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Synthetic Melanin E-Ink Lingqian Chang, Feng Chen, Xiaokang Zhang, Tairong Kuang, Mi Li, Jiaming Hu, Junfeng Shi, Ly James Lee, Huanyu Cheng, and Yiwen Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 28 Apr 2017 Downloaded from http://pubs.acs.org on April 29, 2017

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ACS Applied Materials & Interfaces

Synthetic Melanin E-Ink Lingqian Chang,2, ‡ Feng Chen,3, ‡ Xiaokang Zhang,1 Tairong Kuang,4 Mi Li,5 Jiaming Hu,2 Junfeng Shi,2 Ly James Lee,2 Huanyu Cheng, 6,* and Yiwen Li 1,* 1. College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, China 2. NSF Nanoscale Science and Engineering Center, Ohio State University, Columbus, OH 43209, USA 3. College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China 4. National Engineering Research Center of Novel Equipment for Polymer Processing, The Key Laboratory of Polymer Processing Engineering of Ministry of Education, South China University of Technology, Guangzhou, 510640, China. 5. Institute of Optical Communication Engineering, Nanjing University, Nanjing 210093, China 6. Department of Engineering Science and Mechanics, Materials Research Institute, The Pennsylvania State University, University Park, PA, 16802, USA Corresponding Author Emails: [email protected] (Y.L.); [email protected] (H.C.). ‡

These authors contribute equally to this work.

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Keywords: synthetic melanin, polydopamine, electronic ink, fluorescence display, nanoscale resolution


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ABSTRACT

Extensive efforts have been devoted to the development of surfactant-free electronic ink (E-ink) with excellent display resolution for high-definition (HD) resolution display. Herein we report the using of polydopamine-based synthetic melanin, a class of functional nanoparticles with similar chemical compositions and physical properties as naturally occurring melanin, as new Eink materials. It was found that such E-ink display in aqueous solution could achieve ultrahigh resolution (> 10,000 ppi) and low power consumption (operation voltage of only 1V). Interestingly, simple oxidation of synthetic melanin nanoparticles enable the generation of intrinsic fluorescence, allowing the further development of fluorescent E-ink display with nanoscale resolution. We describe these bioinspired materials in an initial proof-of-concept study and propose that synthetic melanin nanoparticles will be suitable for electronic nano-ink with potential wide range of applications in molecular patterning and fluorescent bioimaging.


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INTRODUCTION There is a continuing quest to fabricate advanced functional nanomaterials for emerging opportunities in energy and biomedical areas. Usually this quest looks back to nature as a source of inspiration, and often the journey leads to nucleic acids, proteins and other kinds of biomolecules. Among them, melanin, a kind of ubiquitous biological pigments widely distributed in living organisms, presents remarkable physicochemical properties, including photo-protection function, anti-oxidant and free radical scavenging behavior, structural coloration, as well as electrical conducting.1 Very recently, the sophisticated use of natural melanin mimics that achieved via the spontaneous oxidation polymerization of dopamine under alkaline conditions, may hold the key to developing new nanodevices in many advanced technology industries.2, 3 Those polydopamine-based synthetic melanin materials possess similar chemical structures and physical properties as natural resources,4 rendering them ideal candidates in functional nanomaterials with improved properties for vast range of applications.5, 6, 7, 8, 9, 10 Synthetic melanin materials are of particular interest as aqueous ink due to their excellent biocompatibility, good dispersity and stability in water, well-controlled size, rich surface chemistry, as well as low cost.2 Recent work has shown that synthetic melanin-based ink can be successfully inkjet printed on both glass and polymer substrates followed by site-selective Ag/Cu electroless plating methods.11, 12 Certainly, besides just simply used as chemical ink, we believe those bioinspired nanomaterials could be further employed as electronic ink (E-ink) candidates for high resolution display techniques. So far, many commercially available display techniques, such as, liquid crystal display (LCD),13, 14 plasma display panel (PDP)15, 16 and light-emitting diode (LED)17, 18, 19, have achieved high-definition (HD) resolution (>1,000 ppi), thus showing high performance in processing photos or films from ultrahigh resolution cameras (e.g. harge coupled device camera)20, 21, 22. Alternatively, E-ink technology has been regarded as another


