphenol (BHT)), and / or one or more photoinitiators.

[0096] Clause 86. The device of any of clauses 59-85, wherein the liquid crystal components of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer are aligned.

[0097] Clause 87. The device of any of clauses 59-86, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer are formed from 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), glyoxal bis(diallyl acetal) (GBDA), and

[0098] Clause 88. The device of any of clauses 59-87, wherein ionic component of the second antibacterial liquid crystal elastomer is formed by doping with an ionic liquid, an imidazolium-functionalized cross-linker comprising the following formula:combinations thereof.

[0099] Clause 89. The device of any of clauses 59-87, wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

[0100] Clause 90. The device of any of clauses 59-89, wherein the first antibacterial liquid crystal elastomer further comprises an ionic component, an electronic conductive material, or combinations thereof.

[0101] Clause 91 . The device of any of clauses 59-90, wherein ionic component is formed by doping with an ionic liquid, an imidazolium-functionalized cross-linker comprising the following formula:wcombinations thereof.

[0102] Clause 92. The device of any of clauses 59-91 , wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

[0103] Clause 93. The device of any of clauses 59-92, wherein the first component is arranged as a sphincter about an opening.

[0104] Clause 94. The device of any of clauses 5992, wherein the first component is arranged as a mesh comprising first isotropic component that expands and contracts in a first direction, and a second isotropic component that expands and contracts in a second direction, such that heating the first isotropic component using the resistive heating component causes contraction of the mesh along the first direction, and heating the second isotropic component using the resistive heating causes contraction of the mesh along the second direction.

[0105] Clause 95. The device of any of clauses 59-94, wherein the first isotropic component is heated by a first resistive heating component and the second isotropic component is independently heated by a second resistive heating component, such that contraction of the first isotropic component may be controlled independently of contraction of the second isotropic component.

[0106] Clause 96. The device of any of clauses 59-95, wherein at least a portion of the first component, the second component, and / or the resistive heating component are encapsulated in a secondary packaging.

[0107] Clause 97. The device of any of clauses 59-96, wherein the secondary packaging comprises a biocompatible polymer (e.g., polydimethylsiloxane (PDMS), parylene).BRIEF DESCRIPTION OF THE DRAWINGS

[0108] The invention will be described with reference to the following drawing figures wherein like reference numbers identify like parts throughout.

[0109] FIG. 1 depicts exemplary mesogenic cores for liquid crystal components as described herein (wavy lines depict bonds forming covalent linkage to additional moieties or groups within the liquid crystal component).

[0110] FIG. 2 depicts an exemplary device of the present invention.

[0111] FIG. 3 is a schematic of an exemplary device set up for inductively coupled actuation.

[0112] FIG. 4 depicts an exemplary first component that is arranged as a mesh and comprising a first isotropic component that expands and contracts in a first direction and a second isotropic component that expands and contracts in a second direction (designed by the arrows with n).

[0113] FIG. 5 is a reaction scheme for the synthesis of an acrylate-functionalized norfloxacin monomer.

[0114] FIGS. 6A-6B depict the synthesis of the antibiotic liquid crystal elastomer. FIG. 6A provides the materials used for the thiol-Michael / thiol— ene reaction. FIG. 6B provides a schematic for the method of synthesizing the antibiotic liquid crystal elastomer and then mechanically aligning the antibiotic liquid crystal elastomer after synthesis and cross-linking.

[0115] FIGS. 7A and 7B are polarizing optical micrographs. FIG. 7A are polarizing optical micrographs of the stretched ALCEs having a molar ratio of 0.18, 0.35, 0.55 of AFN, from left to right, observed at 0° angles with respect to the cross polarizers. FIG. 7B are polarizing optical micrographs of the stretched ALCEs having a molar ratio of 0.18, 0.35, 0.55 of norfloxacin, from left to right, observed at 45°angles with respect to the cross polarizers. In FIGS. 7A and 7B, the letter n with the arrow indicates the nematic direction of the antibacterial liquid crystal elastomer. The scale bar is 500 microns.

[0116] FIGS. 8A and 8B are micro viewer images of stretched ALCEs having a molar ratio of 0.18, 0.35, 0.55 of AFN, from left to right, at 21 °C (FIG. 8A) and the same ALCEs having a molar ratio of 0.18, 0.35, 0.55 of AFN, from left to right at 40 °C (FIG. 8B).

[0117] FIG. 9 is a graph showing the antibiotic liquid crystal elastomer variation of strain as a function of temperature with different molar ratios of AFN.

[0118] FIG. 10 provides the materials used for the thiol-Michael / thiol— ene reaction.

[0119] FIG. 1 1 depicts the extrusion printing process of an ALCE.

[0120] FIG. 12 is a schematic diagram of a hierarchically structured bandage.

[0121] FIG. 13 is a graph showing thermal actuation of liquid crystal elastomer materials.

[0122] FIG. 14 is a graph showing work content of liquid crystal elastomer materials.

[0123] FIG. 15 is a graph showing temperature rise and strain of liquid crystal elastomer materials.

[0124] FIG. 16 is a table showing power transfer and thermal actuation of liquid crystal elastomer materials.

[0125] FIG. 17 is a graph showing work content of liquid crystal elastomer materials.

[0126] FIGS. 18A-18D are x-ray images and graphs showing characterization of liquid crystal elastomer materials.

[0127] FIG. 19 is a schematic showing an artificial sphincter formed of liquid crystal elastomer materials.

[0128] FIG. 20 shows images of artificial sphincters formed of liquid crystal elastomer materials.DESCRIPTION OF THE INVENTION

[0129] Other than in the operating examples, or where otherwise indicated, the use of numerical values in the various ranges specified in this application are stated as approximations as though the minimum and maximum values within the stated ranges are both preceded by the word “about”. In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Also, unless indicated otherwise, the disclosure of ranges is intended as a continuous range including every value between the minimum and maximum values.

[0130] As used herein, “a” and “an” refer to one or more.

[0131] The term “comprising” is open-ended and may be synonymous with “including”, “containing”, or “characterized by”. The term “consisting essentially of” limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting of” excludes any element, step, or ingredient not specified in the claim. As used herein, embodiments “comprising” one or more stated elements or steps also include, but are not limited to embodiments “consisting essentially of” and “consisting of” those stated elements or steps. For definitions provided herein, those definitions refer to word forms, cognates and grammatical variants of those words or phrases.

[0132] As used herein, the terms “patient” or “subject” refer to members of the animal kingdom including but not limited to human beings and “mammal” refers to all mammals, including, but not limited to human beings.

[0133] As used herein, “treatment” or “treating” of a wound or defect means administration to a patient by any suitable dosage regimen, procedure and / or administration route of a composition, device or structure with the object of achieving a desirable clinical / medical end-point, including, for example, preventing infection or healing a wound.

[0134] As used herein, the term “polymer composition” is a composition comprising one or more polymers. As a class, “polymers” includes homopolymers, heteropolymers, copolymers, block polymers, block copolymers and can be both natural and synthetic. Homopolymers contain one type of building block, or monomer, whereas co-polymers contain more than one type of monomer.

[0135] As used herein, the term “oligomer” is a polymer that has a few repeating units.

[0136] A polymer “comprises” or is “derived from” a stated monomer if that monomer is incorporated into the polymer. Thus, the incorporated monomer that the polymer comprises is not the same as the monomer prior to incorporation into a polymer, in that at the very least, certain terminal groups are incorporated into the polymer backbone. A polymer is said to comprise a specific type of linkage, such as an ester, or amide linkage, if that linkage is present in the polymer.

[0137] A “moiety” is a part of a chemical compound, and includes groups, such as functional groups. As such, an antibiotic moiety is an antibiotic agent or compoundthat is modified by attachment to another compound moiety, such as a polymer monomer, e.g. an acrylate monomer as described herein.

[0138] A “functional group” or a “reactive group” is a reactive chemical moiety that can be used to covalently link a chemical compound to another chemical compound, such as include, for example and without limitation: hydroxyl, carbonyl, carboxyl, methoxycarbonyl, sulfonyl, thiol, amine, or sulfonamide.

[0139] The term “alkyl” refers to both branched and straight-chain saturated aliphatic hydrocarbon groups. These groups can have a stated number of carbon atoms, expressed as Cx-y, where x and y typically are integers. For example, C5-12, includes C5, Ce, C7, Cs, C9, C10, C11, or C12. Alkyl groups include, without limitation: methyl, ethyl, propyl, isopropyl, / ?-, s- and t-butyl, n- and s-pentyl, hexyl, heptyl, octyl, etc. Alkyl groups include groups that have two or more points of attachment (e.g., alkylene), and cycloalkyl groups, which are saturated ring groups, such as cyclopropyl, cyclobutyl, or cyclopentyl.

[0140] The term “ether” refers to an alkyl group wherein one or more of the alkyl group’s carbon atoms is replaced with an -O- group.

[0141] “Aryl” alone or in combination refers to an aromatic ring system such as phenyl or naphthyl. “Aryl” also includes aromatic ring systems that are optionally fused with a cycloalkyl ring. A “substituted aryl” is an aryl that is independently substituted with one or more substituents attached at any available atom to produce a stable compound, wherein the substituents are as described herein. “Optionally substituted aryl” refers to aryl or substituted aryl. “Arylene” denotes divalent aryl, and “substituted arylene” refers to divalent substituted aryl. “Optionally substituted arylene” refers to arylene or substituted arylene.

[0142] “Cycloalkyl” refer to monocyclic, bicyclic, tricyclic, or polycyclic, 3- to 14- membered ring systems, which are either saturated, unsaturated or aromatic. The cycloalkyl group may be attached via any atom. Cycloalkyl also contemplates fused rings wherein the cycloalkyl is fused to an aryl or hetroaryl ring. Representative examples of cycloalkyl include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. A cycloalkyl group can be unsubstituted or optionally substituted with one or more substituents as described herein below. “Cycloalkylene” refers to divalent cycloalkyl. The term “optionally substituted cycloalkylene” refers to cycloalkylene that is substituted with 1 , 2 or 3 substituents, attached at any available atom to produce a stable compound, wherein the substituents are as described herein.

[0143] An “acrylate” is an organic compound that includes, whereR is hydrogen or a methyl (i.e., methacrylate) and the dashed line represents the covalent attachment to the remainder of the compound.

[0144] A liquid crystal is a thermodynamic stable phase characterized by anisotropy of properties without the existence of a three-dimensional crystal lattice, generally lying in the temperature range between the solid and isotropic liquid phase, referred to as the mesophase. In the mesophase, the mesogens point along a common axis, called the director, in contrast to molecules in the liquid phase, which have no intrinsic order. In the solid state, molecules are highly ordered and have little translational freedom. The nematic liquid crystal phase is characterized by molecules that have no positional order but tend to point in the same direction (along the director). The smectic state is another distinct mesophase of liquid crystal substances. Molecules in this phase show a degree of translational order not present in the nematic. In the smectic state, the molecules maintain the general orientational order of nematics, but also tend to align themselves in layers or planes. Motion is restricted to within these planes, and separate planes are observed to flow past each other. The smectic state is in increased order compared to the nematic state. In the context of the present disclosure, the liquid crystals are thermotropic, meaning they undergo temperaturedependent phase transition.

