Biofabrication Strategy for Functional Fabrics - Nano Letters (ACS

Publication Date (Web): August 7, 2018 ... On the basis of the inspiration of a phenomenon in an extracurricular experiment for kids, we develop a bio...
0 downloads 0 Views 917KB Size
Subscriber access provided by STEPHEN F AUSTIN STATE UNIV

Communication

A Biofabrication Strategy for Functional Fabrics Muyu Yan, Xiaohong Ma, Yijun Yang, Xi Wang, Weng-Chon Cheong, Zhenhong Chen, Xianghui Xu, Yanjie Huang, Shuo Wang, Lian Chao, and Yadong Li Nano Lett., Just Accepted Manuscript • DOI: 10.1021/acs.nanolett.8b02905 • Publication Date (Web): 07 Aug 2018 Downloaded from http://pubs.acs.org on August 8, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

A Biofabrication Strategy for Functional Fabrics Muyu Yan†, a, Xiaohong Ma†, b, Yijun Yang a, Xi Wang a, Weng-Chon Cheong c, Zhenhong Chen b, Xianghui Xu d, Yanjie Huang e, Shuo Wang b,*, Chao Lian a,*, and Yadong Li c,* a

Department of Chemistry, School of Science, Beijing Jiaotong University, Beijing, 100044,

China b

College of Textiles and Garments, Hebei University of Science and Technology, Shijiazhuang,

050018, China c

Department of Chemistry, Tsinghua University, Beijing, 100084, China

d

College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009,

China e

South China National Centre of Metrology, Guangdong Institute of Metrology, Guangzhou,

510405, China

KEYWORDS. Feeding; Functional fabrics; Luminescent textile; Photoluminescence; Silk

ABSTRACT. Functional fabrics with various unique properties are necessary for making fantastic superior costumes just like superhero suit in Marvel Comics, which are not only dreams

ACS Paragon Plus Environment

1

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 16

of boys but also emerging textiles to facilitate human life. Based on the inspiration of a phenomenon in an extracurricular experiment for kids, we develop a biofabrication strategy to endow silk textiles with various unique physical and chemical properties of functional nanomaterials, where the functional textiles are weaved using silk spun by silkworms that are fed with functional nanomaterials. To confirm the feasibility of this strategy, a photoluminescent plain weave was prepared successfully via feeding biocompatible luminescent nanoparticles to Bombyx mori silkworms. As the functional nanomaterials are enclosed in the silkfibers, the given special properties will be permanent for further application. Considering the wondrous diversity of properties that a variety of nanomaterials possesses may be given to silk fabric, it is promising to see various miraculous costumes in the coming future.

Nano-fabrication technology provides a fascinating avenue bridging science fiction and reality, which has brought about huge changes in our life by preparing all sorts of miraculous raw materials and devices. For instance, flexible nano-devices make wearable electronics possible;1-3 nanocatalysts bring us necessary fuels and chemicals;4, 5 nanochips boost the micromation and the high integration of our intelligent electronic devices.6,

7

In numerous fictional works,

miraculous clothing and accessories for various super heroes not only make boys crazy but also inspire researchers to create technological innovations. In order to make the fantastic superior costumes a reality, however, functional fabrics with various miraculous properties are indispensable. Due to the lustrous appearance and remarkable mechanical properties, silk has been spread to Central and Southern Asia, Europe and North Africa to become a worldwide popular

ACS Paragon Plus Environment

2

Page 3 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

high-end fabric since its first development in ancient China.8, 9 Nowadays, silkworm-feeding has become a classic extracurricular experiment for kids in china to observe metamorphosis of insects, and some interesting gadgets related to the extracurricular experiment are commercial available. For instance, special diets, based on the phenomenon that dyes can be incorporated into silk by feeding Bombyx mori silkworms with dye-containing diets,10-12 can be acquired to feed domesticated silkworms so that the silkworms spin colored silk finally. It is, moreover, attempted to utilize this phenomenon to improve the ultraviolet resistance and mechanical performance for textile application.13,

