US 20190187331A1 ( 19) United States (12 ) Patent Application Publication (10 ) Pub. No. : US 2019 /0187331 A1 Omenetto et al. (43 ) Pub . Date : Jun . 20 , 2019 ( 54 ) PATTERNED SILK INVERSE OPAL Publication Classification PHOTONIC CRYSTALS WITH TUNABLE , (51 ) Int. Cl. GEOMETRICALLY DEFINED STRUCTURAL GO2B 1 / 00 (2006 . 01 ) COLOR C30B 29 /58 ( 2006 .01 ) B33Y 70 / 00 ( 2006 .01 ) (71 ) Applicant : Trustees of Tufts College , Medford , B29D 11 /00 ( 2006 .01 ) MA (US ) C08H 1 / 00 ( 2006 .01 ) ( 52 ) U . S . CI. (72 ) Inventors : Fiorenzo G . Omenetto , Lexington , MA CPC G02B 1 /005 (2013 . 01 ) ; C30B 29 /58 (US ) ; Yu Wang , Medford , MA (US ) (2013 .01 ) ; B33Y 10 /00 (2014 . 12 ) ; B29D 11 / 0074 ( 2013 .01 ) ; C08H 1 / 00 ( 2013 .01 ) ; (21 ) Appl . No .: 16 /319 , 466 B33Y 70 / 00 ( 2014 . 12 ) (57 ) ABSTRACT ( 22 ) PCT Filed : Aug. 1, 2017 The present disclosure relates to patterned photonic crystals . Provided photonic crystals are large scale silk inverse opals PCT/ US2017 / 044953 with tunable , geometrically defined structural color . Pro ( 86 ) PCT No .: vided photonic crystals exhibit structural color or a photonic $ 371 ( c )( 1 ) , band gap (“ PBG ” ) . Provided photonic crystals are is found ( 2 ) Date : Jan . 21, 2019 to be highly sensitive to water vapor and UV irradiation . Provided multicolored photonic macro - or micro - patterns are shown by selectively applying water vapor or UV Related U . S . Application Data irradiation through a shadow mask . The present disclosure (60 ) Provisional application No . 62 /369 , 630 , filed on Aug . also provides methods for making and using the same . 1 , 2016 . Specification includes a Sequence Listing . Hit ANN ER ! PS colloidal ? , Amorphous Introduction PS spheres Crystalline PS monolayer crystal multilayers silk fibroin . ser: - ii, B - sheet B formation - ïi, Degradation Aqueous - of silk chain Silk inverse opal Silk/ PS composite silk solution - vii W ör UV : : : : : I- UV . - W W in ww -sheet mer Amorphous Chain Patterning Non - uniformNO Short polypeptide * H20 molecule anisotropicUniform shrinkage anisotropic shrinkage Patent Application Publication Jun . 20 , 2019 Sheet 1 of 22 US 2019 /0187331 A1 internetowwww wwwwwwwwwwwwwwwwwwwwwwwwww . : . : . i . 34 . Aqueous silksolution Non-uniformanisotropicshrinkage . PScolloidal . vitit Silk/PScomposite Uniformanisotropicshrinkage . ' . IntroductionPSspheresCrystallinemonolayercrystalmultilayers . FIG.1 . SEX Silkinverseopal FH materials ViiWorUV Patterning - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - silkfibroin ofsilkchain i,Amorphous ii,B-sheet formation iii,Degradation Shortpolypeptide*H20molecule iii wB-sheetmerAmorphousChain Patent Application Publication Jun . 20 , 2019 Sheet 2 of 22 US 2019 /0187331 A1 KIKISIKAN IVIRANI WS SEK KORAKVESTAVRAWKIA VALAIKU TAKTNAh KVINI w KIEL LAUNCH VIRTUAL CATEVE 500 nm 500 nm KANAKASIKVISININ BATAINA TK2KABSSTRAAT ERRENTALKUTCHES WHOVA OM BA ERKO WWURUKAVIK BODIKUSKIKKININKININKARASAASASKINERCUTIARA V KRAINIANW ASISWA A 500 nms 500 nm 500 nm WWWWISATA ESSEX - 1 layer -- - 3 layers -- - 5 layers T XXN Normalizedreflectance Normalizedreflectance cm " 1 cm 400Wavelength 600 /800 nm Wavelength400 600 / 800nm 1?? . 