[0145] An elastomer, such as an elastomer useful in conjunction with the LCE materials described herein, is a viscoelastic polymer with desired physical parameters, such as hardness, elongation at break, abrasion resistance, and tear resistance. An elastomer may be bioerodable, or may be non-bioerodable. In the context of the present disclosure, for example for use in artificial muscle, the elastomer may be non- bioerodable (e.g., do not degrade substantially or to an acceptable degree over 2 or more years when implanted in a patient), but biocompatible, such that it provides no, or substantially no, toxic or other undesirable effects in an organism or cells, such as when implanted in a human patient, and does not degrade to any substantial degree when implanted. Non-limiting examples of non-biodegradable, biocompatible (e.g., medical grade) elastomers include: polysiloxanes, silicone, polyurethanes,polyurethane siloxane copolymers, polyolefin elastomers, styrenic block copolymers, PVC, and liquid crystal materials.

[0146] Provided herein is an antibacterial liquid crystal elastomer (ALCE). The ALCE comprises a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety. The liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component. The ALCE comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from 30 °C to 45 °C.

[0147] The “nominal nematic-isotropic transition temperature (TNI)” as used herein is the temperature at which a nematic liquid crystal material transitions to an isotropic liquid crystal material. The TNI of the antibacterial liquid crystal elastomer is in a range of from 30 °C to 45 °C, or such as from 35 °C to 45 °C, such that it is useful in bioengineering and wound healing applications as described herein. For example, the antibacterial liquid crystal elastomer may have a TNI of 30 °C, 31 °C, 32 °C, 33 °C, 34 °C, 35 °C, 36 °C, 37 °C, 38 °C, 39 °C, 40 °C, 41 °C, 42 °C, 43 °C, 44 °C, 45 °C, or increments there between.

[0148] A “liquid crystal component” or “liquid crystal moiety” is an organic moiety that exhibits temperature dependence in its phase transition states, and can be referred to as “thermoresponsive” or “thermotropic”. The liquid crystal component is formed from a liquid crystal monomer.

[0149] The liquid crystal monomers used herein comprise a first terminal acrylate functional group, a second terminal acrylate functional group, a mesogenic core comprising a first end and a second end, a first flexible linker connecting the first terminal acrylate functional group to the first end of the mesogenic core, and a second flexible linker connecting the second terminal acrylate functional group to the second end of the mesogenic core.

[0150] The first terminal acrylate functional group comprises the following structure:The dotted line shows where the first terminal acrylate functional group is connected to the first flexible linker.

[0151] The second terminal acrylate functional group comprises the following structure:The dotted line shows where the second terminal acrylate functional group is covalently bonded to the second flexible linker.

[0152] The first flexible linker of the liquid crystal monomer covalently links the first terminal acrylate functional group to the first end of the mesogenic core. The first flexible linker may comprise an aliphatic carbon chain optionally substituted with an oxygen atom. For example, the aliphatic carbon chain may be a C3 - C10 aliphatic carbon chain, such as a C3 - Ce aliphatic carbon chain. For example, the first flexible linker may comprise the following structure:where n is an integer from two to nine, such as from two to five, the first dashed line attached to the carbon atom shows where the first flexible linker is covalently attached to the oxygen atom of the first terminal acrylate functional group, and the second dashed line attached to the oxygen atom shows where the first flexible linker is covalently attached to the first end of the mesogenic core.

[0153] The second flexible linker of the liquid crystal monomer covalently links the second terminal acrylate functional group to the second end of the mesogenic core. The second flexible linker may comprise an aliphatic carbon chain optionally substituted with an oxygen atom. For example, the aliphatic carbon chain may be a C3 - C10 aliphatic carbon chain, such as a C3 - Ce aliphatic carbon chain. For example, the second flexible linker may comprise the following structure:where n is an integer from two to nine, such as from two to five, the first dashed line attached to the oxygen atom shows where the second flexible linker is covalently attached to the second end of the mesogenic core, and the second dashed line attached to the carbon atom shows where the second flexible linker is covalently attached to the second terminal acrylate group.

[0154] The first flexible linker and the second flexible linker may be the same flexible linker. The first flexible linker and the second flexible linker may be different flexible linkers. The first flexible linker and the second flexible linker may further comprise a polyethylene glycol (“PEG”) group. The PEG group may have the structure -(O-CH2- CH2)n- or - (CH2-CH2-O)n-, where n is an integer ranging from two to fifty.

[0155] The mesogenic core of the liquid crystal monomer includes a first end and a second end, where the first flexible linker is covalently attached to the first end of the mesogenic core and the second flexible linker is covalently attached to the second end of the mesogenic core. The mesogenic core may comprise from one to three aromatic or aliphatic rings in linear arrangement (rod-shaped molecules) or flat disclike molecules consisting of a core of adjacent aromatic rings (discotics). The mesogen core may comprise a phenylbenzene moiety, a diphenylbenzene moiety, a benzoate moiety, or a phenyl 4-benzoyloxybenzoate moiety, for example as shown in FIG. 1. The first wavy line in the mesogenic cores depicted in FIG. 1 depict bonds forming a covalent linkage to the first flexible linker and the second wavy line in the mesogenic cores depicted in FIG. 1 depict bonds forming a covalent linkage to the second flexible linker. The mesogenic cores depicted in FIG. 1 may be modified by substitution and / or inclusion of hetero-atoms to modify the TNI of the material. Rings in the mesogen may be aromatic (e.g., aryl) or aliphatic, and may be hetero-substituted with one or more hetero atoms, such as N, O, or S. The rings in the mesogen may be optionally substituted with an alkyl group, an ether group, an ester group, a halogen, a hydroxyl group, or combinations thereof. For example, one or more of the rings may be substituted with a methyl group (see, e.g., RM82 with the center ring of the phenyl 4-benzoyloxybenzoate moiety, comprising a methyl substitution). Alternatively, one or more of the rings may be substituted with a fluoro group, or any other suitable group that is consistent with the abilities of the overall liquid crystal material to exhibit desirable thermoresponsiveness and / or to tune the thermoresponsiveness of the material. Substitutions on the one or more rings can destabilize smectic phases and thus, introduce additional ways to tune and destabilize order. Many suitable mesogenic core materials are commercially available, and / or are readily synthesized by a person of ordinary skill, e.g. as described herein.

[0156] Non-limiting examples of suitable liquid crystal monomers include, but are not limited to: 1 ,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene) (RM82)4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE)2-Methyl-1 ,4-phenylene-bis[4[3(acryloyloxy)propyloxy]benzoate] (RM257), and combinations thereof.

[0157] Additional liquid crystal monomers comprising a single terminal acrylate functional group may also be used in combination with the above described liquid crystal monomers. These additional liquid crystal monomers may be used in combination with the above described liquid crystal monomers to form the liquid crystal component and to control the cross-link density of the liquid crystal polymer network.

[0158] The additional liquid crystal monomers may comprise a terminal acrylate functional group, a terminal reactive functional group, a mesogenic core comprising a first end and a second end, a first flexible linker connecting the terminal acrylatefunctional group to the first end of the mesogenic core, and a second flexible linker connecting the terminal reactive functional group to the second end of the mesogenic core. The mesogenic cores of the additional liquid crystal monomers may be any of the mesogenic cores described herein. The first flexible linker and the second flexible linker of the additional liquid crystal monomers may be any of the first and second flexible linkers described herein.

[0159] The terminal acrylate functional group of the additional liquid crystal monomers comprises the following structure:The dotted line shows where the terminal acrylate functional group is connected to the first flexible linker.

[0160] The terminal reactive functional group of the additional liquid crystal monomers may be any reactive group, such as a nitrile group (-C=N), an epoxy group, or a terminal alkene group.

[0161] A non-limiting example of a suitable additional liquid crystal monomer includes, but is not limited to 4-cyanophenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (RM23):

[0162] A “chain extending component” or “chain extending moiety” is an organic moiety that is present within the antibacterial liquid crystal elastomer to increase the molecular weight of the elastomer and to tune the TNI of the elastomer. The chain extending component is formed from one or more chain extending monomers.

[0163] The one or more chain extending monomers may be thiol based chain extending monomers. For example, the one or more chain extending monomers may comprise a C2-C6 aliphatic carbon chain or one or more ether groups and from two or four terminal thiol groups. Non-limiting examples of suitable thiol based chain extending monomers include but are not limited to: ethane-1 ,2-dial bis(3-mercaptopropanoate) (GDMP), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), 1 ,4-benzenedimethanethiol (BDMT), a mixture thereof, or a combination thereof. For example, the TNI of the elastomer can be tuned by selecting a thiol based chain extending monomer having a longer aliphatic carbon chain. For example, the chain extending component may be formed from GDMP. Alternatively, the chain extending component may be formed from the combination of EDDT and PETMP.

[0164] The one or more chain extending monomers may be amine-based chain extending monomers. For example, the one or more chain extending monomers may comprise a C2-C6 aliphatic carbon chain and from one to two amine groups. Nonlimiting example of suitable amine based chain extending monomers include, but are not limited to: n-butylamine, polypropylene glycol) bis(2-aminopropyl ether).

[0165] The ALCEs described herein comprise pendant antibiotic moieties. A “pendant antibiotic moiety” is an antibiotic that is covalently attached to the liquid crystal oligomers that are used to form the liquid crystal polymer network of the ALCE. Antibiotics are any compound with antibacterial properties, including but not limited to antibiotic peptides. The pendant antibiotic moiety may be provided in the liquid crystal oligomer as the pendant antibiotic moiety component. The pendant antibiotic moiety may be covalently attached to a surface of the liquid crystal oligomer as the pendant antibiotic moiety component.

[0166] Non-limiting examples of antibiotic moieties include, but are not limited to norfloxacin, acyclovir, afloxacin, ampicillin, amphotericin B, atovaquone, azithromycin, ciprofloxacin, clarithromycin, clindamycin, clofazimine, dapsone, diclazaril, doxycycline, erythromycin, ethambutol, fluconazole, fluoroquinolones, foscarnet, ganciclovir, gentamicin, iatroconazole, isoniazid, ketoconazole, levofloxacin, lincomycin, miconazole, neomycin, ofloxacin, paromomycin, penicillin, pentamidine, polymyxin B, pyrazinamide, pyrimethamine, rifabutin, rifampin, sparfloxacin, streptomycin, sulfadiazine, tetracycline, tobramycin, trifluorouridine, trimethoprim sulphate, Zn-pyrithione, or vancomycin. As an example, the pendant antibiotic moiety is norfloxacin. The antibiotic molecules may be linked to the ALCEs and / or to the as- formed ALCE matrix by any effective covalent linking method, and may preferably form a labile or enzymatically-digestible (e.g., in vivo) bond, such as an ester or amide bond with a reactive group as are generally present in antibiotics such as the listed antibiotics, such as, for example and without limitation, a carboxyl, amine, phosphate,sulfhydryl, or hydroxyl group. In non-limiting embodiments, the antibiotic moiety may be an antimicrobial peptide. Covalent attachment of antibiotic moieties may occur such that antibiotic moieties are evenly distributed throughout the bulk of the ALCE material, concentrated at the surface of the bulk of the ALCE material, or otherwise distributed throughout the bulk of the ALCE material.