14

However, these efforts are still stay at the stage to

improve properties related to textile application, which inspired us to consider whether it is possible to endow fabrics with other unique properties by feeding silkworms with something interesting. Nanomaterials exhibit various unique physical and chemical properties, such as optical property,15, 16 magnetic property,17, 18 electrical property19-21 and catalytic property.22, 23 These desired fancy properties may contribute to superior functional textiles exceeding traditional clothing. We hence propose a strategy that functional textiles are prepared via feeding silkworms with various functional nanomaterials (Figure 1a). As the silkworms grow up, the ingested functional nanomaterials will be accumulated in the organs of the nanomaterials-fed silkworms, which will be further enclosed in the silkfibers when the silkworms spin cocoons. As long as the performance of the enclosed nanomaterials can be maintained, functional silkfibers with specific physical and chemical properties will be obtained. Using these functional silkfibers as raw materials, functional fabrics with special properties can be directly woven.

ACS Paragon Plus Environment

3

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 16

Figure 1. (a) Scheme for preparing functional textiles via feeding functional nanomaterials to silkworms. (b) TEM image of the LNPs. Photographs of a colloidal solution of the LNPs under (c) ambient and (d) 365 nm UV illumination, LNPs-treated mulberry leaf under (e) ambient and (f) 365 nm UV illumination, (g) silkworm-B, (h) silkworm-L, (i) cocoon-B, (j) cocoon-L, (k) silkworm-L and (l) cocoon-L under 365 nm UV illumination. Cross-section TEM images of (m) silkfiber-B and (n) silkfiber-L. Microscopy images of (o) silkfiber-B and (p) silkfiber-L. (q) Cross-section HAADF-STEM images and corresponding EDX elemental mapping profiles of silkfiber-L. (r) Luminescence microscopy image of silkfiber-L excited with blue light.

ACS Paragon Plus Environment

4

Page 5 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

To confirm the feasibility of the strategy mentioned above, biocompatible luminescent nanoparticles (LNPs) are chosen as model nanomaterial in this work. By feeding Bombyx mori silkworms with LNPs, the luminescent characteristic of the nanoparticles was successfully rendered to silk. The as-obtained silk was sequently weaved into a plain weave with durable photoluminescent feature. This typical instance demonstrate the validity of this strategy in which a variety of properties of nanomaterials are promising to transfer into silk fabrics, superior functional textiles in science fictions may be close to becoming a reality. It is worth noting that the functional nanomaterials that are fed to silkworms have to be nontoxic and biocompatible. To this end, an established method is selected to encapsulate a traditional luminescent complex, tris(8-hydroxyquinoline) aluminum (Alq3), in water-dispersible and biocompatible nanoparticles of poly (methyl methacrylate-co-methacrylic acid) (PMMA-coMAA). This preparation method has been used to synthesize nanoprobes for biomedical imaging, where the toxicity and biocompatibility of the prepared PMMA-co-MAA nanoparticle capsules have been adequately investigated.24, 25 As shown in Figure 1b-d, the as-prepared spherical LNPs with diameters of ca. 100 nm can be well dispersed in water, and in the meanwhile, inherit the photoluminescent property of the encapsulated green-emitting Alq3. By spraying mulberry leaves with an aqueous colloidal solution of LNPs (Figure 1e, f), LNPs with mulberry leaves were fed to silkworms. Because the ingested nanomaterial may exert some uncertain influence on the physiological behavior of silkworms,26 the sizes of the silkworms fed with LNPs (silkworms-L) and the corresponding cocoons (cocoons-L) are smaller than those of silkworms fed with untreated mulberry leaves (silkworms-B) and the corresponding cocoons (cocoons-B), respectively (Figure 1g-j). During digestion and metabolism, the ingested LNPs are accumulated in the body of silkworms. Consequently, silkworms-L become