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promising display strategy with impressive advantages on the low-cost fabrication, less power consumption, eye-protection from ambient light source (reducing eye stress).23, 24, 25, 26 It already has been reflected in several commercial products, such as electronic readers, smart phones and laptops. However, the further development of HD displays based on current E-ink materials has met with profound challenges, which are yet to be resolved. For example, pigments in current devices are electrophoretically actuated within artificial microcapsules (typically 30 µm in diameter) in organo-solvents,23, 25, 27, 28 strongly limiting a general display resolution of 300 ppi (or even less) in the devices.27, 28, 29, 30 Synthetic melanin materials with uniformly small sizes, high reflective index, and welldispersion in electrophoretic solution seem to be the ideal E-ink candidate for high-resolution display.2 Compared to most established materials in current E-ink systems (i.e. prototypes with microcapsules of pigments), synthetic melanin shows significant advantages in several aspects: (1) synthetic melanin E-ink exhibits environmental friendly features by working in surfactantfree aqueous solution instead of non-degradable organic solvents with large quantity of surfactants as traditional systems performed; 31, 32 (2) synthetic melanin E-ink with uniform small size (< 200 nm) and surface native charge (< -10 mV) enables a rapid response time (< 1 s) at a low voltage, as well as ultrahigh resolution (>10,000 ppi);33 (3)The simple surface engineering of synthetic melanin E-ink allows the further development of a unique fluorescent display for nanoscale images.34, 35 In this study, we describe a simple implementation of electrophoretic manipulation of synthetic melanin nanomaterials for E-ink display in aqueous solution, which achieved ultrahigh resolution with nanoscale features. To the best of our knowledge, such kind of green and versatile inks for HD displays has not been reported. The proposed synthetic melanin E-ink-based devices, with


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environmental friendliness and low power consumption, enable a wide variety of applications in bio-imaging, including photoacoustic imaging36,

37, 38

, functional electronic thin-films39,

40, 41

,

molecular patterning/labeling techniques42, 43, 44, and HD resolution display electronics22, 45, 46.

RESULTS AND DISCUSSION Preparation of Synthetic Melanin E-ink Display Device. The E-ink platform for electrophoretic display is shown in Figure 1. Operation of the electrophoresis was controlled by a pair of indium tin oxide (ITO)-coated glass plates, between which the synthetic melanin inks were randomly dispersed in the aqueous solution (Figure 1a). Transparent and dielectric features were patterned on the top ITO electrode. Note that synthetic melanin nanoparticles cannot be attracted on the features without additional electric field, and there was no clear feature displayed on the top electrode. Under a low-voltage electric field (i.e. 1V), the synthetic melanin nanoparticles, with an intrinsic negative charge of -18 mV (Table S1), were driven to the anode (top electrode) and filled in the exposed regions on the top ITO film (Figure 1b). A positive tone feature (with darker color) focused on the focal plane (top ITO electrode), could be observable to either naked eyes (similar to the commercial E-ink display) or microscope (for ultrahigh resolution measurement with micro-/nano-scale features) (Inset of Figure 1b). The synthetic melanin nanoparticles can be prepared according to the previous literature with minor modifications.5 By tuning the reaction parameters during the spontaneous oxidation polymerization of dopamine hydrochloride aqueous solution, the particle size can be easily controlled below 200 nm.2, 5 The resulting sample was characterized by transmission electron microscopy (TEM) (Figure 1c), cryo-TEM (Figure 1d), scanning electron microscopy (SEM) (Figure 1e), and dynamic light scattering (DLS) (Table S1) to quantify their size and uniformity.


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The combination of TEM, cryo-TEM and SEM is able to demonstrate highly spherical particles with diameter of (138 ± 20) nm, which is in good agreement with the result obtained by DLS with an average size of 150 nm (Table S1). Notably, the well dispersion and good stability of synthetic melanins in aqueous solution could be clearly confirmed by cryo-TEM images (Figure 1d); no obvious particle aggregation can be observed. Additionally, the Zeta-potential testing showed an intrinsic negative surface charge of -18 mV (Table S1) for the nanoparticles, again demonstrating their high stability in water. Different from conventional E-ink devices based on microcapsule (30 µm size) and massive surfactants those were coated on display pigments (usually 1~5 µm size), each individual nanoparticle without any surfactants in this newly developed system is actuated independently and counted as one pixel. Therefore, the pixel size is significantly miniaturized.