[0167] The pendant antibiotic moiety component of the liquid crystal oligomers may be formed from a monomer comprising the antibiotic moiety. The monomer comprising the antibiotic moiety may comprise the following structure:where Ri is the antibiotic moiety described herein, X is -NH-, -S-, -O-, or -OC(O)-, and Y is a bond or a linker. When X is -NH-, the antibiotic moiety or the linker (when present) is attached to the monomer through an amide bond. When X is -S-, the antibiotic moiety or the linker (when present) is attached to the monomer through a thioester bond. When X is -O- the antibiotic moiety or the linker (when present) is attached to the monomer through an ester bond. When X is -OC(O)-, the antibiotic moiety or the linker (when present) is attached to the monomer through an anhydride bond. The linker, when present, facilitates the attachment of the antibiotic to the acrylate portion of the monomer, where the linker has no substantial negative effect on the activity of the antibiotic moiety. The linker may be attached to the antibiotic moiety by any suitable linkage, such as by a carbon-carbon bond, an ester, a thioester, an amine, an ether, an amide, a carbonate, or a carbamate linage. The linker may be a hydrocarbyl that is including only carbons and hydrogens, or optionally comprising one or more hetero-atoms, such as N, O, and / or S. The linker may comprise an ether group. Alternatively, the linker may comprise an aliphatic carbon chain that is optionally substituted with a hydroxyl group. These monomers comprising the antibiotic moiety can be prepared in any useful manner, and of ordinary skill in the art would be able to modify acrylates, such as meth acrylates, with antibiotics. According to the type of chemical bond used to attach the antibiotic moiety, the elastomers will either elute the antibiotic according to specific controlled release profiles, or anchor the antibiotic for contact-kill. The monomer comprising the antibiotic moiety may be a monomer comprising norfloxacin and may comprise the following structure:

[0168] The liquid crystal oligomers may further comprise a non-liquid crystalline component. The “non-liquid crystalline component” or “non-liquid crystalline moiety” is an organic moiety that is not the liquid crystal component or the chain extending component and is present within the antibacterial liquid crystal elastomer to tune the TNI of the elastomer. The non-liquid crystalline component is formed from a non-liquid crystalline monomer.

[0169] A non-limiting example of a non-liquid crystalline monomer includes, but is not limited to glyoxal bis(diallyl acetal) (GBDA).

[0170] The liquid crystal oligomers formed from liquid crystal monomers, the monomer comprising the antibiotic moiety (when present), the chain extending monomers, and optionally the non-liquid crystalline monomers, may be formed from a composition that has a molar ratio of the liquid crystal monomers to the monomers comprising the antibiotic moiety to the chain extending monomers to the noncrystalline monomers of 0.1 -1 .5:0.05-0.65:0.01 -1 .5:0-0.5, such as 0.5-1 :0.10-0.55:0.5- 1 :0-0.2.

[0171] The liquid crystal oligomers comprising the liquid crystal component, the chain extender component, and the pendant antibiotic moiety component may be crosslinked using a cross-linker in the presence of one or more catalysts, one or more inhibitors of thermal polymerization, and / or one or more photoinitiators.

[0172] Alternatively, the liquid crystal oligomers comprising the liquid crystal component, the chain extender component, the pendant antibiotic moiety component (when present), and the non-liquid crystalline component may be cross-linked without a cross-linker. For example, the liquid crystal oligomers comprising the liquid crystal component, the chain extender component, the pendant antibiotic moiety component (when present), and the non-liquid crystalline component may be cross-linked in the presence of one or more catalysts, one or more inhibitors of thermal polymerization, and / or one or more photoinitiators.

[0173] The cross-linker is included to connect the liquid crystal oligomers together to form the liquid crystal polymer network. Non-limiting examples of suitable crosslinkers include, but are not limited to: 1 ,3,5-triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)- trione (TATATO), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, an imidazolium-functionalized cross-linker, mixtures thereof, and combinations thereof.

[0174] The imidazolium-functionalized cross-linker may be incorporated into the liquid crystal monomers to provide an ionic component. The imidazolium- functionalized cross-linker may comprise the following structure:

[0175] The cross-linker, when present, may be used in a molar ratio of the liquid crystal monomer to the cross-linker of 1 : 0.2 to 0.4.

[0176] The one or more catalysts are included to increase the polymerization rate. Non-limiting examples of suitable catalysts include, but are not limited to: triethylamine (TEA), dipropylamine (DIPA), mixtures thereof, and combinations thereof. The catalyst, when present, may be used in an amount ranging from 0.01 mole % to 0.1 mole %, based on the total amount of liquid crystal monomer in the composition.

[0177] The one or more inhibitors are included to prevent any undesirable polymerization of the liquid crystal oligomers during processing, such as during the melting process of the monomers. Non-limiting examples of suitable inhibitors of thermal polymerization include, but are not limited to: 2,6-Di-tert-butyl-4-methylphenol (BHT), methylhydroquinone, mixtures thereof, and combinations thereof. The inhibitor, when present, may be used in an amount ranging from 1 .0 weight percent (wt. %) to 3.0 wt. %, based on the total amount of monomer in the composition.

[0178] The one or more photoinitiators are included to initiate the polymerization of the liquid crystal oligomers when subject to ultraviolet (UV) radiation. Non-limiting examples of suitable photoinitiators include, but are not limited to those of the Irgacure family of photoinitiators and free radical initiators capable of generating free radicals,such as organic peroxy compounds, acetophenones, or benzophenones. For example, the photoinitiator may be 2-Benzyl-2-(dimethylamino)-4’- morpholinobutyrophenone (Irgacure 369; 1-369). The photoinitiator, when present, may be used in an amount ranging from 1 .0 wt. % to 3.0 wt. %, based on the total amount of monomer in the composition.

[0179] In one non-limiting example, the liquid crystal oligomers used to form the antibacterial liquid crystal elastomer may be formed from the combination of C6BAPE, EDDT, PETMP, GBDA, andin the presence of a catalyst, an inhibitor of thermal polymerization, and a photoinitiator.

[0180] Conductive or ionic additives to the elastomers described herein produce a resistive heater that heats the ALCE to actuate contraction of the elastomer. For example, the ALCE may further comprise an ionic component, an electronic conductive material, or combinations thereof.

[0181] The ionic component may be formed by doping the ALCE with an ionic liquid, the inclusion of the imidazolium-functionalized cross-linker described above, or combinations thereof.

[0182] The ionic liquid may include, but is not limited to 1 -hexyl-3-methylimidazolium bis(trifluormethylsuflonyl)imide, 1 -hexyl-3-methylimidazolium hexafluorophosphate, or combinations thereof. Doping the ALCE with an ionic liquid may be completed during the preparation of the ALCE, after the formation of the ALCE, or combinations thereof. For example, the liquid crystal oligomers used to form the ALCE may be doped with up to 0.07 moles of an ionic liquid with respect to 1 .0 moles of liquid crystal monomer. Alternatively, the ALCE may be doped with an ionic liquid after the ALCE is formed, for example, by submerging the ALCE in the ionic liquid. The ALCE may be doped with the ionic liquid during the preparation of the liquid crystal oligomers and may then also be submerged in the ionic liquid after the ALCE is formed. Useful electronic conductive materials to add to the ALCE include, for example and without limitationeutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires (e.g., silver nanowires or gold nanowires), integral / segmented / fractured metallic coatings (e.g., silver coatings or gold coatings), conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof. The electronic conductive material may be added to the composition prior to forming cross-linking and forming the liquid crystal polymer network. Alternatively, the electronic conductive material may be added after cross-linking and forming the liquid crystal polymer network. For example, a metallic coating, such as a silver coating or a gold coating, may be applied onto the surface of the ALCE. Those of skill will appreciate that other conductive materials and coatings may be applied to the surface of the ALCE, including, without limitation, PEDOT:PSS, Carbon Nanotubes, and / or eGain Liquid Metal.

[0183] The liquid crystal components of the liquid crystal oligomers may be aligned. The liquid crystal components of the liquid crystal oligomers may be aligned prior to cross-linking the liquid crystal oligomers. Alternatively, the liquid crystal components of the liquid crystal oligomers may be aligned after cross-linking the liquid crystal oligomers. The aligning of the liquid crystal components can be any method known to one of ordinary skill in the art, such as through the application of a shear force (e.g., stretching or extrusion printing), electrospinning, fiber drawing from the melt, surface alignment using alignment layers (e.g., rubbed polyimides, poly(vinyl alcohol), or photo-patterned azobenzene-based dyes), or magnetic fields. As an example, the aligning of the liquid crystal components of the liquid crystal oligomers is completed through stretching. Alternatively, the liquid crystal oligomers can be deposited in an extrusion printing process which aligns the liquid crystal components of the liquid crystal oligomers.

[0184] The ALCEs as described herein can be used as an artificial muscle. Those of skill in the art will appreciate that the ALCEs described herein may be used to produce an artificial form of any type of muscle, including, without limitation, smooth muscle, striated muscle, skeletal muscle, cardiac muscle, sphincters, and the like. For example, the ALCE described herein may undergo a reversible change in shape in response to an external stimulus, such heat generated by resistive heating. For example, the ALCE described herein may further include an ionic component, an electronic conductive material, or combinations thereof and may undergo a reversible change in shape in response to an external stimulus, such heat generated by resistiveheating. As may be appreciated, since the ALCEs described herein may be used to form any sort of muscle, they may similarly be arranged in any shape, arrangement, and / or orientation. In non-limiting embodiments, the ALCEs are arranged in an accordion arrangement. Without wishing to be bound by the theory, it is believed that an accordion arrangement allows for heating of the ALCEs, and thus a change in orientation of the ALCE material as described herein, without concomitant heating of surrounding tissue.

[0185] Also provided herein is a method of making an ALCE. The method comprises: forming liquid crystal oligomers comprising a pendant antibiotic moiety, depositing the liquid crystal oligomers onto the surface of a substrate; aligning the liquid crystal components of the liquid crystal oligomers; and cross-linking the liquid crystal oligomers to form a liquid crystal polymer network. The liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component. Forming the liquid crystal oligomers comprises: preparing a mixture of liquid crystal monomers, chain extender monomers, optionally, monomers comprising an antibiotic moiety, and optionally, non-liquid crystalline monomers, and heating the mixture to form the liquid crystal oligomers. The liquid crystal monomers, chain extending monomers, monomers comprising the antibiotic moiety, and the non-liquid crystalline monomers can be any of the monomers described herein and used in any of the amounts described herein. The ALCE comprises a TNI in a range of from 30 °C to 45 °C.

[0186] The liquid crystal monomers, the chain extender monomers, the monomers comprising the antibiotic moiety, and the non-liquid crystalline monomers may be any of the liquid crystal monomers, the chain extender monomers, the monomers comprising the antibiotic moiety, and the non-liquid crystalline monomers described herein.