ACS Paragon Plus Environment

5

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 16

luminescent green under ultraviolet (UV) illumination, which results from the photoluminescent characteristic of the LNPs within silkworms-L (Figure 1k). When the silkworms-L grow up to spin cocoons, a part of LNPs accumulated in the silkworms mix with silk gland secretions to form luminescent silk that incorporate with LNPs. As shown in Figure 1l, the green luminescence of cocoon-L under UV illumination can be observed by the naked eye. Silkfibers were reeled from the cocoons, and 35 ppm of Al are detected in the silkfibers spun by silkworms-L (silkfibers-L), which is about two times higher than that in the silkfibers spun by silkworms-B (silkfibers-B; Table S1). These results well confirm our presumption mentioned before. Microscopy images and cross-section transmission electron microscopy (TEM) images of the silkfibers reveal that a single silkfiber contains a pair of primary triangular prism-like filaments which are stuck together by sericin (Figure 1m-p). The average diameters of both silkfibers-B and silkfibers-L are measured to be ca. 23 nm (Table S1), and no obvious difference in the appearance of silkfibers from silkworms fed with different diets are observed (Figure S1). Cross-section high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image and Energy-dispersive X-ray spectroscopy (EDS) mapping images show that LNPs in a state of aggregation are encapsulated in the silkfibers-L (Figure 1q). By virtue of the photoluminescent property of the enclosed LNPs, silkfibers-L exhibited obvious photoluminescent feature as well (Figure 1r).

ACS Paragon Plus Environment

6

Page 7 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

Figure 2. (a) TGA curves of the silkfibers (The inset shows the first derivative plots of the TGA curves). (b) The deconvolution of FT-IR spectra in amide I band of the silkfibers. The plots show the original spectra (black dotted line), the fitting line (black solid line), and their deconvoluted traces (three smooth Gaussian curves). (c) The azimuthal intensity distributions of WAXD patterns of the silkfibers. (d) 1D SAXS patterns of the silkfibers (The inset shows the q2I(q)-q-2 curves based on the modified Porod formula, where I(q) represents the scattering intensity and q represents the scattering vector). (e) Stress-strain curves of the silkfibers (The error bars show the standard deviation of elongation at break and fracture strength). The thermal degradation properties of the prepared silkfibers were explored by thermogravimetric analysis (TGA, Figure 2a). However, it differs from those of silks spined by silkworms fed with common inorganic materials which always improve the thermal stability of silkfibers.14, 26-28 We believe this opposite situation stems from the specific structure of LNPs.

ACS Paragon Plus Environment

7

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 16

The LNPs used in this work, in which Alq3 molecules are encapsulated in PMMA-co-MAA nanoparticle capsules, look more like organic polymer nanoparticles. First, the presence of PMMA-co-MAA nanoparticles subtly alter the wetability of silkfiber so that residual water, the initial weight loss before 100 ℃, in silkfibers-L (3.4%) is less than that in silkfibers-B (6.1%). Second, the doping of LNPs in silkfibers-L decreases the thermal stability of the fibers. The silkfibers-B exhibit significant weight loss at ca. 297 ℃, with a peak degradation temperature at ca. 330 ℃. This weight loss, however, occurs at lower temperature for silkfibers-L at ca. 281 ℃, with a peak degradation temperature at ca. 320 ℃. Since the thermal stability of LNPs is higher than that of silkfibers-B (Figure S2), we believe that the interaction between the silkfiber matrix and the encapsulated LNPs changes the secondary structure of silk protein to form a structure that is readily to be degradated at elevated temperature. Finally, the residue masses of silk fiberB and silk fiber-L at 800 are 23.6% and 25.6%, respectively. Excluding the different weight loss of residual water, a difference of 0.7% is due to the larger weight loss of LNPs at high temperature (Figure S2a). It is generally accepted that the nanomaterials fed to silkworms do not change the basic structure of silkworm silks but affect the secondary structure of silk protein.13,

14, 26

Both

silkfibers-B and silkfibers-L possess identical absorption peaks in the Fourier transform-infrared (FT-IR) spectra (Figure S3). The deconvolutions of the FT-IR spectra in amide I band (1600~1700 cm-1) of the fibers, however, show different secondary structure contents. As shown in Figure 2b, the peaks centered at 1615~1640 cm-1, 1655~1660 cm-1 and 1690~1700 cm-1 are attributed to the β-sheet, random coil (or α-helical conformation or both) and β-turn conformations, respectively.13, 14, 29, 30 Because the complicated interactions between LNPs and silk fibroin will hinder the conformation transition of the silk fibroin from random coil/α-helix to