Ultrahigh Resolution by Synthetic Melanin E-ink Display. We first investigated the performance of synthetic melanin E-ink for display of eye-distinguishable character (dimension: ~ 3 mm), comparable to the display of letters in commercial E-readers. A transparent dielectric film was pattern on the top ITO film (see SI). The electrophoretic chamber was filled with synthetic melanin nanoparticles slurries (concentration: 1 wt%). A stereomicroscope47 with the magnification of 5× was used for real-time recording and quantitative analysis, though the feature can be directly identified with naked eyes (Figure S1). A clear character, with negative tone (brighter color), was rapidly shown up once the electric field was turned on (Figure 2a). Herein, two kinds of commercial E-ink materials, TiO2 nanoparticles (average size: 500 nm, white pigment) and carbon black microspheres (average size of 1100 nm, black pigment),25, 27 and the prepared synthetic melanins were employed in this study. In general cases for


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micropatterns in E-ink technology, both two materials were usually loaded into organic capsules with ~ 10-100 µm sizes for electrophoresis in the device, thereby exhibiting micropattern displays with only ~ 10-100 µm resolution. To further approach to nanoscale resolution, single particles were directly used for electrophoretic display.23, 25 It was observed that the display from TiO2 nanoparticles was blurry under the same electric field (Figure 2b) (Movie S1); and the carbon black materials barely enabled visible display (Figure 2c), but serious aggregation was observed both in the solution and on the ITO film (Movie S2). The spatial light intensity analysis demonstrates that synthetic melanin ink could perform better display uniformity/stability (Figure 2d) and light contrast (Figure 2e) compared with TiO2 nanoparticles and carbon black (Movie S3). Notably, the concentration of ink materials applied for display is much less than that used in previous work.3,5,6,7 We next demonstrated the ultrahigh resolution E-ink display with direct electrophoretic actuation of synthetic melanin nanoparticles (Figure 3). Small features (1-10 µm) were patterned on the top electrode. It was observed that our device with synthetic melanin E-ink can clearly display a micro-feature (an eagle, line width: 10 µm) within 1s (Movie S4); however, large aggregates could be also observed in carbon black material display although its pattern feature is also clear (Movie S5). The aggregation problems can be avoided by using another kind of black nano-pigment, carbon nanotubes (CNTs); However, limited contrast of such display can only be achieved when more complex micropattern was used (Figure 3b and Movie S6, also see Figure 3a and Movie S7 for the pattern by synthetic melanin). Repeated display experiments show the synthetic melanin E-ink can be used for multiple times without causing aggregation and particle degradation (Figure 3c-e). Moreover, the capability of display of the ‘inner branch of the feature’ with a line width of 2 µm is corresponding to the resolution of 10,000 ppi, 30 times higher than


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the maximum resolution of E-ink devices reported so far (Figure 3c). An analytical model was established to study the parameters that control the motility of synthetic melanin nanoparticles (see SI). The model indicates the motility of the charged nanoparticles (v) under electric yield is governed by the equation (1)

v = qU ( γ d )

(1)

Where q is the charge of the nanoparticles, U is the electric field, γ is drag coefficient, d is the distance between two electrodes. The response time is linearly proportional to the square of the distance and inverse proportional to the biased voltage with the function as equation (2)

t = d v ∝ d2 U

(2)

It has been validated by the experimental results shown in Figure 3f. In all of our experiments, the gap between the electrodes was confined less than 100 µm, by which we achieved the rapid response time, less than 1 V. The voltage applied in this system (i.e. 1-5 V) is significantly lower than most of the previously reported E-ink devices (with ~ 20 V), leading to a low power consumption.

Nanoscale Fluorescent Display. The catecholamine functional groups on the polydopaminebased synthetic melanins can be oxidized into diquinone anion radicals.34, 35 Interestingly, the oxidized synthetic melanin nanoparticles show intrinsic green fluorescence upon the excitation of 488 nm laser (transmission wavelength range from 510 to 550 nm) in our system, providing fluorescence E-ink display which has not been reported in previous research. Note that the surface charge of ink nanoparticles may change during the chemical oxidation process, which can be confirmed by the distinct Zeta-potential values of freshly-prepared synthetic melanins and their oxidized products (Table S1). Figure 4a shows fluorescence hexagonal micropatterns