[0187] Additional liquid crystal monomers, cross-linkers, one or more catalysts, one or more inhibitors of thermal polymerization, and / or one or more photoinitiators, as described herein, may be added to the mixture of the liquid crystal monomers, the chain extender monomers, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers prior to heating. The additional liquid crystal monomers may be any of the additional liquid crystal monomers described herein. The cross-linkers, one or more catalysts, one or more inhibitors of thermal polymerization, and / or one or more photoinitiators can be any of the cross-linkers, oneor more catalysts, one or more inhibitors of thermal polymerization, and / or one or more photoinitiators described herein. An ionic liquid as described herein, an electronic conductive material as described herein, or combinations thereof may be added to the mixture of the liquid crystal monomers, the chain extender monomers, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers prior to heating.

[0188] The liquid crystal oligomers may be deposited onto the surface of a substrate. The substrate can be any substrate that easily releases the ALCE after cross-linking. For example, the substrate may be a glass substrate. The substrate may be coated with a composition that allows for easy release of the ALCE after cross-linking. The liquid crystal oligomers may be poured directly onto the substrate after the heating step. Alternatively, the liquid crystal oligomers may be deposited onto the substrate in an extrusion printing process.

[0189] In the extrusion printing process, the liquid crystal oligomers are extruded through a print-head orifice that moves along a print direction to form an extruded film of ALCE. The liquid crystal oligomers can be printed in any three-dimensional shape and are cured. For example, a layer of liquid crystal oligomers may be applied and then cured to form a filament (e.g., a film) and a subsequent layer of the liquid crystal oligomers may be applied on top of the filament and then cured to form a filament (e.g., a film). This process may be repeated until the desired three-dimensional shape is achieved. The liquid crystal oligomers may be stored in a reservoir above the print- head and are extruded from the reservoir through the orifice in the print-head by applying pressure to the liquid crystal oligomers in the reservoir, such that shear forces are applied to the extruded ink as it passes through the orifice. The application of such shear forces substantially aligns the liquid crystal components in the print direction.

[0190] Also provided herein is a device. The device comprises a first component comprising a first ALCE, a second component comprising a second ALCE comprising an ionic component, an electronic conductive material, or combinations thereof, wherein the second component is in direct contact with the first component, and a resistive heating component in electrical contact with the second component, wherein the first component and the second component undergo a reversible change in shape in response to activation of the resistive heating component. The first ALCE comprises a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystalcomponent, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, and comprises a TNI in a range of from 30 °C to 45 °C, such as from 35 °C to 45 °C. The first ALCE can be any of the ALCEs described herein. The liquid crystal oligomers of the first ALCE can be any of the liquid crystal oligomers described herein. The liquid crystal component, chain extender component, pendant antibiotic moiety component, and non-liquid crystalline component of the liquid crystal oligomers of the first ALCE can be any of the liquid crystal component, chain extender component, pendant antibiotic moiety component, and non-liquid crystalline component, respectively, described herein. The second ALCE comprises an ionic component, an electronic conductive material, or combinations thereof and a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, and comprises a TNI in a range of from 30 °C to 45 °C, such as from 35 °C to 45 °C. The second ALCE can be any of the ALCEs described herein. The liquid crystal oligomers of the second ALCE described herein can be any of the liquid crystal oligomers described herein. The liquid crystal component, chain extender component, pendant antibiotic moiety component, and non-liquid crystalline component of the liquid crystal oligomers of the second ALCE can be any of the liquid crystal component, chain extender component, pendant antibiotic moiety component, and non-liquid crystalline component, respectively, described herein.

[0191] An exemplary device 10 is provided in FIG. 2 and comprises a first component 12, a second component 14, and a resistive heating component 16. The second component 14 is in direct contact with the first component 12. The resistive heating component 16 is in contact with the second component 14.

[0192] A “resistive heating component” generates heat by the passage of an electric current through a conductor. The heat generated by the resistive heating component causes the first ALCE of the first component and the second ALCE of the second component to undergo a temperature-dependent phase transition, such as a reversible change in shape.

[0193] The first ALCE of the first component 12 may be the same as the second ALCE of the second component 14. The first ALCE of the first component 12 may be different from the second ALCE of the second component 14.

[0194] The liquid crystal components of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer may be aligned. The liquid crystal components of the liquid crystal oligomers of the second antibacterial liquid crystal elastomer may be aligned. The liquid crystal components of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the liquid crystal components of the liquid crystal oligomers of the second antibacterial liquid crystal elastomer may be aligned in the same orientation.

[0195] The first ALCE of the first component 14 may further comprises an ionic component, an electronic conductive material, or combinations thereof, as described herein.

[0196] The first component 12 may be adhered to the second component 14. For example, a polymerizable monomer composition may be added to the surface of the first component 12. The second component 14 may be placed in contact with the polymerizable monomer composition present on the first component 12 and then cured. The polymerizable monomer composition may be any suitable polymerizable monomer composition and may be applied by any suitable method, such as through spin coating. For example, the polymerizable monomer composition may be the same composition that is used to form the liquid crystal oligomers described herein. Alternatively, the polymerizable monomer composition may comprise a single monomer of the monomers described herein. The polymerizable monomer composition may further comprise an ionic component, an electronic conductive material, or combinations thereof, which may be any of the ionic components or electronic conductive materials described herein.

[0197] When a current is applied to the resistive heating component 16 (e.g., one or more electrodes) in contact with the second component 14, the second component 14 actuates the first component 12, making the first component 12 behave like a muscle.

[0198] The device 10 may further comprise an inductive coupling receiver 18 and an inductive coupling transmitter 20. The inductive coupling receiver 18 may be configured to produce a current through the resistive heating component 16 by inductive coupling with the inductive coupling transmitter 20. An exemplary diagram for the device 10 comprising an inductive coupling receiver 18 and an inductive coupling transmitter 20 is provided in FIG. 3, where Ct and Cr are capacitors that are electrically connected to the inductive coupling transmitter 20 and the inductive coupling receiver 18, respectively. The value of Lt on the inductive coupling transmitter20 side and the value of Lron the inductive coupling receiver 18 side may be matched to efficiently couple the device 10 and the inductive coupling receiver 18 to the inductive coupling transmitter 20, remotely. The inductive coupling transmitter 20 and the capacitor Ct create an LC circuit (i.e., an electrical circuit that includes an inductor and a capacitor connected together) which can transmit power to the resistive heating component 16 of the device 10. A system as shown in FIG. 3 may include an optional conditioning circuit 30.

[0199] Inductive coupling, or magnetic field coupling, occurs when energy is coupled from an inductive coupling transmitter to inductive coupling receiver through a magnetic field. The inductive coupling is performed at hundreds of Kilohertz (kHz) to gigahertz (GHz) frequencies, for example about 1 kHz to about 1 GHz, about 100 kHz to about 100 MHz, about 100 kHz to about 90 MHz, about 100 kHz to about 80 MHz, about 100 kHz to about 70 MHz, about 100 kHz to about 60 MHz, about 100 kHz to about 50 MHz, about 100 kHz to about 40 MHz, about 100 kHz to about 30 MHz, about 100 kHz to about 20 MHz, and / or about 100 kHz to about 10 MHz, all values and subranges therebetween inclusive.

[0200] The inductive coupling receiver 18 may be spaced apart from the inductive coupling transmitter 20. For the example, the space between the inductive coupling receiver 18 and the inductive coupling transmitter 20 may range from several milliliters to several centimeters.

[0201] The inductive coupling receiver 18 may be fabricated from conductive soft polymers, metals, or combinations thereof. For example, the inductive coupling receiver 18 may comprise a metal coil. The conductive soft polymer may include polydimethylsiloxane (PDMS) or Ecoflex™ (i.e., a silicone rubber) composited with an electronic conductive material. The electronic conductive material may be any of the electronic conductive materials described herein. For example, the inductive coupling receiver 18 may include a combination of PDMS and eGain. Alternatively, the inductive coupling receiver 18 may include a combination of a liquid crystal elastomer (LCE) and eGain. Alternatively, the inductive coupling receiver 18 may include a combination of a LCE and carbon nanotubes.

[0202] The inductive coupling transmitter 20 is connected to a power source, such as a battery or AC-DC power supply / adaptor, and may activated by a wireless actuator, for example, a remote. The inductive coupling transmitter 20 may comprise a metal coil.

[0203] The device 10 may be an implantable device. “Implantable device” means that the device can be partially or wholly implanted into a patient. For example, the inductive coupling transmitter 20 may be adhered to a patient’s skin, and the device 10 comprising the inductive coupling receiver 18 may be implanted into the body of the patient. The inductive coupling used to activate the device 10 remains within the energy thresholds of 10 Watts per kilogram per 10 grams (W / kg per 10 g) of tissue.

[0204] In some examples, the resistive heating component 16 is electrically and / or mechanically connected to the second component 14. For example, the resistive heating component 16 may be electrically connected to the second component 14, such as through one or more wires. For example, the resistive heating component 16 may be mechanically connected to the second component 14. In this case, the second component 14 is the substrate on which the resistive heating component 16 resides, as shown in FIG. 2. For example, the resistive heating component 16 may be both electrically and mechanically connected to the second component 14, such as through an electrical connector. The electrical connector may comprise a material that is similar to those described for the inductive coupling receiver 18.

[0205] The inductive coupling receiver 18 may be placed in direct contact with the device 10. Alternatively, the inductive coupling receiver 18 may be connected to the device 10 through one or more wires, as shown in FIG. 3. Alternatively, the device 10 can be used as the inductive coupling receiver 18.

[0206] The first component 12 may be arranged as a sphincter about an opening. For example, the sphincter may be a urological, bladder, urethral, gastrointestinal, bowel, or anal sphincter. As used herein, sphincter may be any device which opens, closes, or modulates the flow or movement of a substance through a lumen. It can also be used as fallopian tube clips for on-command reversible tubal ligation (reversible birth control).

[0207] Alternatively, the first component 12 may be arranged as a mesh comprising a first isotropic component 22 that expands and contracts in a first direction and a second isotropic component 24 that expands and contracts in a second direction (FIG. 4). Heating the first isotropic component, using resistive heating, causes a contraction of the mesh along the first direction. Heating the second isotropic component 24, using resistive heating, causes a contraction of the mesh along the second direction. The first isotropic component 22 may be heated by a first resistive heating component and the second isotropic component 24 may be independently heated by a secondresistive heating component. Therefore, the contraction of the first isotropic component 22 may be controlled independently of the contraction of the second isotropic component 24. The mesh may be placed on a wound and the generated contractions can be used for wound healing, such as scar-free wound healing.

[0208] The device 10 may be at least partially encapsulated in a secondary packaging. For example, at least a portion of the first component 12, the second component 14, and / or the resistive heating component 16 may be encapsulated in the secondary packaging. The secondary packaging may be any biocompatible or biostable material, such as a biocompatible polymer. For example, the secondary packaging may comprise a biocompatible polymer such as polydimethylsiloxane (PDMS) or parylene. For example, the first component 12, the second component 14, the inductive coupling receiver 18, and any microelectronic components associated with the inductive coupling receiver may be contained in the secondary package, where the secondary package still allows the first component 12 and second component 16 to undergo the temperature-dependent phase transition, such as a reversible change in shape.