ACS Paragon Plus Environment

8

Page 9 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

β-sheet, silkfibers-L contain, compared with silkfibers-B, higher random coil/α-helix and β-turn contents but lower β-sheet contents. Two-dimensional wide-angle X-ray diffraction (2D-WAXD) analysis is used to investigate the crystalline structures and orientations of the silkfibers (Figure 2c and Figure S4). The Herman’s orientation function and crystalline structural parameters acquired from 2DWAXD are calculated according to reference.31, 32 It is found that no obvious difference between the crystalline structures of silkfibers-B and silkfibers-L can be detected. Nevertheless, the crystallinities of silkfibers-B and silkfibers-L are measured to be 46.6% and 42.1%, respectively. Based on the azimuthal width of the (210) and (020) peaks, the Herman’s orientation function (fc) of silkfibers-B and silkfibers-L are calculated to be 0.924 and 0.895, respectively. In addition, the existence of the mesophase in these silkworm silks is also demonstrated by small angle X-ray scattering (SAXS) measurements (Figure S5). Figure 2d shows the 1D SAXS patterns of the silkfibers and the corresponding q2I(q)-q-2 curves on the basis of the modified Porod law, which is used to calculate the interface factor (σ) and the thickness of interface (Table S2).33 Due to the uptake of LNPs, the interface factor of silkfibers-L is smaller than that of silkfibers-B, which implies that silkfibers-L has a thinner interface than silkfibers-B (Figure 2d). It has been reported that nanomaterials in the silkfibers may act “knots” that will form a relatively soft “cross-linked” network with the crystallites to facilitate the tensile deformation and the dissipation of additional fracture energy.13, 14, 33 Moreover, blending of fibroin with guest polymers can efficiently enhance the strength and ductility by the intermolecular hydrogen bonding between fibroin and the guest-polymer.34, 35 It can be expected that the modification of LNPs may give rise to a mechanical enhancement for the silkfibers. The stress-strain curves of the silkfibres are shown in Figure 2d. Silkfibers-L exhibits an enhanced mechanical property

ACS Paragon Plus Environment

9

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 16

with fracture strength, elongation-at-break and initial modulus of 3.18 cN/dtex, 25.82% and 61.14 cN/dtex, respectively, which obviously exceed those of silkfibers-B (2.77 cN/dtex, 22.78% and 52.83 cN/dtex, see detailed data in Tables S3 and S4).

Figure 3. Photographs of (a) silk weave-B and (b) silk weave-L (The inserts show the microscopy images of corresponding silk weaves). (c) Luminescent emission spectra (λex = 400 nm) of Alq3, LNPs, silk weave-B and silk weave-L with the fitting line and the deconvoluted traces. (d) Photograph of silk weave-L under 365 nm UV illumination (The insert shows the luminescence microscopy image of silk weave-L excited with blue light). To obtain silk fabrics, the silkfibers were entwist into yarns, and then weaved into plain weaves manually (see the “Supporting Information” for details). As shown in Fig. Figure 3a, b, two loose plain weaves, denoted as silk weave-B and silk weave-L respectively, were successfully fabricated by silk fiber-B and silk fiber-L. When Alq3 is encapsulated into the PMMA-co-MAA nanoparticle capsules, the UV/Vis absorption characteristic is essentially maintained, and furthermore the absorption characteristic leads to a slight broad absorption of silk weave-L at ca. 390 nm (Figure S7). The excitation spectrum of Alq3 exhibits a broad

ACS Paragon Plus Environment

10

Page 11 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

excitation band from 300 to 475 nm,36 while the excitation band higher than 400 nm partly decays in LNPs and this excitation characteristic is further maintained in silk weave-L as well (Figure S8). By virtue of the inheritance of luminescent property for the luminescent Alq3 complex, the silk weave-L displays a blue-green emission with wavelength centered at 480 nm, which stems from the superposition of emission of LNPs at 515 nm and autofluorescence of silk at 471 nm, under 400 nm irradiation (Figure 3c). Therefore, it is believed that the photoluminescent characteristic of LNPs is bestowed on the silk weave based on the strategy mentioned before (Figure 3d). It is distinct from modification of functional materials on fibers, the encapsulation of nanomaterials in this work will make the additional materials difficult to peel off during the daily use and wash. The durability of the luminescent property for the prepared silk weave-L was investigated by dry crocking test and laundering test that simulate actual situation during the daily use and wash (see the “Supporting Information” for details). It is found that the photoluminescent feature is well maintained even after these destructive tests (Figure S10), which implies that the functional textiles prepared by this method are durable for practical application. In summary, a luminescent fabric with blue-green luminescent feature is successfully prepared to confirm the feasibility of strategy to weave functional fabrics using silk spun by silkworms that are fed with functional nanomaterials. Since the functional nanomaterials are encapsulated in the silkfibers, the additional features for the silk textiles, photoluminescent property in this work, exhibit good durability during actual using and washing processes. This work opens a new avenue to develop novel functional textiles. It is possible to endow varieties of

