The field of engineered living materials lies at the intersection of materials science and synthetic biology with the aim of developing materials that can sense and respond to the environment. In this study, we use 3D printing to fabricate a cyanobacterial biocomposite material capable of producing multiple functional outputs in response to an external chemical stimulus and demonstrate the advantages of utilizing additive manufacturing techniques in controlling the shape of the fabricated photosynthetic material. As an initial proof-of-concept, a synthetic riboswitch is used to regulate the expression of a yellow fluorescent protein reporter in
Neither of us can remember people talking about stimuli‐responsive polymers when we were students. Even though this was still in the last century, it was almost 70 years after Staudinger's seminal paper “Über Polymerisation”![1]By the time we entered graduate school in the early 1990 s, the first papers on polymer light emitting diodes appeared, while research on electrically conducting, nonlinear optical, and other “functional” polymers was already in full swing. Looking back, there were some stimuli‐responsive materials that were around at the time,[2–6]but it took the better part of the last 30 years until the field had developed into what we think is one of the most vibrant areas of polymer science.[8–12]Before the potential usefulness of this class of materials was recognized, researchers were focused on developing polymeric materials that would not respond to external influences, and in fact maintain (in particular) their mechanical properties in a wide range of environments. This has led to the development of many environmentally robust polymers, which have come to impact basically every aspect of our daily life. Ironically, this long‐sought stability now comes back to haunt us in the form of plastic pollution, but this is another story. The concept of materials that adapt their properties in response to changing environmental conditions might appear like a complete reversal with respect to the original goals of creating stable materials. However, eventually a) it was recognized that materials that respond to a specific stimulus in a predictable and useful manner would significantly broaden the potential usefulness of polymers, and b) the field of polymer science had developed to the point where the rational design, preparation, and characterization of such materials became possible. The expression
- NSF-PAR ID:
- 10120966
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Israel Journal of Chemistry
- Volume:
- 60
- Issue:
- 1-2
- ISSN:
- 0021-2148
- Page Range / eLocation ID:
- p. 100-107
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Synechococcus elongatus PCC 7942 within a hydrogel matrix. Subsequently, a strain ofS. elongatus is engineered to produce an oxidative laccase enzyme; when printed within a hydrogel matrix the responsive biomaterial can decolorize a common textile dye pollutant, indigo carmine, potentially serving as a tool in environmental bioremediation. Finally, cells are engineered for inducible cell death to eliminate their presence once their activity is no longer required, which is an important function for biocontainment and minimizing environmental impact. By integrating genetically engineered stimuli-responsive cyanobacteria in volumetric 3D-printed designs, we demonstrate programmable photosynthetic biocomposite materials capable of producing functional outputs including, but not limited to, bioremediation. -
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Ever-increasing demands for energy, particularly being environmentally friendly have promoted the transition from fossil fuels to renewable energy.1Lithium-ion batteries (LIBs), arguably the most well-studied energy storage system, have dominated the energy market since their advent in the 1990s.2However, challenging issues regarding safety, supply of lithium, and high price of lithium resources limit the further advancement of LIBs for large-scale energy storage applications.3Therefore, attention is being concentrated on an alternative electrochemical energy storage device that features high safety, low cost, and long cycle life. Rechargeable aqueous zinc-ion batteries (ZIBs) is considered one of the most promising alternative energy storage systems due to the high theoretical energy and power densities where the multiple electrons (Zn2+) . In addition, aqueous ZIBs are safer due to non-flammable electrolyte (e.g., typically aqueous solution) and can be manufactured since they can be assembled in ambient air conditions.4As an essential component in aqueous Zn-based batteries, the Zn metal anode generally suffers from the growth of dendrites, which would affect battery performance in several ways. Second, the led by the loose structure of Zn dendrite may reduce the coulombic efficiency and shorten the battery lifespan.5
Several approaches were suggested to improve the electrochemical stability of ZIBs, such as implementing an interfacial buffer layer that separates the active Zn from the bulk electrolyte.6However, the and thick thickness of the conventional Zn metal foils remain a critical challenge in this field, which may diminish the energy density of the battery drastically. According to a theretical calculation, the thickness of a Zn metal anode with an areal capacity of 1 mAh cm-2is about 1.7 μm. However, existing extrusion-based fabrication technologies are not capable of downscaling the thickness Zn metal foils below 20 μm.
Herein, we demonstrate a thickness controllable coating approach to fabricate an ultrathin Zn metal anode as well as a thin dielectric oxide separator. First, a 1.7 μm Zn layer was uniformly thermally evaporated onto a Cu foil. Then, Al2O3, the separator was deposited through sputtering on the Zn layer to a thickness of 10 nm. The inert and high hardness Al2O3layer is expected to lower the polarization and restrain the growth of Zn dendrites. Atomic force microscopy was employed to evaluate the roughness of the surface of the deposited Zn and Al2O3/Zn anode structures. Long-term cycling stability was gauged under the symmetrical cells at 0.5 mA cm-2for 1 mAh cm-2. Then the fabricated Zn anode was paired with MnO2as a full cell for further electrochemical performance testing. To investigate the evolution of the interface between the Zn anode and the electrolyte, a home-developed in-situ optical observation battery cage was employed to record and compare the process of Zn deposition on the anodes of the Al2O3/Zn (demonstrated in this study) and the procured thick Zn anode. The surface morphology of the two Zn anodes after circulation was characterized and compared through scanning electron microscopy. The tunable ultrathin Zn metal anode with enhanced anode stability provides a pathway for future high-energy-density Zn-ion batteries.
Obama, B., The irreversible momentum of clean energy.
Science 2017, 355 (6321), 126-129.Goodenough, J. B.; Park, K. S., The Li-ion rechargeable battery: a perspective.