[0209] It will be readily appreciated by those skilled in the art that modification may be made to the invention without departing from the concepts disclosed in the foregoing description. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof. Examples

[0210] To develop smart antibacterial liquid crystal elastomers (ALCEs) for actuation within the human body within a biocompatible temperature window (30-40 °C), nonliquid crystalline acrylate functionalized Norfloxacin has been covalently incorporated into the ALCE matrix. The antibacterial properties of Norfloxacin and polymerized acrylate-functioned Norfloxacin have been reported (see Dizman et al. “Synthesis, characterization, and antibacterial activities of novel methacrylate polymers containing norfloxacin”, Biomacromolecules, 2005, 6(1 ): 514-520 and Moon et al. “Antimicrobial activity of a monomer and its polymer based on quinolone”, Journal of applied polymer science, 2003, 90(7): 1797-1801 ). The tunability of the thermomechanical properties of these ALCEs can be used as a customizable platform to enable biomedical devices that can actively modulate biomechanical stress states using biocompatible stimuli, while presenting antibacterial responses to prevent the onset of secondary infectionsfollowing implantation. This study focuses on the development of smart ALCEs using acrylate-functionalized Norfloxacin as the antibacterial agent.Example 1 - Synthesis and Evaluation of Antibacterial Liquid Crystal Elastomer A

[0211] An ALCE was synthesized by incorporating acrylate functionalized norfloxacin (AFN) into a liquid crystal elastomer backbone, the backbone prepared from 1 ,4-Bis- [4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene (RM82), thiol chain extenders / crosslinkers, thermal inhibitors and photoinitiators. The compositions modulate the thermomechanical response of the antibacterial liquid crystal elastomer to be within a biocompatible temperature window.Materials and Methods

[0212] Synthesis of an Acrylate-Functionalized Norfloxacin (AFN) Monomer: Norfloxacin (1 ) and glycidyl methacrylate (2) were added in a 1 :1.1 mole ratio to a round bottom flask, dissolved into dimethylformamide, and then stirred at 40 degrees Celsius (°C) for 24 hours (FIG. 5). The completion of the reaction was confirmed by thin layer chromatography. The reaction mixture was cooled to room temperature, poured into water, and then extracted with chloroform. The chloroform was concentrated in a vacuum using rotary vapor to give the crude product. The crude product was recrystallized using chloroform and hexane solvents. The purity and structure of AFN (1 -ethyl-6-fluoro-7-(4-(2-hydroxy-3-(methacryloyloxy)propyl)piperazin-1 -yl)-4-oxo-1 ,4-dihydroquinoline-3 carboxylic acid) (3) was characterized using NMR.

[0213] Synthesis of ALCE A: The chemical structures of the materials used in the synthesis reaction are provided in FIG. 6A and a schematic of the method for preparing the ALCE is provided in FIG. 6B.

[0214] 1 mole of ethane-1 ,2-dial bis(3-mercapto propanoate) (GDMP) and two drops of triethyl amine (TEA) were added to a glass vial and mixed well. 1 mole of RM82 and the synthesized AFN, in a molar ratio of 0.18, 0.37, or 0.55, were added to the glass vial and were melted using a hot gun and were vortexed for 30 seconds. 0.3 moles of 1 ,3,5-Triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)-trione (TATATO), 2 weight percent (wt. %) of butylated hydroxytoluene (BHT) based on the total monomer concentration (i.e., RM82, GDMP, AFN, and TATATO), and 2 wt. % of 2-Benzyl-2- (dimethylamino)-4'-morpholinobutyrophenone (I-369) based on the total monomerconcentration were added to the same vial, melted using a hot gun, and the vortexed for 30 seconds.

[0215] The mixture was transferred onto an Ease-release coated glass substrate with 250 pm spacers and was kept at 100 °C on a hot plate in order to maintain the mixture in a molten state. Another glass substrate, which was also coated with Ease-release, was positioned over the mixture in the molten state and the two glass substrates were clipped together at the edges of the glass using binding clips. This glass cell assembly was kept at 80 °C for 1 hour, such as on a hot plate or in an oven, to complete the thiol- Michael / thiol-ene reaction.

[0216] The liquid crystal oligomer mixture was cured by exposing both sides of the glass cell assembly with ultraviolet (UV; Omni Cure, Lumen Dynamics) light intensity of 50 milliWatts per square centimeter (mW / cm2) at 80 °C for 40 minutes.

[0217] The glass cell assembly was opened by removing the binding clips and the glass substrates were removed from the cured ALCE. The ALCEs were cut to size, kept in a translation stage, and then stretched in a single direction to 250% strain.

[0218] Confirmation of Alignment: The alignment of the liquid crystal component after stretching was confirmed using a polarizing optical microscope (POM) at 0° and 45° angles with respect to the cross polarizers.

[0219] Thermomechanical Property Evaluation: The thermomechanical properties of the uniaxial stretched elastomers, which were approximately 5 millimeters (mm) wide by 100 microns (pm) thick, were measured as a function of temperature from 25 °C to 60 °C. A temperature-controlled hotplate was used to perform this experiment and a micro viewer was used to capture images of the initial length of the elastomers at 21 °C and the final length of the elastomers at 40 °C.Results

[0220] The stretching of ALCE caused the mesogen of the liquid crystal component to align parallel to the stretching direction to form a uniaxial aligned antibacterial liquid crystal elastomer, as shown in FIGS. 7A and 7B. Thus, a uniaxial aligned antibacterial liquid crystal elastomer was prepared.

[0221] The change in length of the elastomers from 21 °C to 40 °C is shown in FIGS. 8A and 8B, where increasing the temperature of the elastomers caused a decrease in the length of the elastomer along the prior stretching direction, which defined the molecular / nematic orientation (FIG. 8B). The TNI of ALCE A was approximately 40 °C.

[0222] The thermal strain response of the antibacterial liquid crystal elastomers was determined using the following formula:where LT represents the length of the sample at temperature T, and Lo is the initial length.

[0223] As shown in FIG. 9, the strain of the antibiotic liquid crystal elastomer increased from 21 % to 28% at body temperature (37°C) when the molar ratio of AFN was increased from 0.18 to 0.55, while keeping RM82, GDMP, and TATATO constant. Example 2 - Synthesis and Evaluation of Antibiotic Liquid Crystal Elastomer B

[0224] An antibacterial liquid crystal elastomer was synthesized by incorporating AFN into a liquid crystal elastomer backbone, the backbone prepared from 4-(6- (acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy)benzoate (C6BAPE), thiol chain extenders / crosslinkers, non-liquid crystalline monomers, thermal inhibitors and photoinitiators.Materials and Methods

[0225] Synthesis of Antibacterial Liquid Crystal Elastomer B: C6BAPE was synthesized as previously described in Bauman et al. (Angewandte Chemie International Edition, 2022). AFN was synthesized as described in Example 1 . 2, 2’- (ethylenedioxy) diethanethiol (EDDT), glyoxal bis(diallyl acetal) (GBDA), photoinitiator Irgacure 369 (I-369), radical inhibitor butylated hydroxytoluene (BHT), and basecatalyst dipropylamine (DIPA) were purchased from Alrich. The chemical structures of the materials used in the synthesis reaction are provided in FIG. 10.

[0226] The solid reagents, C6BAPE, AFN, I-369, and BHT, were added to a 5 milliliter (mL) glass vial, melted using a hot gun, and vortexed for 30 seconds. To this mixture, GBDA, DPA, EDDT, and PETMP, sequentially, were added to the vial. The mixture was melted using a hot gun and vortexed for 1 minute, 30 seconds. The molar ratio of C6BAPE, AFN, EDDT, PETMP, and GBDA was 0.9:(0.1 , 0.2, 0.3): 0.9: 0.1 : 0.1. Here, the amount of C6BAPE, EDDT, PETMP, and GBDA were held constant while the molar ratio of AFN was varied at 0.1 moles, 0.2 moles, or 0.3 moles. The mixture included 1 .5 wt. % of I-369, 1 wt. % of BHT, and 0.5 wt. % of DIPA, based on the total monomer concentration (i.e., C6BAPE, AFN, EDDT, PETMP, and GBDPA).

[0227] The mixture was transferred onto an Ease-release coated glass substrate with 250 pm spacers and was kept at 80 °C on a hot plate to maintain the mixture in amolten state. Another glass substrate, which was also coated with Ease-release, was positioned over the mixture in the molten state and the two glass substrates were clipped together at the edges of the glass using binding clips. The glass cell assembly was kept at about 80 °C to 85 °C for 1 hour, such as on a hot plate or in an oven, to complete the thiol-Michael / thiol— ene reaction.

[0228] Thermomechanical Training for Reversible Actuation: A glass cell assembly was opened by removing the binding clips and the glass substrates were removed from the cured antibiotic liquid crystal elastomer. The antibacterial liquid crystal elastomer was cut to the desired dimensions. One side of the antibacterial liquid crystal elastomer was fixed in a custom-made stretching / cooling apparatus. The antibacterial liquid crystal elastomer was stretched to 250% strain and the elastomer was cooled to 5 °C for 5 minutes. The film was then photo-polymerized at 10 °C with 365 nanometers UV (Omni Cure, Lumen Dynamics) light at an intensity of 125 mW / cm2for 15 minutes while mechanically retaining the strain.

[0229] Thermomechanical Training for Irreversible Actuation: After 24 hours in an oven at about 80 °C to 85 °C, a glass cell assembly was brought to room temperature and then cooled to 5*0 for 5 min. The liquid crystal oligomer mixture was cured by exposing both sides of the glass cell assembly with UV (Omni Cure, Lumen Dynamics) light intensity of 125 mW / cm2at 10 °C for 15 minutes. The glass cell assembly was opened by removing the binding clips and the glass substrates were removed from the cured antibiotic liquid crystal elastomer. The antibiotic liquid crystal elastomers were cut to size, kept in a translation stage, and then stretched in a single direction to 250% strain.Results

[0230] The process of stretching the antibacterial liquid crystal elastomers for reversible actuation, caused the mesogens of the liquid crystal component to align parallel to the stretching direction, which formed a uniaxial aligned planar antibacterial liquid crystal elastomer. The photopolymerization after stretching served to “freeze in” the alignment since the strain was mechanically retained during polymerization.

[0231] The process of stretching the antibacterial liquid crystal elastomers for irreversible actuation, caused the mesogens of the liquid crystal component to align parallel to the stretching direction.Prophetic Example 1 - Three-Dimensional Printing of Antibacterial Liquid Crystal Elastomers

[0232] The composition used to prepare ALCE A or the composition used to prepare ALCE B will be loaded into the reservoir of a print-head as an “ink”, as shown in FIG. 1 1 . The temperature of extrusion will be chosen to be within the nematic temperature window of the compositions. A range of patterns will be printed to align the director orientation with the raster direction and then the printed component will be cured.