ACS Paragon Plus Environment

11

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 16

unique physical and chemical properties of nanomaterials on textiles so that some miraculous suits maybe not only appear in Marvel Comics in the future.

ASSOCIATED CONTENT Supporting Information. Experimental details including reagents, characterization, dry crocking test, laundering test, and the preparation and detailed characterization results of luminescent nanoparticles, silkfibers and silk fabrics.

AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]. * E-mail: [email protected]. * E-mail: [email protected]. Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. †These authors contributed equally. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT

ACS Paragon Plus Environment

12

Page 13 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

This work was jointly supported by the National Natural Science Foundation of China (21603011, 21701007). REFERENCES (1)

Stoppa, M.; Chiolerio, A. Sensors 2014, 14, 11957-11992.

(2)

Gao, W.; Emaminejad, S.; Nyein, H. Y. Y.; Challa, S.; Chen, K.; Peck, A.; Fahad, H. M.;

Ota, H.; Shiraki, H.; Kiriya, D.; Lien, D.; Brooks, G. A.; Davis, R. W.; Javey, A. Nature 2016, 529, 509-514. (3)

Yokota, T.; Zalar, P.; Kaltenbrunner, M.; Jinno, H.; Matsuhisa, N.; Kitanosako, H.;

Tachibana, Y.; Yukita, W.; Koizumi, M.; Someya, T. Sci. Adv. 2016, 2, e1501856. (4)

Wu, Y. E.; Wang, D. S.; Li, Y. D. Chem. Soc. Rev. 2014, 43, 2112-2124.

(5)

Yan, M. Y.; Wu, T.; Chen, L. F.; Yu, Y. L.; Liu, B.; Wang, Y.; Chen, W. X.; Liu, Y;

Lian, C.; Li, Y. D. ChemCatChem 2018, 10, 2433-2441. (6)

Hutcheson, G. D. Sci. Am. 2004, 290, 76-83.

(7)

Kyeremateng, N. A.; Brousse, T.; Pech, D. Nat. Nanotech. 2017, 12, 7-15.

(8)

Vainker, S. Chinese Silk: A Cultural History, British Museum Press, London, 2004.

(9)

Shao, Z. Z.; Vollrath, F. Nature 2002, 418, 741-741.

(10)

Tansil, N. C.; Li, Y.; Teng, C. P.; Zhang, S. Y.; Win, K. Y.; Chen, X.; Liu, X. Y.; Han,

M. Y. Adv. Mater. 2011, 23, 1463-1466. (11)

Tansil, N. C.; Koh, L. D.; Han, M. Y. Adv. Mater. 2012, 24, 1388-1397.

ACS Paragon Plus Environment

13

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(12)

Page 14 of 16

Nisal, A.; Trivedy, K.; Mohammad, H.; Panneri, S.; Sen Gupta, S.; Lele, A.; Manchala,

R.; Kumar, N. S.; Gadgil, M.; Khandewal, H.; More, S.; Laxman, R. S. Acs Sustain. Chem. Eng. 2014, 2, 312-317. (13)

Cai, L. Y.; Shao, H. L.; Hu, X. C.; Zhang, Y. P. Acs Sustain. Chem. Eng. 2015, 3, 2551-

2557. (14)

Wang, Q.; Wang, C. Y.; Zhang, M. C.; Jian, M. Q.; Zhang, Y. Y. Nano Lett. 2016, 16,

6695-6700. (15)

Wang, Y.; Li, X. M.; Zhao, X.; Xiao, L.; Zeng, H. B.; Sun, H. D. Nano Lett. 2016, 16,

448-453. (16)

Pu, C. D.; Qin, H. Y.; Gao, Y.; Zhou, J. H.; Wang, P.; Peng X. G. J. Am. Chem. Soc.