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displayed by oxidized synthetic melanin E-ink, which were visualized by the fluorescence microscope (see SI).48 Such E-ink device provides unique dual-channel (bright field and fluorescence) image display (Figure 4b & c). Fluorescent display of microscale pattern (Figure 4a-4c, S3), up to nanoscale resolution based on single or several nanoparticles was further demonstrated. In addition, a nano-circle array (500 nm size) was patterned on the top electrode. Note that no green fluorescence feature was observed without external electric field (Figure 4d). Also, there is no significant difference of the fluorescence intensities between the nano-circles (red line, measured from the straight line between the two red arrows in Figure 4d) and the background (purple line, indicated from the purple arrows), as shown in Figure 4f. With the electric field on, a visible fluorescent nano-circle array was displayed (Figure 4e), with a sharp contrast to the background (Figure 4f). The fluorescence signal of the nano-circle shows nanoscale resolution and good uniformity (Figure 4f). The high dispersion and aqueous stability are two major factors to provide the possibility of achieving nanoscale fluorescence display in our E-ink system.

CONCLUSION In summary, we have reported a novel yet simple implementation of an E-ink device based on bioinspired synthetic melanin nanoparticles, offering ultrahigh resolution and unique fluorescence display. Comparing with typical commercial E-ink materials loaded in microcapsules in organo-solvents, the synthetic melanin E-ink could be electrophoretically actuated for direct display in water, which achieved an ultrahigh resolution (10,000 ppi), strong background contrast, and low power consumption (operation voltage of 1 V). The unique characteristic of nanoscale fluorescent display also promises new routes for molecular patterning and fluorescent bioimaging.


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EXPERIMENTAL SECTION Synthesis and characterization of synthetic melanin nanoparticles: Detailed synthesis procedure of synthetic melanin nanoparticles is described in SI. The synthesized synthetic melanin nanoparticles were then dispersed in deionized water and ultrasounded for 10 min. The suspension was centrifuged at 4000 rpm for 5 min, followed by dilution to a certain concentration (e.g. 1 wt%). To prepare oxidized synthetic melanin nanoparticles, 1 mL dispersed synthetic melanin nanoparticles (1 wt% in H2O) was reacted with 1 mL H2O2 solution (30 wt% in H2O, Sigma-Aldrich) for 24 h at 20 oC in a lucifugous condition, which in turn gave a maroon solution after centrifugation. Oxidized synthetic melanin nanoparticles with intrinsic fluorescence are shown in SI. The particle diameter and zeta-potential are summarized in Table S1. Synthetic melanin E-ink platform: One ITO glass without pattern was used as the bottom electrode, and the other ITO glass coated with micro-/nano-features was used as the top electrode. Between the pair of electrodes, a PDMS spacer (Sylgard 184, Dow Corning, MI) served as an insulated chamber, controlling the spacing between two electrodes. Prior to assembly, the ITO glasses were connected to external DC power supply (BK Precision, Melrose, MA). The microscope was focused on the top ITO electrode to visualize the change of micro/nano-feature in all the experiments. Details of the electrophoresis based E-ink display are given in SI. Microscopy Characterization: For quantitative analysis of the ultrahigh resolution E-ink display, microscopes were applied in our experiments. Stereomicroscope can provide pseudo-3D visions


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in microscale resolution with a noticeable depth of the field, similar to the function of human eyes. It involves high sensitivity for color change, dynamic microscopic imaging, and high resolution, leading to quantitative analysis of the display resolution, intensity, and response time. With high contrast and resolution (< 200 nm), total internal reflection fluorescence (TIRF) microscope was used for fluorescence display of nanoscale features from the oxidized synthetic melanin nanoparticles. Green fluorescence (excitation/emission wavelength: 488 nm/510-550 nm) used in this study is discussed in SI.

ASSOCIATED CONTENT Supporting Information Additional information on the synthesis and characterization of the ink materials, E-ink platform set-up and display, and micro-/nanoscale pattern features by E-inks.

Those materials are

available free of charge via the Internet at http:// pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (Y.L.) *E-mail: [email protected] (H.C.)

Author Contributions L.Chang and F. Chen contributed equally to this work.


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Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT We are grateful to Nanotech West Lab of Ohio State University for providing technical support of micro-/nano-patterning, and Dr. Xinmei Wang for training on DLS and Z-potentials measurement. Y. L. thanks financial support from State Key Laboratory of Polymer Materials Engineering, Sichuan University (No. sklpme2016-3-03). The authors acknowledge the support from the National Natural Science Foundation of China (No. 21274131, 51273178, 51203139 and 51303158) and Natural Science Foundation of Zhejiang Province (No. LY15E030005). H.C. acknowledges the start-up fund provided by Pennsylvania State University.