[0233] The extrusion printing system will also be used to deposit functionally graded assemblies of composite antibacterial liquid crystal elastomers (cALCE), where different portions of the actuator can be triggered at different temperatures and / or electrical inputs (when a conductive material is included). As a result, powering the actuators can enable sequential actuation of different portions of the device to deliver dynamic actuation profiles. An extrusion printing process will be adapted from the process provided in U.S. Patent No. 1 1 ,014,285, which is incorporated herein by reference in its entirety.

[0234] A conductive material, such as eGain or carbon nanotubes, will also be mixed into the compositions prior to extrusion to allow the actuation of the antibacterial liquid crystal elastomers using an electrical stimulus.Prophetic Example 2 - Remote Actuation of cALCE

[0235] Harnessing the large strain actuation in a cALCE within the human body will be accomplished by wirelessly powering the cALCE, such as through inductive coupling. For example, inducting coupling at 100’s MHz to GHz frequencies will be used to optimize the coupling efficiency with a miniaturized antenna. Near field and far field coupling strategies will be used to couple energy to cALCE actuators, while remaining within energy thresholds of 10 Watts per kilogram per 10 grams (W / kg per 10 g) of tissue.

[0236] As shown in FIG. 3 a receiver coil will be coupled to the transmitter coil at the resonant condition and the transferred energy is transduced into mechanical actuation via resistive heating of the cALCE, where the separation of the coils can range from millimeters to several centimeters.

[0237] The ALCE can be ALCE A of Example 1 or ALCE B of Example 2, further comprising a conductive material that is dispersed through the volume.Prophetic Example 3 - Self-regulated contactless actuation

[0238] The cALCE may also be used as a receiver coil or innervates the cALCE actuator with a deformable receiver coil. In this configuration, the contactless actuation of the cALCE powers the actuation using biocompatible stimuli. The resulting actuationmodulates the geometry of the receiving coil and in turn will disrupts the inductive coupling to the transmitter coil. This presents a framework for self-regulating the actuation by nascently self-limiting the actuation.

[0239] Following the decoupling from the transmitter coil, the actuator will relax and the inductor will revert to the prior configuration, where it is coupled to the transmitter. Having done so, the actuator actuates again and the cycle will continue. This framework also allows for hierarchical actuation profiles using assemblies of cALCE with different thresholds for triggering actuation, defined as a function of their composition and 3D printing / alignment process parameters.Prophetic Example 4 - Adaptive Bandage

[0240] A hierarchically structured bandage according to FIG. 12 will be prepared. An ALCE, such as the elastomers prepared according to Examples 1 or 2, will prepared in an isotropic mesh-like configuration. This ALCE in the mesh-like configuration will be cross-linked and then biaxially stretched. This highly deformable antibacterial liquid crystal elastomer topology would be capable of large irreversible biaxial contraction when subjected to a biocompatible heat treatment.

[0241] This cross-linked and then biaxially stretched antibacterial liquid crystal elastomer in the mesh-like configuration will be augmented with monodomain cALCE (which are uniaxially aligned in the nematic state) so that the cALCE can generate contractile strains when subjected to an electrical stimulus. These cALCE will stretch the central mesh-like configuration, on-demand, when subjected to an electrical stimuli, such as less than 5 Volts (V). Thus, the bandage can initially apply a large compressive stress field that can be dynamically modulated.Prophetic Example 5 - Artificial Sphincters and Assistive Devices

[0242] A three-dimensional cALCE will be printed in the form a sphincter that can be remotely powered. Actuation profiles will be remotely powered and modulated to allow for dynamic actuation profiles that open and close a lumen on-command, while generating pulsatile and peristaltic profiles. For example, the sphincter may be a urological, bladder, urethral, gastrointestinal, bowel, or anal sphincter.Example 6

[0243] Characteristics of liquid crystal elastomeric (LCE) materials as described herein was assessed as described below.

[0244] The strain behavior in response to temperature increase was characterized using the Tracker Video Analysis Tool. Uniaxially aligned LCEs with varyingconcentrations of C6BAPE (0.1 , 0.2, 0.3) were placed on a hotplate. The temperature was ramped from room temperature up to 60eC. The temperature measurements were recorded using two thermocouple probes (OMEGA HH802U) attached to the hotplate surface, and the readings were averaged. The contraction of the samples was recorded using a USB digital microscope camera, and results are shown in FIG. 13. The graph shows the strain response to a temperature ramp for three variations of the liquid crystal elastomer composition. As can be appreciated, by adjusting the fraction of C6BAPE, the TNI can be tuned to reach a suitable temperature range for the human body.

[0245] The work content for LCEs as described herein was measured for three configurations: LCE (No Au), LCE with a gold layer on one side (LCE / Gold), and LCE with gold layers on both sides (Gold / LCE / Gold). The actuators were vertically loaded with varying weights and placed near a hotplate to induce contraction. The maximum displacement was recorded, and the work was calculated as W=mgy_ma , where m is the attached mass, g is the gravitational acceleration constant, and ymax is the maximum displacement. The temperature of the hotplate was set to 120 °C such that the sample reaches its maximum displacement. Both the work and the applied weights were normalized with respect to the mass of the actuator, and results are shown in FIG. 14. The figure shows the normalized work against normalized applied weights under three gold coatings condition. The coatings serve as the joule heating source. Results show that the gold coating does not impede actuation.

[0246] Characteristics of wireless power transfer and thermal actuation for LCEs as described herein was measured with an oscillator generating an alternating current at a frequency of 180 kHz. The oscillator was powered using a DC power supply (GW INSTEK GPS-4303 4CH). A transmitting coil was connected to the oscillator and a receiving coil was connected to the gold-coated C6BAPE-LCE sample. An Infrared camera (FLIR 325A) was used to measure the temperature while a USB digital microscope camera is used to record the contraction.

[0247] The strain behavior in response to the increase in temperature was characterized using the Tracker Video Analysis Tool. The distance between the receiver and transmitter coils was varied causing an increase in temperature as the coils moved closer and more power was transferred. Transmitter coil: D = 200 mm, L = 13.5 uH. Receiver coil: D = 50 mm, L = 51.2 uH. The LCE artificial muscle is wirelessly powered using a transmitting coil located outside the human body and areceiver connected directly to the LCE that is coated with a conductive Joule heater. The relationship between the temperature rise, resulting strain, and the distance between the two coils is shown in FIGS. 15 and 16.

[0248] Work content of LCEs as described herein was assessed with actuators, vertically loaded with varying weights, and the maximum displacement ymax was recorded. The work (W) was calculated using the formula W=mgyma*, where m is the attached mass, g is the gravitational acceleration constant, and ymax is the maximum displacement. Both the work and the applied weights were normalized with respect to the mass of each actuator. The results are shown in FIG. 17, which illustrates that limiting behavior of the artificial muscle under wireless power transfer, shows that it is unable to lift heavier weights due to the limited heating. Unlike the work content under direct heat, where heating is unrestricted, the study of work content under wireless power transfer helps to identify potential limitations of wireless power delivery and the muscle’s performance under realistic heating conditions.

[0249] Additional characterizations of LCEs as described herein were also performed, with results shown in FIGS. 18A-18D. Wide Angle X-ray Scattering (WAXS): WAXS data were obtained using the Xeuss system. A thin strip (2 x 10 mm) was cut from the polymer sheet in a direction parallel to the stretching direction (nematic director) to prepare the sample.

[0250] The sample was mounted on a custom-built holder designed to keep it straight without adding any extra stretch. It was then exposed to X-rays at a 90° angle relative to the nematic director, using Cu Ka radiation with a wavelength of 1.5418 A. Two- dimensional images were captured with a Rigaku Mercury CCD detector during 5- minute scans, with the sample positioned approximately 93 mm from the CCD.

[0251] To analyze the WAXS data, the images were rotated 90° counterclockwise and mirrored horizontally. The scattering was primarily concentrated on the equator in the right-hand quadrant. MATLAB code was used to apply the analysis and calculate the chain order parameter.

[0252] Dynamic Mechanical Analyzer (DMA): A Perkin Elmer 8000 DMA was used to measure the storage modulus of samples along the nematic director. The experiments were conducted in strain control mode using a tension fixture, at a frequency of 1 Hz, and with a temperature sweep from -50 °C to 100 °C. Results were processed and analyzed using MATLAB code. Wide Angle X-ray Scattering is employed to determine the order parameter (0.364), which is relevant for the liquidcrystal unique properties. Additionally, the glass transition temperature was measured using a Dynamic Mechanical Analyzer and found to be -32 ± 1 ,5eC. The glass transition temperature was measured from the peak in Tan 8 peak measured using DMA. Example 7

[0253] FIGS. 19 (schematic) and 20 (photographic) show LCEs arranged as sphincters for use with an exemplary system, in the urinary tract. A soft clip deforms to open using the liquid crystal elastomers as a powering muscle. The integration of LCE with suspensory structures can enable optimization of the modalities for modulating the biomechanical stress. Thus, the development of a clip-like device for treating urinary incontinence by modulating the biomechanical stress on the urethra is provided herein.

[0254] FIG. 20 shows an early prototype demonstrating the liquid crystal elastomer wirelessly powering the opening of a clip (transition shown from top to bottom). The scale bar is 5 mm. Ongoing implementations are focusing on miniaturing the coil and optimizing the design of the actuator and to improve thermal isolation and efficiency of actuation. Note that the integration of the suspensory structures with LCE can enable the development of implantable soft robotic devices for a range of applications, including reversible birth control, artificial sphincters to treat fecal incontinence, and devices to manage gastroesophageal reflux disease (GERD) by modulating the biomechanical stress state of the esophageal sphincter.

[0255] The present invention has been described with reference to certain exemplary embodiments, dispersible compositions and uses thereof. However, it will be recognized by those of ordinary skill in the art that various substitutions, modifications or combinations of any of the exemplary embodiments may be made without departing from the spirit and scope of the invention. Thus, the invention is not limited by the description of the exemplary embodiments, but rather by the appended claims as originally filed.

Claims

WHAT IS CLAIMED IS:1 . An antibacterial liquid crystal elastomer comprising: a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, wherein the antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 30 °C to about 45 °C.

2. The antibacterial liquid crystal elastomer of claim 1 , comprising a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

3. The antibacterial liquid crystal elastomer of claim 1 or 2, wherein the liquid crystal component is formed from a liquid crystal monomer comprising: a first terminal acrylate functional group; a second terminal acrylate functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the first terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the second terminal acrylate functional group to the second end of the mesogenic core.

4. The antibacterial liquid crystal elastomer of claim 3, wherein the mesogenic core comprises from one to three aromatic rings, wherein one or more of the aromatic rings are optionally substituted with an alkyl group, an ether group, an ester group, a halogen, a hydroxyl group, or combinations thereof.

5. The antibacterial liquid crystal elastomer of claim 3 or claim 4, wherein the first flexible linker and the second flexible linker comprise an aliphatic carbon chain optionally substituted with an oxygen atom.

6. The antibacterial liquid crystal elastomer of claim 5, wherein the first flexible linker and the second flexible linker comprise a C3 - C10 aliphatic carbon chain.