15 mm 15 mm FIG . 2 Patent Application Publication Jun . 20 , 2019 Sheet 3 of 22 US 2019 /0187331 A1 FIG.3 mm mm12 100um WN 1500nm WK W * . WWW . mm 100um 500nm =5s . MMMMIIN800 800 700 .W www R 500600700Wavelength/nm * X 600 mm 100um * 500nm 500 400 400 Normalized reflectance 2 mm 100um 5500nm .-WVtreatmentfor5s291621_-Wtreatmentfor1h ControlAmidel 160015001400Wavenumbers/cm Absorbance 1700 Patent Application Publication Jun . 20 , 2019 Sheet 4 of 22 US 2019 / 0187331 A1 t = 0 h . =. 0 .. 5 . h . 1h 1 .5 h 999 72h 792 .5h 6377 MM HIV Normalizedreflectance Wavelength/nm 400 500 600 700 Wavelength / nm - 1h -- - -- 1. 5 h 2h Time1 2 3 Normalizedreflectance - 2. 5 h gor 400 500 600 700 800 Wavelength / nm Amide ! Oh 1638 Amide II - 1h N - - - 1 .5 h Absorbance - .. - 2 .5 h t = 1h Elsh 1700 1600 1500 1400 T- 2 .5h Wavenumbers / cm FIG . 4 Patent Application Publication Jun . 20 , 2019 Sheet 5 of 22 US 2019 /0187331 A1 1mm opora 700 Inair -Inisopropanol-Inmethanol 500600 Wavelength/nm 400 1mm Normalized reflectance FIG.5 . T S 800 Inair -Inisopropanol-Inmethanol C _ _ _ 600700 Wavelength/nm 1mm so wwmmmm IN beplanningen XXXXXX 500 WWE bideetano400 Normalized reflectance Patent Application Publication Jun . 20 , 2019 Sheet 6 of 22 US 2019 /0187331 A1 MMM W W ? / ? 2.5 , 5-0 0. .5 0 0 . 5 0 X / A 0.5 FIG . 6 Patent Application Publication Jun . 20 , 2019 Sheet 7 of 22 US 2019 / 0187331 A1 1 .66 1. 64 1 .62 1 .60 1 .584 1 . 56 1 . 54 1 .52 400 600 800 1000 1200 1400 Wavelength / nm FIG . 7 Patent Application Publication Jun . 20 , 2019 Sheet 8 of 22 US 2019 /0187331 A1 Layer 1 XXXX Layer 2 Layer 3 FIG . 8 Patent Application Publication Jun . 20 , 2019 Sheet 9 of 22 US 2019 /0187331 A1 B 500 nm HJE: We W BRA BA WW WX ho444 5 cm 10 um FIG . 9 Patent Application Publication Jun . 20 , 2019 Sheet 10 of 22 US 2019 /0187331 A1 Amorphous silk film Amide 1 - SIO 1638 1621 - Crystalline SIO Absorbance 17 00 1600 1500 1400 1300 1 200 Wavenumbers / cm ? FIG . 10 Patent Application Publication Jun . 20 , 2019 Sheet 11 of 22 US 2019 /0187331 A1 -1layer 800 -3layers -5layers 500600700 Wavelength/nm NA 400 100T Reflectance / % B FIG.11 -1layer 3layers -5layers 600 NAWAWUWY 500 Wavelength/nm 400 ' ' A100T Reflectance % Patent Application Publication Jun . 20 , 2019 Sheet 12 of 22 US 2019 /0187331 A1 50 5mm 5mm THEAS wwwwwwwww 40 2030 Incidentangle/° 10 5mm 5mm 0 600 450+ Wavelength / nm V FIG.12 5mm 30- 35- 40 •??wscentissimis 11.' -45 na800 So 700 bmm Wavelength/nm 500600 . 5mm 400 1005 50 Reflectance / % ???????????????????? ?????????? ?? ?? ?????? 000000000000 D Patent Application Publication Jun . 20 , 2019 Sheet 13 of 22 US 2019 /0187331 A1 SWSV 100 um FIG . 13 Patent Application Publication Jun . 20 , 2019 Sheet 14 of 22 US 2019 /0187331 A1 t = 1s 1 = S7 too nm 500 nm ht= 35 t = 5 S VA WMV WA 9 WS S 500 nm MMMMM 500 nm IS 500nm FIG . 14 Patent Application Publication Jun . 