J Am Chem Soc 2013, 135 (4), 1167-76.Li, C.; Xie, X.; Liang, S.; Zhou, J., Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc‐ion Batteries.
Energy & Environmental Materials 2020, 3 (2), 146-159.Jia, H.; Wang, Z.; Tawiah, B.; Wang, Y.; Chan, C.-Y.; Fei, B.; Pan, F., Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries.
Nano Energy 2020, 70 .Yang, J.; Yin, B.; Sun, Y.; Pan, H.; Sun, W.; Jia, B.; Zhang, S.; Ma, T., Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives.
Nanomicro Lett 2022, 14 (1), 42.Yang, Q.; Li, Q.; Liu, Z.; Wang, D.; Guo, Y.; Li, X.; Tang, Y.; Li, H.; Dong, B.; Zhi, C., Dendrites in Zn-Based Batteries.
Adv Mater 2020, 32 (48), e2001854.Acknowledgment
This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.
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pH-responsive polymeric nanoparticles are an exciting class of stimuli-responsive materials that can respond to changes in pH and, as a result, have been developed for numerous applications in biomedicine, such as the loading and delivery of various cargoes. One common transformation is nanoparticle swelling due to the protonation or deprotonation of specific side chain moieties in the polymer structure. When the pH trigger is removed, the swelling can be reversed, and this process can be continually cycled by adjusting the pH. In this work, we are leveraging this swelling–deswelling–reswelling mechanism to develop a simple, fast, and easy loading strategy for a class of cross-linked polymeric nanoparticles, poly-2-(diethylamino) ethyl methacrylate (pDEAEMA), that can reversibly swell below pH 7.3, and a dye, rhodamine B isothiocyanate (RITC), as a proof-of-concept cargo molecule while comparing to poly(methyl methacrylate) (pMMA) nanoparticles as a nonswelling control. A free radical polymerization was used to generate pDEAEMA nanoparticles at three different sizes by varying the synthesis temperature. Their pH-dependent swelling and deswelling were extensively characterized using dynamic light scattering and transmission electron microscopy, which revealed a reversible increase in size for pDEAEMA nanoparticles in acidic media, whereas pMMA nanoparticles remain constant. Following dye loading, pDEAEMA nanoparticles show significant fluorescence intensity when compared to pMMA nanoparticles, suggesting that the reversible swelling is key for successful loading. Upon acidic treatment, there is a significant decrease in the fluorescence intensity when compared to the dye-loaded nanoparticles in basic media, which could be due to dilution of the dye when released in the acidic medium solution. Interestingly, nanoparticle size had no impact on dye loading properties, suggesting that the dye molecules only go so far into the polymer nanoparticle. Additionally, confocal microscopy images reveal pDEAEMA nanoparticles with higher RITC fluorescence intensity in acidic media but a lower RITC fluorescence intensity in basic media, while pMMA nanoparticles show no differences. Together, these results showcase a size reversibility-driven cargo loading mechanism that has the potential to be applied to other beneficial cargoes and for various applications.more » « less
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ABSTRACT With recent developments in the field of smart textiles, researchers have been working toward fabricating architectures of nanofibers, known as nanoyarns, which mimic the geometry of a conventional yarn. In doing so, one can leverage the unique properties of nanoscale fibers, including high surface‐to‐volume ratio and tunable porosity, for the development of smart garments. In the last 5 years, researchers have produced nanoyarns from a limited number of polymers, including polyacrylonitrile (PAN) and poly(vinylidene fluoride) and its co‐polymers. However, to our knowledge, there has been little research on the solution properties and electrospinning parameters needed to fabricate these higher‐order architectures from nonwoven mats. In this work, a modified electrospinning setup, enclosed in a humidity‐controlled chamber, was developed to fabricate nanoyarns for integration into knitted textiles. We fabricated nanofibers and nanoyarns from PAN/DMF solutions and conducted a systematic study to analyze the effect of solution conductivity, viscosity, and electrospinning parameters (applied voltage, collector distance, and humidity) on fiber and yarn fabrication and morphology. Polymer concentration had a significant effect on fibrous cone and yarn fabrication. Low polymer concentrations resulted in poor cone formation, whereas high concentration resulted in dense cones that were difficult to draw into nanoyarns. Overall, the matrix of electrospinning parameters that resulted in the formation of homogenous nanofiber mats was larger than that of nanoyarn formation. Nanoyarn formation required higher polymer concentration and/or applied voltage than nonwoven mat formation. The influence of these parameters on nanoyarn formation and fiber diameter can be used to expand the library of spinnable nanoyarns and optimize their properties for specific applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci.
2018 ,135 , 46404. -
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Abstract With the development of modern polymer synthesis techniques, polymer therapeutics have emerged and rapidly grown into a research hotspot and a promising tool for biomedical applications owing to their outstanding advantages in comparison to conventional drug therapy. Among an enormous number of polymers developed for therapeutic purposes, pyridyl disulfide (PD) group functionalized polymers have attracted increasing attention over the past decades. The highly reactive PD group could be replaced by almost any thiol‐containing groups, leading to the production of a disulfide bond. More importantly, the redox‐sensitive disulfide bond generated from the replacement can be exploited to develop stimuli‐responsive polymer therapeutics which will protect the loaded cargoes from premature leakage, while programmably releasing them in response to endogenous redox stimuli such as glutathione. Herein, the development of PD‐incorporated polymers and summarized PD‐based monomers that have been synthesized to prepare various functional polymeric architectures are reviewed. Moreover, this review also discusses the difference between polymers with PD as repeating pendants or terminal groups and emphasizes on the diverse promising applications of these polymers as nanotherapeutic platforms in the biomedical field.