7. The antibacterial liquid crystal elastomer of any one of claims 3 to6, wherein the liquid crystal monomer comprises 1 ,4-bis-[4-(6- acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene) (RM82), 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2- Methyl-1 ,4-phenylene-bis[4[3(acryloyloxy) propyloxy]benzoate] (RM257), or combinations thereof.

8. The antibacterial liquid crystal elastomer of any one of claims 1 to7, wherein the liquid crystal component is further formed from an additional liquid crystal monomer comprising: a terminal acrylate functional group; a terminal reactive functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the terminal reactive functional group to the second end of the mesogenic core.

9. The antibacterial liquid crystal elastomer of claim 8, wherein the additional liquid crystal monomer comprises 4-cyanophenyl 4-((6- (acryloyloxy)hexyl)oxy)benzoate (RM23).

10. The antibacterial liquid crystal elastomer of any one of claims 1 to 9, wherein the chain extending component is formed from one or more chain extending monomers comprising a C2-C6 aliphatic carbon chain or one or more ethergroups and from two or four terminal thiol groups, a C2-C6 aliphatic carbon chain and from one to two amine groups, or combinations thereof.1 1 . The antibacterial liquid crystal elastomer of claim 10, wherein the one or more chain extending monomers are selected from the group consisting of ethane-1 ,2-dial bis(3-mercapto propanoate) (GDMP), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), 1 ,4- benzenedimethanethiol (BDMT), mixtures thereof, and combinations thereof.

12. The antibacterial liquid crystal elastomer of any one of claims 1 to1 1 , wherein the pendant antibiotic moiety comprises norfloxacin, acyclovir, afloxacin, ampicillin, amphotericin B, atovaquone, azithromycin, ciprofloxacin, clarithromycin, clindamycin, clofazimine, dapsone, diclazaril, doxycycline, erythromycin, ethambutol, fluconazole, fluoroquinolones, foscarnet, ganciclovir, gentamicin, iatroconazole, isoniazid, ketoconazole, levofloxacin, lincomycin, miconazole, neomycin, ofloxacin, paromomycin, penicillin, pentamidine, polymyxin B, pyrazinamide, pyrimethamine, rifabutin, rifampin, sparfloxacin, streptomycin, sulfadiazine, tetracycline, tobramycin, trifluorouridine, trimethoprim sulphate, Zn-pyrithione, or vancomycin.

13. The antibacterial liquid crystal elastomer of any one of claims 1 to12, wherein the pendant antibiotic moiety comprises norfloxacin.

14. The antibacterial liquid crystal elastomer of any one of claims 1 to 1 1 , wherein the pendant antibiotic moiety comprises an antibacterial peptide.

15. The antibacterial liquid crystal elastomer of any one of claims 1 to 14, wherein the pendant antibiotic moiety component is covalently bonded to a surface of the cross-linked liquid crystal oligomers.

16. The antibacterial liquid crystal elastomer of any one of claims 1 to 14, wherein the pendant antibiotic moiety component is formed from a monomer comprising the antibiotic moiety, wherein the monomer comprising the antibiotic moiety comprises the following structure:wherein:Ri is the antibiotic moiety;X is -NH-, -S-, -O-, or -OC(O)-; andY is a bond or a linker, and wherein the monomer comprising the antibiotic moiety is cross-linked with the liquid crystal component, the chain extender component, and optionally, the non-liquid crystalline component.

17. The antibacterial liquid crystal elastomer of any one of claims 1 to 16, wherein the liquid crystal oligomers further comprise a non-liquid crystalline component, wherein the non-liquid crystalline component is formed from a non-liquid crystalline monomer.

18. The antibacterial liquid crystal elastomer of claim 17, wherein the non-liquid crystalline monomer is glyoxal bis(diallyl acetal) (GBDA).

19. The antibacterial liquid crystal elastomer of any one of claims 1 to 16, wherein the liquid crystal oligomers comprising the liquid crystal component, the chain extender component, and the pendant antibiotic moiety component are crosslinked using a cross-linker in the presence of one or more catalysts, one or more inhibitors of thermal polymerization (e.g., 2,6-Di-tert-butyl-4-methylphenol (BHT)), and / or one or more photoinitiators.

20. The antibacterial liquid crystal elastomer of claim 19, wherein the cross-linker is selected from the group consisting of 1 ,3,5-triallyl-1 ,3,5-triazine- 2, 4, 6(1 H,3H,5H)-trione (TATATO), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclo- tetrasiloxane, mixtures thereof, and combinations thereof.21 . The antibacterial liquid crystal elastomer of any one of claims 1 to 18, wherein the liquid crystal oligomers comprising the liquid crystal component, the chain extender component, the pendant antibiotic moiety component, and the nonliquid crystalline component are cross-linked in the presence of one or more catalysts, one or more radical one or more inhibitors of thermal polymerization, and / or one or more photoinitiators.

22. The antibacterial liquid crystal elastomer of any one of claims 1 to21 , wherein the liquid crystal components of the liquid crystal oligomers are aligned.

23. The antibacterial liquid crystal elastomer of any one of claims 1 to 16, wherein the liquid crystal oligomers are formed from 4-(6- (acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2,2’- (ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), glyoxal bis(diallyl acetal) (GBDA), and24. The antibacterial liquid crystal elastomer of any one of claims 1 to23, further comprising an ionic component, an electronic conductive material, or combinations thereof.

25. The antibacterial liquid crystal elastomer of claim 24, wherein the ionic component is formed by doping with an ionic liquid, an imidazolium-functionalized cross-linker comprising the following formula:wherein X’ isor combinations thereof.

26. The antibacterial liquid crystal elastomer of claim 24, wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

27. An artificial muscle comprising the antibacterial liquid crystal elastomer of any one of claims 1 to 26.

28. The artificial muscle of claim 27, wherein the antibacterial liquid crystal elastomer undergoes a reversible change in shape in response to an external stimuli.

29. The artificial muscle of claim 27, wherein the antibacterial liquid crystal elastomer comprises an ionic component, an electronic conductive material, or combinations thereof and the external stimuli is heat generated by resistive heating.

30. A method of making an antibacterial liquid crystal elastomer, the method comprising: forming liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a nonliquid crystalline component, wherein forming the liquid crystal oligomers comprises: preparing a mixture of liquid crystal monomers, chain extender monomers, optionally, monomers comprising an antibiotic moiety, and optionally, non-liquid crystalline monomers, and heating the mixture to form the liquid crystal oligomers;depositing the liquid crystal oligomers onto the surface of a substrate; aligning the liquid crystal components of the liquid crystal oligomers; and cross-linking the liquid crystal oligomers to form a liquid crystal polymer network, wherein the antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from 30 °C to 45 °C.

31. The method of claim 30, wherein cross-linking the liquid crystal oligomers is completed after aligning the liquid crystal components of the liquid crystal oligomers.

32. The method of claim 30, wherein cross-linking the liquid crystal oligomers is completed before aligning the liquid crystal components of the liquid crystal oligomers.

33. The method of any one of claims 30 to 32, wherein aligning the liquid crystal components of the oligomers is completed through stretching.

34. The method of any one of claims 28 to 33, wherein the liquid crystal oligomers are deposited in an extrusion printing process, wherein the extrusion printing process aligns the liquid crystal components of the liquid crystal oligomers.

35. The method of any one of claims 30 to 34, further comprising adding an ionic liquid, an imidazolium-functionalized cross-linker, an electronic conductive material, or combinations thereof to the mixture of the liquid crystal monomers, the chain extender monomers, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers.

36. The method of claim 35, wherein the imidazolium-functionalized cross-linker comprises the following formula:wherein X’ is37. The method of claim 35, wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

38. The method of any one of claims 30 to 37, further comprising adding cross-linkers, one or more catalysts, one or more inhibitors of thermal polymerization (e.g., 2,6-Di-tert-butyl-4-methylphenol (BHT)), and / or one or more photoinitiators to the mixture of the liquid crystal monomers, the chain extender monomers, optionally, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers.

39. The method of claim 38, wherein the cross-linker is selected from the group consisting of 1 ,3,5-triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)-trione (TATATO), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, mixtures thereof, and combinations thereof.

40. The method of any one of claims 30 to 39, wherein the liquid crystal monomers comprise: a first terminal acrylate functional group; a second terminal acrylate functional group; a mesogenic core comprising a first end and a second end;a first flexible linker connecting the first terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the second terminal acrylate functional group to the second end of the mesogenic core.41 . The method of claim 40, wherein the mesogenic core comprises from one to three aromatic rings, wherein one or more of the aromatic rings are optionally substituted with an alkyl group, an ether group, an ester group, a halogen, a hydroxyl group, or combinations thereof.

42. The method of claim 40 or 41 , wherein the first flexible linker and the second flexible linker comprise an aliphatic carbon chain optionally substituted with an oxygen atom.

43. The method of claim 42, wherein the first flexible linker and the second flexible linker comprise a C3 - C10 aliphatic carbon chain.

44. The method of any one claims 30 to 43, wherein the liquid crystal monomers comprise 1 ,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene) (RM82), 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2-methyl-1 ,4-phenylene-bis[4[3(acryloyloxy) propyloxy]benzoate] (RM257), or combinations thereof.

45. The method of any one of claims 30 to 44, further comprising adding an additional liquid crystal monomer to the mixture of the liquid crystal monomers, the chain extender monomers, optionally, the monomers comprising the antibiotic moiety, and optionally, the non-liquid crystalline monomers, wherein the additional liquid crystal monomer comprises: a terminal acrylate functional group; a terminal reactive functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the terminal acrylate functional group to the first end of the mesogenic core; anda second flexible linker connecting the terminal reactive functional group to the second end of the mesogenic core.

46. The method of claim 45, wherein the additional liquid crystal monomer comprises 4-cyanophenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (RM23).

47. The method of any one of claims 30 to 46, wherein the chain extending monomers comprise a C2-C6 aliphatic carbon chain or one or more ether groups and from two or four terminal thiol groups, a C2-C6 aliphatic carbon chain and from one to two amine groups, or combinations thereof.

48. The method of claim 47, wherein the chain extending monomers are selected from the group consisting of ethane-1 ,2-dial bis(3-mercapto propanoate) (GDMP), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3- mercapto propionate) (PETMP), 1 ,4-benzenedimethanethiol (BDMT), mixtures thereof, and combinations thereof.

49. The method of any one of claims 30 to 48, wherein the pendant antibiotic moiety comprises norfloxacin, acyclovir, afloxacin, ampicillin, amphotericin B, atovaquone, azithromycin, ciprofloxacin, clarithromycin, clindamycin, clofazimine, dapsone, diclazaril, doxycycline, erythromycin, ethambutol, fluconazole, fluoroquinolones, foscarnet, ganciclovir, gentamicin, iatroconazole, isoniazid, ketoconazole, levofloxacin, lincomycin, miconazole, neomycin, ofloxacin, paromomycin, penicillin, pentamidine, polymyxin B, pyrazinamide, pyrimethamine, rifabutin, rifampin, sparfloxacin, streptomycin, sulfadiazine, tetracycline, tobramycin, trifluorouridine, trimethoprim sulphate, Zn-pyrithione, or vancomycin.