REFERENCES (1) d'Ischia, M.; Wakamatsu, K.; Cicoira, F.; Di Mauro, E.; Garcia-Borron, J. C.; Commo, S.; Galvan, I.; Ghanem, G.; Kenzo, K.; Meredith, P.; Pezzella, A.; Santato, C.; Sarna, T.; Simon, J. D.; Zecca, L.; Zucca, F. A.; Napolitano, A.; Ito, S., Melanins and Melanogenesis: from Pigment Cells Tohuman Health and Technological Applications. Pigm. Cell Melanoma Res. 2015, 28, 520-544. (2) Liu, Y.; Ai, K.; Lu, L., Synthesis and Promising Applications in Energy, Environmental, and Biomedical Fields. Chem. Rev. 2014, 114, 5057-5115. (3) Ju, K.-Y.; Lee, J. W.; Im, G. H.; Lee, S.; Pyo, J.; Park, S. B.; Lee, J. H.; Lee, J.-K., Bioinspired, Melanin-Like Nanoparticles as a Highly Efficient Contrast Agent for T1-weighted Magnetic Resonance Imaging. Biomacromolecules 2013, 14, 3491-3497. (4) d'Ischia, M.; Napolitano, A.; Ball, V.; Chen, C.-T.; Buehler, M. J., Polydopamine and Eumelanin: From Structure–Property Relationships to a Unified Tailoring Strategy. Acc. Chem. Res. 2014, 47, 3541–3550. (5) Xiao, M.; Li, Y.; Allen, M. C.; Deheyn, D. D.; Yue, X.; Zhao, J.; Gianneschi, N. C.; Shawkey, M. D.; Dhinojwala, A., Bio-Inspired Structural Colors Produced via Self-Assembly of Synthetic Melanin Nanoparticles. ACS Nano 2015, 9, 5454-5460.