2017, 139, 3302-3311. (17)

Zhou, J.; Wang, Q.; Sun, Q.; Chen, X. S.; Kawazoe, Y.; Jena, P. Nano Lett. 2009, 9,

3867-3870. (18)

Wang, D.; Astruc, D. Chem. Rev. 2014, 114, 6949-6985.

(19)

Tisdale, W. A.; Williams, K. J.; Timp, B. A.; Norris, D. J.; Aydil, E. S.; Zhu, X. Y.

Science 2010, 328, 1543-1547. (20) Zou, X. L.; Liu, Y. Y.; Yakobson, B. I. Nano Lett. 2013, 13, 253-258. (21)

Klein, D. L.; Roth, R.; Lim, A. K. L.; Paul Alivisatos, A.; McEuen, P. L. Nature 2016,

389, 699-701.

ACS Paragon Plus Environment

14

Page 15 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Nano Letters

(22)

Grirrane, A.; Corma, A.; García, H. Science 2008, 322, 1661-1664.

(23)

Lin, L. L.; Zhou, W.; Gao, R.; Yao, S. Y.; Zhang, X.; Xu, W. Q.; Zheng, S. J.; Jiang, Z.;

Yu, Q. L.; Li, Y. W.; Shi, C.; Wen, X. D.; Ma, D. Nature 2017, 544, 80-83. (24)

Shao, G. S.; Han, R. C.; Ma, Y.; Tang, M. X.; Xue, F. M.; Sha, Y. L.; Wang, Y. Chem.-

Eur. J. 2010, 16, 8647-8651. (25)

Fan, Y. Y.; Liu, H. L.; Han, R. C.; Huang, L.; Shi, H.; Sha, Y. L.; Jiang, Y. Q. Sci. Rep.-

Uk 2015, 5, 9908. (26)

Cheng, L.; Huang, H. M.; Chen, S. Y.; Wang, W. L.; Dai, F. Y.; Zhao, H. P. Mater.

Design 2017, 129, 125-134. (27)

Wang, J. T.; Li, L. L.; Feng, L.; Li, J. F.; Jiang, L. H.; Shen, Q. Int. J. Biol. Macromol.

2014, 63, 205-209. (28)

Wang, J. T.; Li, L. L.; Zhang, M. Y.; Liu, S. L.; Jiang, L. H.; Shen, Q. Mat. Sci. Eng. C-

Mater. 2014, 34, 417-421. (29)

Chen, X.; Shao, Z. Z.; Knight, D. P.; Vollrath, F. Proteins 2007, 68, 223-231.

(30)

Jin, H. J.; Kaplan, D. L. Nature 2003, 424, 1057-1061.

(31)

Dickerson, M. B.; Fillery, S. P.; Koerner, H.; Singh, K. M.; Martinick, K.; Drummy, L.

F.; Durstock, M. F.; Vaia, R. A.; Omenetto, F. G.; Kaplan, D. L.; Naik, R. R. Biomacromolecules 2013, 14, 3509-3514.

ACS Paragon Plus Environment

15

Nano Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(32)

Page 16 of 16

Riekel, C.; Burghammer, M.; Dane, T. G.; Ferrero, C.; Rosenthal, M. Biomacromolecules

2017, 18, 231-241. (33)

Pan, H.; Zhang, Y. P.; Shao, H. L.; Hu, X. C.; Li, X. H.; Tian, F.; Wang, J. J. Mater.

Chem. B 2014, 2, 1408-1414. (34)

Wang, Y. Z.; Kim, H. J.; Vunjak-Novakovic, G. D.; Kaplan, L. Biomaterials 2006, 27,

6064-6082. (35)

Koh, L. D.; Cheng, Y.; Teng, C. P.; Khin, Y. W.; Loh, X. J.; Tee, S. Y.; Low, M.; Ye, E.;

Yu, H. D.; Zhang, Y. W.; Han, M. Y. Prog. Polym. Sci. 2015, 46, 86-110. (36)

Yawalkar, P. W. Dhoble, S. J.; Kalyani, N. T.; Atram, R. G.; Kokode, N. S.

Luminescence 2013, 28, 63-68.

Table of Contents Graphic

ACS Paragon Plus Environment

16