50. The method of any one of claims 30 to 49, wherein the pendant antibiotic moiety comprises norfloxacin.51 . The method of any one of claims 30 to 48, wherein the pendant antibiotic moiety comprises an antibiotic peptide.

52. The method of any one of claims 30 to 51 , further comprising reacting the pendant antibiotic moiety component with a surface of the cross-linked liquid crystal oligomers to covalently bond the pendant antibiotic moiety component to the surface of the cross-linked liquid crystal oligomers.

53. The method of any one of claims 30 to 51 , wherein the mixture comprises liquid crystal monomers, chain extender monomers, monomers comprising an antibiotic moiety, and optionally, non-liquid crystalline monomers.

54. The method of claim 53, wherein the monomers comprising the antibiotic moiety comprise the following structure:wherein:Ri is the antibiotic moiety;X is -NH-, -S-, -O-, or -OC(O)-; andY is a bond or a linker.

55. The method of claim 53 or claim 54, wherein the mixture comprises a molar ratio of the liquid crystal monomers to the monomers comprising the antibiotic moiety to the chain extending monomers to the non-crystalline monomers of 0.1 -1 .5: 0.05-0.65 : 0.01 -1 .5 : 0-0.5.

56. The method of any one of claims 30 to 55, wherein the liquid crystal oligomers further comprise non-liquid crystalline components.

57. The method of any one of claims 30 to 56, wherein the non-liquid crystalline monomer is glyoxal bis(diallyl acetal) (GBDA).

58. The method of any one of claims 30 to 57, wherein the antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

59. A device, comprising: a first component comprising a first antibacterial liquid crystal elastomer, wherein the first antibacterial liquid crystal elastomer comprises a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, and wherein the first antibacterial liquid crystal elastomer of the first component comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 30 °C to about 45 °C; a second component comprising a second antibacterial liquid crystal elastomer comprising an ionic component, an electronic conductive material, or combinations thereof, wherein the second component is in direct contact with the first component, wherein the second antibacterial liquid crystal elastomer comprises a liquid crystal polymer network of cross-linked liquid crystal oligomers comprising a pendant antibiotic moiety, wherein the liquid crystal oligomers comprise a liquid crystal component, a chain extender component, a pendant antibiotic moiety component, and optionally, a non-liquid crystalline component, and wherein the second antibacterial liquid crystal elastomer of the second component comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 30 °C to about 45 °C; and a resistive heating component in electrical contact with the second component, wherein the first component and the second component undergo a reversible change in shape in response to activation of the resistive heating component.

60. The device of claim 59, wherein the device further comprises an inductive coupling receiver configured to produce a current through the resistive heating component by inductive coupling with an inductive coupling transmitter.61 . The device of claim 60, wherein the inductive coupling receiver is fabricated from conductive soft polymers, metals, or combinations thereof.

62. The device of claim 60 or claim 61 , wherein the inductive coupling transmitter is activated by a wireless actuator.

63. The device of any one of claims 60 to 62, wherein the resistive heating component is electrically and / or mechanically connected to the second component.

64. The device of claim 63, wherein the resistive heating component is electrically connected to the second component through one or more wires.

65. The device of any one of claims 59 to 64, wherein the first antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

66. The device of any one of claims 59 to 65, wherein the second antibacterial liquid crystal elastomer comprises a nominal nematic-isotropic transition temperature (TNI) in a range of from about 35 °C to about 45 °C.

67. The device of any one of claims 59 to 66, wherein the liquid crystal component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is formed from a liquid crystal monomer comprising: a first terminal acrylate functional group; a second terminal acrylate functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the first terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the second terminal acrylate functional group to the second end of the mesogenic core.

68. The device of claim 67, wherein the mesogenic core comprises from one to three aromatic rings, wherein one or more of the aromatic rings are optionally substituted with an alkyl group, an ether group, an ester group, a halogen, a hydroxyl group, or combinations thereof.

69. The device of claim 67 or claim 68, wherein the first flexible linker and the second flexible linker comprise an aliphatic carbon chain optionally substituted with an oxygen atom.

70. The device of claim 69, wherein the first flexible linker and the second flexible linker comprise a C3 - C10 aliphatic carbon chain.71 . The device of any one claims 67 to 70, wherein the liquid crystal monomer comprises 1 ,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-ethylbenzene) (RM82), 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6-(acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2-methyl-1 ,4-phenylene-bis[4[3(acryloyloxy) propyloxy]benzoate] (RM257), or combinations thereof.

72. The device of any one of claims 59 to 71 , wherein the liquid crystal component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is further formed from an additional liquid crystal monomer comprising: a terminal acrylate functional group; a terminal reactive functional group; a mesogenic core comprising a first end and a second end; a first flexible linker connecting the terminal acrylate functional group to the first end of the mesogenic core; and a second flexible linker connecting the terminal reactive functional group to the second end of the mesogenic core.

73. The device of claim 72, wherein the additional liquid crystal monomer comprises 4-cyanophenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate (RM23).

74. The device of any one of claims 59 to 73, wherein the chain extending component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is formed from one or more chain extending monomers comprising a C2-C6 aliphatic carbon chain or one or more ether groups and from two or four terminal thiol groups, a C2-C6 aliphatic carbon chain and from one to two amine groups, or combinations thereof.

75. The device of claim 74, wherein the one or more chain extending monomers are selected from the group consisting of ethane-1 ,2-dial bis(3-mercapto propanoate) (GDMP), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), 1 ,4-benzenedimethanethiol (BDMT), mixtures thereof, and combinations thereof.

76. The device of any one of claims 59 to 75, wherein the pendant antibiotic moiety of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprises norfloxacin, acyclovir, afloxacin, ampicillin, amphotericin B, atovaquone, azithromycin, ciprofloxacin, clarithromycin, clindamycin, clofazimine, dapsone, diclazaril, doxycycline, erythromycin, ethambutol, fluconazole, fluoroquinolones, foscarnet, ganciclovir, gentamicin, iatroconazole, isoniazid, ketoconazole, levofloxacin, lincomycin, miconazole, neomycin, ofloxacin, paromomycin, penicillin, pentamidine, polymyxin B, pyrazinamide, pyrimethamine, rifabutin, rifampin, sparfloxacin, streptomycin, sulfadiazine, tetracycline, tobramycin, trifluorouridine, trimethoprim sulphate, Zn-pyrithione, or vancomycin.

77. The device of any one of claims 59 to 76, wherein the pendant antibiotic moiety of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprises norfloxacin.

78. The device of any one of claims 59 to 75, wherein the pendant antibiotic moiety of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprises an antibacterial peptide.

79. The device of any one of claims 59 to 78, wherein the pendant antibiotic moiety component of the first antibacterial liquid crystal elastomer and thesecond antibacterial liquid crystal elastomer is covalently bonded to a surface of the cross-linked liquid crystal oligomers.

80. The device of any one of claims 59 to 78, wherein the pendant antibiotic moiety component of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer is formed from a monomer comprising the antibiotic moiety, wherein the monomer comprising the antibiotic moiety comprises the following structure:wherein:Ri is the antibiotic moiety;X is -NH-, -S-, -O-, or -OC(O)-; andY is a bond or a linker, wherein the monomer comprising the antibiotic moiety is cross-linked with the liquid crystal component, the chain extender component, and optionally, the non-liquid crystalline component.81 . The device of any one of claims 59 to 80, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer further comprise a non-liquid crystalline component, wherein the non-liquid crystalline component is formed from a non-liquid crystalline monomer.

82. The device of claim 81 , wherein the non-liquid crystalline monomer is glyoxal bis(diallyl acetal) (GBDA).

83. The device of any one of claims 59 to 80, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprising the liquid crystal component, the chain extender component, and optionally, the pendant antibiotic moiety component arecross-linked using a cross-linker in the presence of one or more catalysts, one or more inhibitors of thermal polymerization (e.g., 2,6-Di-tert-butyl-4-methylphenol (BHT)), and / or one or more photoinitiators.

84. The device of claim 83, wherein the cross-linker is selected from the group consisting of 1 ,3,5-triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)-trione (TATATO), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, mixtures thereof, and combinations thereof.

85. The device of any one of claims 59 to 82, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer comprising the liquid crystal component, the chain extender component, optionally, the pendant antibiotic moiety component, and the non-liquid crystalline component are cross-linked in the presence of one or more catalysts, one or more one or more inhibitors of thermal polymerization (e.g., 2,6-Di-tert-butyl-4- methylphenol (BHT)), and / or one or more photoinitiators.

86. The device of any one of claims 59 to 85, wherein the liquid crystal components of the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer are aligned.

87. The device of any one of claims 59 to 82, wherein the liquid crystal oligomers of the first antibacterial liquid crystal elastomer and the second antibacterial liquid crystal elastomer are formed from 4-(6-(acryloyloxy)hexyloxy)phenyl-4-(6- (acryloyloxy)hexyloxy) benzoate) (C6BAPE), 2,2’-(ethylenedioxy) diethanethiol (EDDT), pentaerythritol tetrakis(3-mercapto propionate) (PETMP), glyoxal bis(diallyl acetal) (GBDA), and88. The device of any one of claims 59 to 87, wherein ionic component of the second antibacterial liquid crystal elastomer is formed by doping with an ionic liquid, an imidazolium-functionalized cross-linker comprising the following formula:or combinations thereof.

89. The device of any one of claims 59 to 87, wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

90. The device of any one of claims 59 to 89, wherein the first antibacterial liquid crystal elastomer further comprises an ionic component, an electronic conductive material, or combinations thereof.

91. The device of claim 90, wherein ionic component is formed by doping with an ionic liquid, an imidazolium-functionalized cross-linker comprising the following formula:wherein X’ isor combinations thereof.

92. The device of claim 90, wherein the electronic conductive material comprises eutectic gallium-indium (eGain), a conductive carbon allotrope (e.g., carbon nanotubes, graphite, graphene), inorganic nanowires, integral / segmented / fractured metallic coatings, conductive polymers (e.g., poly(3,4 ethylenedioxythiophene sulfonate, polypyrrole, polyaniline), and combinations thereof.

93. The device of any one of claims 59 to 92, wherein the first component is arranged as a sphincter about an opening.

94. The device of any one of claims 59 to 92, wherein the first component is arranged as a mesh comprising first isotropic component that expands and contracts in a first direction, and a second isotropic component that expands and contracts in a second direction, such that heating the first isotropic component using the resistive heating component causes contraction of the mesh along the first direction, and heating the second isotropic component using the resistive heating causes contraction of the mesh along the second direction.

95. The device of claim 94, wherein the first isotropic component is heated by a first resistive heating component and the second isotropic component is independently heated by a second resistive heating component, such that contraction of the first isotropic component may be controlled independently of contraction of the second isotropic component.

96. The device of any one of claims 59 to 95, wherein at least a portion of the first component, the second component, and / or the resistive heating component are encapsulated in a secondary packaging.

97. The device of claim 96, wherein the secondary packaging comprises a biocompatible polymer (e.g., polydimethylsiloxane (PDMS), parylene).

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