13


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(6) Xiao, M.; Li, Y.; Zhao, J.; Wang, Z.; Gao, M.; Gianneschi, N. C.; Dhinojwala, A.; Shawkey, M. D., Stimuli-Responsive Structurally Colored Films from Bioinspired Synthetic Melanin Nanoparticles. Chem. Mater. 2016, 28, 5516-5521. (7) Liu, Y.; Ai, K.; Liu, J.; Deng, M.; He, Y.; Lu, L., Dopamine-Melanin Colloidal Nanospheres: An Efficient Near-Infrared Photothermal Therapeutic Agent for in Vivo Cancer Therapy. Adv. Mater. 2013, 25, 1353-1359. (8) Li, Y.; Huang, Y.; Wang, Z.; Carniato, F.; Xie, Y.; Patterson, J. P.; Thompson, M. P.; Andolina, C.; Ditri, T. B.; Millstone, J.; Figueroa, J. S.; Rinehart, J. D.; Scadeng, M.; Botta, M.; Gianneschi, N. C., Polycatechol Nanoparticle MRI Contrast Agents. Small 2016, 12, 668-677. (9) Li, Y.; Xie, Y.; Wang, Z.; Zang, N.; Carniato, F.; Huang, Y.; Andolina, C.; Parent, L. R.; Ditri, T. B.; Walter, E. D.; Botta, M.; Rinehart, J. D.; Gianneschi, N. C., Structure and Function of Iron-Loaded Synthetic Melanin. ACS Nano 2016, 10, 10186-10194. (10) Wang, X.; Zhang, J.; Wang, Y.; Wang, C.; Xiao, J.; Zhang, Q.; Cheng, Y., Multiresponsive Photothermal-Chemotherapy with Drug-loaded Melanin-Like Nanoparticles for Synergetic Tumor Ablation. Biomaterials 2016, 81, 114-124. (11) Ma, S.; Liu, L.; Bromberg, V.; Singler, T. J., Electroless Copper Plating of Inkjet-Printed Polydopamine Nanoparticles: a Facile Method to Fabricate Highly Conductive Patterns at Near Room Temperature. ACS Appl. Mater. Interfaces 2014, 6, 19494-19498. (12) Ma, S.; Liu, L.; Bromberg, V.; Singler, T. J., Fabrication of Highly Electrically Conducting Fine Patterns via Substrate-Independent Inkjet Printing of Mussel-Inspired Organic Nano-Material. J. Mater. Chem. C 2014, 2, 3885-3889. (13) Hu, Y.; Zhang, Y.; Xu, C.; Zhu, G.; Wang, Z. L., High-Output Nanogenerator by Rational Unipolar Assembly of Conical Nanowires and Its Application for Driving a Small Liquid Crystal Display. Nano Lett. 2010, 10, 5025-5031. (14) Schadt, M.; H., S.; Schuster, A., Optical patterning of multidomain liquid-crystal displays with wide viewing angles. Nature 1996, 318, 212-215. (15) Holliman, N. S.; Dodgson, N. A.; Favalora, G. E.; Pockett, L., Three-Dimensional Displays: A Review and Applications Analysis. IEEE Trans. Broadcast. 2011, 57, 362-371. (16) Kim, T.; Ra, J. M.; Lee, J. H.; Moon, S. H.; Choi, K. Y., 3D Crosstalk Compensation to Enhance 3D Image Quality of Plasma Display Panel. IEEE Trans. Consum. Electron. 2011, 57, 1471-1477. (17) Park, S. H. K.; Hwang, C. S.; Ryu, M.; Yang, S.; Byun, C.; Shin, J.; Lee, J. I.; Lee, K.; Oh, M. S.; Im, S., Transparent and Photo-stable ZnO Thin-film Transistors to Drive an Active Matrix Organic-Light-Emitting-Diode Display Panel. Adv. Mater. 2009, 21, 678-682. (18) Withers, F.; Del Pozo-Zamudio, O.; Mishchenko, A.; Rooney, A. P.; Gholinia, A.; Watanabe, K.; Taniguchi, T.; Haigh, S. J.; Geim, A. K.; Tartakovskii, A. I.; Novoselov, K. S., Light-Emitting Diodes by Band-Structure Engineering in Vander Waals Heterostructures. Nat. Mater. 2015, 14, 301-306. (19) Yang, Y. X.; Zheng, Y.; Cao, W. R.; Titov, A.; Hyvonen, J.; Manders, J. R.; Xue, J. G.; Holloway, P. H.; Qian, L., High-Efficiency Light-Emitting Devices Based on Quantum Dots with Tailored Nanostructures. Nat. Photonics 2015, 9, 259-266. (20) Shen, C. T.; Liu, H. H.; Yang, M. H.; Hung, Y. P.; Pei, S. C., Viewing-distance Aware Super-resolution for High-Definition Display. IEEE Trans. Image Process. 2015, 24, 403-418. (21) Matsuo, Y.; Iwasaki, S.; Yamamura, Y.; Katto, J., Super-resolution From Digital Cinema to Ultra High Definition Television Using Image Registration of Wavelet Multi-scale


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Components. 2013 IEEE International Conference on Consumer Electronics (Icce) 2013, 159160. (22) Reineke, S.; Lindner, F.; Schwartz, G.; Seidler, N.; Walzer, K.; Lussem, B.; Leo, K., White Organic Light-emitting Diodes with Fluorescent Tube Efficiency. Nature 2009, 459, 234238. (23) Graham-Rowe, D., Electronic Paper Rewrites the Rulebook for Displays. Nat. Photonics 2007, 1, 248-251. (24) Graham-Rowe, D., Electronic Paper Targets Colour Video. Nat. Photonics 2008, 2, 204205. (25) Harris, S., Emergence of the E-book. Nat. Photonics 2010, 4, 748-749. (26) Wisnieff, R., Display technology - Printing screens. Nature 1998, 394, 225-227. (27) Meng, X. W.; Qiang, L.; Su, X. F.; Ren, J.; Tang, F. Q., Synthesis of Black Magnetic Electrophoretic Particles for Magnetic-Electric Dual-Driven Electronic Paper. ACS Appl. Mater. Interfaces 2013, 5, 622-629. (28) Comiskey, B.; Albert, J. D.; Yoshizawa, H.; Jacobson, J., An Electrophoretic Ink for AllPrinted Reflective Electronic Displays. Nature 1998, 394, 253-255. (29) Gelinck, G. H.; Huitema, H. E. A.; Van Veenendaal, E.; Cantatore, E.; Schrijnemakers, L.; Van der Putten, J. B. P. H.; Geuns, T. C. T.; Beenhakkers, M.; Giesbers, J. B.; Huisman, B. H.; Meijer, E. J.; Benito, E. M.; Touwslager, F. J.; Marsman, A. W.; Van Rens, B. J. E.; De Leeuw, D. M., Flexible Active-matrix Displays and Shift Registers Based on Solution-processed Organic Transistors. Nat. Mater. 2004, 3, 106-110. (30) Oh, S. W.; Kim, C. W.; Cha, H. J.; Pal, U.; Kang, Y. S., Encapsulated-Dye All-Organic Charged Colored Ink Nanoparticles for Electrophoretic Image Display. Adv. Mater. 2009, 21, 4987-4991. (31) Park, J. G.; Kim, S. H.; Magkiriadou, S.; Choi, T. M.; Kim, Y. S.; Manoharan, V. N., Full-Spectrum Photonic Pigments with Non-iridescent Structural Colors through Colloidal Assembly. Angew. Chem., Int. Ed. 2014, 53, 2899-2903. (32) Hong, L.; Simon, J. D., Current Understanding of the Binding Sites, Capacity, Affinity, and Biological Significance of Metals in Melanin. J. Phys. Chem. B 2007, 111, 7938-7947. (33) Kanazawa, M.; Hamada, K.; Kondoh, I.; Okano, F.; Haino, Y.; Sato, M.; Doi, K., An Ultrahigh-Definition Display Using the Pixel-offset Method. J. Soc. Inf. Disp. 2004, 12, 93-103. (34) Zhang, X.; Wang, S.; Xu, L.; Feng, L.; Ji, Y.; Tao, L.; Li, S.; Wei, Y., Biocompatible Polydopamine Fluorescent Organic Nanoparticles: Facile Preparation and Cell Imaging. Nanoscale 2012, 4, 5581-5584. (35) Chen, X.; Yan, Y.; Müllner, M.; Van Koeverden, M. P.; Noi, K. F.; Zhu, W.; Caruso, F., Engineering Fluorescent Poly(dopamine) Capsules. Langmuir 2014, 30, 2921-2925. (36) Repenko, T.; Fokong, S.; De Laporte, L.; Go, D.; Kiessling, F.; Lammers, T.; Kuehne, A. J. C., Water-Soluble Dopamine-Based Polymers for Photoacoustic Imaging. Chem. Commun. 2015, 51, 6084-6087. (37) Pu, K. Y.; Shuhendler, A. J.; Jokerst, J. V.; Mei, J. G.; Gambhir, S. S.; Bao, Z. N.; Rao, J. H., Semiconducting Polymer Nanoparticles as Photoacoustic Molecular Imaging Probes in Living Mice. Nat. Nanotechnol. 2014, 9, 233-239. (38) Song, K.; Huang, P.; Yi, C.; Ning, B.; Hu, S.; Nie, L.; Chen, X.; Nie, Z., Photoacoustic and Colorimetric Visualization of Latent Fingerprints. ACS Nano 2015, 9, 12344-12348. (39) Lee, H.; Dellatore, S. M.; Miller, W. M.; Messersmith, P. B., Mussel-Inspired Surface Chemistry for Multifunctional Coatings. Science 2007, 318, 426-430.


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(40) Ryu, D. Y.; Shin, K.; Drockenmuller, E.; Hawker, C. J.; Russell, T. P., A Generalized Approach to the Modification of Solid Surfaces. Science 2005, 308, 236-239. (41) Ahn, J. H.; Kim, H. S.; Lee, K. J.; Jeon, S.; Kang, S. J.; Sun, Y. G.; Nuzzo, R. G.; Rogers, J. A., Heterogeneous Three-Dimensional Electronics by Use of Printed Semiconductor Nanomaterials. Science 2006, 314, 1754-1757. (42) Eichelsdoerfer, D. J.; Liao, X.; Cabezas, M. D.; Morris, W.; Radha, B.; Brown, K. A.; Giam, L. R.; Braunschweig, A. B.; Mirkin, C. A., Large-Area Molecular Patterning with Polymer Pen Lithography. Nat. Photonics 2013, 8, 2548-2560. (43) Hirtz, M.; Oikonomou, A.; Georgiou, T.; Fuchs, H.; Vijayaraghavan, A., Multiplexed Biomimetic Lipid Membranes on Graphene by Dip-Pen Nanolithography. Nat. Commun. 2013, 4, 2591. (44) Biswas, S.; Shalev, O.; Shtein, M., Thin-Film Growth and Patterning Techniques for Small Molecular Organic Compounds Used in Optoelectronic Device Applications. Annu. Rev. Chem. Biomol. 2013, 4, 289-317. (45) d'Ischia, M.; Napolitano, A.; Pezzella, A.; Meredith, P.; Sarna, T., Chemical and Structural Diversity in Eumelanins: Unexplored Bio-Optoelectronic Materials. Angew. Chem., Int. Ed. 2009, 48, 3914-3921. (46) Arsenault, A. C.; Puzzo, D. P.; Manners, I.; Ozin, G. A., Photonic-Crystal Full-Colour Displays. Nat. Photonics 2007, 1, 468-472. (47) Liao, W. H.; Aggarwal, S. J.; Aggarwal, J. K., The Reconstruction of Dynamic 3D Structure of Biological Objects Using Stereo Microscope Images. Mach. Vision. Appl. 1997, 9, 166-178. (48) Mashanov, G. I.; Tacon, D.; Knight, A. E.; Peckham, M.; Molloy, J. E., Visualizing Single Molecules Inside Living Cells Using Total Internal Reflection Fluorescence Microscopy. Methods 2003, 29, 142-152.


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Figure 1. Synthetic melanin E-ink-based device for feature display in aqueous solution. (a) The schematic of the working principle of the E-ink controlled by a couple of electrodes (ITO glass). To-be-displayed patterns were fabricated on the top electrode. (b) The direction and motilities of the negatively charged E-inks were controlled with a low voltage electric field. (Inset: the nanopattern was displayed from synthetic melanin electrophoretic absorption.) The synthetic melanin nanoparticles were characterized with (c) TEM, (d) Cryo-TEM and (e) SEM, respectively. Scale bar: (c) 200 nm, (d) 150 nm, (e) 200 nm.


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Figure 2. An eye distinguishable character was displayed by using synthetic melanin nanoparticles, TiO2 and Carbon black particles, respectively. (a) A clear negative tone character was shown up once the electric field was turned on in synthetic melanin nanoparticles based Eink platform. (b) In comparison, TiO2 ink materials cannot clearly show the feature. (c) Carbon black easily aggregated on the surface of the electrode. (d) The display uniformity in terms of the normalized light intensities, were compared in three groups. (e) The display to background color contrast (S/ N ratio) was compared in three groups.


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Figure 3. Synthetic melanin nanoparticles with ultrahigh resolution E-ink display under a low voltage electric field. (a) A small and complicated feature (an eagle, scale bar, 100 µm) was displayed by the synthetic melanin E-ink within 1s under 1 V (left: without electric field; right: with electric field). In comparison, (b) another surface charged nanomaterial, CNTs, didn’t properly display the feature. (c) ‘Show-and-erase’ performance for a microscale feature (scale bar, 50 µm) by alternating the electric field direction. (d) Spatial light intensities over a line feather in the pattern (red solid lines in c). (e) Multi-cycle repeatability (with 20 repeats) was indicated by the light intensities measured with stereomicroscope. (f) The experimental data (symbols) and theoretical predictions (solid lines) of the response time as functions of the applied voltages for various gaps between two electrodes.


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Figure 4. Fluorescent images display with nanoscale resolution by exploiting oxidized synthetic melanin nanoparticles E-ink system. (a) Fluorescence display of hexagonal micropatterns. (b, c) The oxidized synthetic melanin nanoparticles supported display with dual-channels (light intensity and fluorescence) for an image that can be observed by fluorescence microscope. (d) A nano-circle array, with 500 nm in diameter, was patterned on the top ITO film. Without external electric field, there was no fluorescence display, as validated by spatial fluorescence analyzed in (f). (e) Once an electric field turned on, individual E-ink nanoparticle trapped in the nano-circle pattern resulted in an array of fluorescent nano-dots. Spatial fluorescence intensities of displayed nano-patterns and the background (f) prior to and (g) after the electric field turned on. Scale bar, (a) 10 µm; (b) 100 µm; (c) 30 µm; (d) and (e) 10 µm.


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Synthetic Melanin E-Ink - ACS Applied Materials & Interfaces (ACS

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