20 , 2019 Sheet 15 of 22 US 2019 /0187331 A1 m . - - - W Os ( Theory ) -- - - W is ( Theory ) W Os ( Exper ) - -- -- W 1s (Exper ) Normalizedreflectance TOUR Normalizedreflectance www 400 500 600 700 800 400 500 600 700 800 Wavelength / nm Wavelength / nm - -- WV 2s (Theory ) - -- W3s (Theory ) - - - - -W 2s (Exper ) -- W 3s (Exper ) * * Normalizedreflectance * reflectanceNormalizedNormalizedreflectance South 400 500 600 700 800 400 500 600 700 800 Wavelength / nm Wavelength / nm 7 - - -W 5s (Theory ) 7 Experimental value - -- - -WV 58 (Exper ) Theoretical value Normalizedreflectance Compressionfactor: . N 400 500 600 700 800 : Wavelength / nm FIG . 15 Time / s Patent Application Publication Jun . 20 , 2019 Sheet 16 of 22 US 2019 /0187331 A1 C - - - - - - Os -- - manon- - 1 s Normalizedreflectance 5 s WILW Hit ! W . UNAINT . willhemmmm 1 . S mamia U 400 500 600 700 800 Wavelength / nm FIG . 16 Patent Application Publication Jun . 20 , 2019 Sheet 17 of 22 US 2019 /0187331 A1 . S SSRLOURRBCEBES Reflectance - - 350 . 400 . 450 . 500 . 550 . 600 Wavelength / nm FIG . 17 Patent Application Publication Jun . 20 , 2019 Sheet 18 of 22 US 2019 /0187331 A1 5 4 32 Time/h i ) F009 Wavelength / nm FIG.18 * * -0.5h -4.5h -2.5h -1.5h -3.5h u4h -5h -3h -Oh -2h -1h 800 . 700 . Wavelength/nm 500600 . 400 .. w WEL . 300 Normalized reflectance Patent Application Publication Jun . 20 , 2019 Sheet 19 of 22 US 2019 /0187331 A1 -17nm . 23nm33mm h1=t N11nm17 t=2.5h . mm33um 0. 2x 19.FIG 00nm h2.5=t um0.2:x W Wh v:titrovinini2.0 um y:2.0 um 23.0nm then 23.0nm 15.0 15.00.10 1-33.0 WE5.0 1-33.0 A Buradio 500nm wiWWW we t=1.5h Wissen 2012 500nm 500nm TA 117WEILDIRIM * TimeofUV/h a iii . W 500mm SAL=1h AN 21nmno 79 nm13 0.51.052.05 t=Oh t=1.5h ohnm26 SV um0.2 um0.2 :x 11 3.0) 0.5- 2.0 1.011 541.nm/Rms y:2.0 um Vsistemisiunii:2 .0 um C t=Oh 20 00nm 23.0nm 15.010.0 8.3 T17.8nm 10.0 5.0 0, 0.10--15.0 -20.0 0.33- *-5.0-10.0 0.15- . 1 WWWWWWWWWWWWWWW uvi hun 500nm ygg 500nm w Patent Application Publication Jun . 20 , 2019 Sheet 20 of 22 US 2019 /0187331 A1 U ih (Theory ) -- - - - WV 1. 5h ( Theory ) - -- -- UV 1h (Exper ) - -- -- UV 1. 5h (Exper ) Normalizedreflectance Normalizedreflectance whothe PA 400 500 600 700 800 400 500 600 700 800 Wavelength / nm Wavelength / nm -- - - UV 2h (Theory ) -- - UV 2. 5h (Theory ) -- - - - UV 2h (Exper ) UV 2. 5h (Exper ) Normalizedreflectance Normalizedreflectance MER 400 500 600 700 800 400 500 600 700 800 Wavelength / nm Wavelength / nm FIG . 20 Patent Application Publication Jun . 20 , 2019 Sheet 21 of 22 US 2019 /0187331 A1 . - - - In air ( Theory ) - -- - - - In air (Theory ) -- - - - In air (Exper ) - -- - - In air (Exper ) Normalizedreflectance Normalizedreflectance 400 500 600 700 800 400 500 600 700 800 Wavelength / nm Wavelength / nm -- - In isopropanol ( Theory) AM - - - In isopropanol (theory ) -- In isopropanol ( Exper ) / -- In isopropanol (Exper ) Normalizedreflectance Normalizedreflectance www NES ALLT S . REE . th AN 400 500 600 700 800 Wh 400 500 Wavelength600 700/ nm 800 Wavelength / nm -- - - - -In methanol ( Theory ) mante in methanol (Theory ) , - In methanol (Exper ) - - - In methanol ( Exper ) . w Normalizedreflectance Sea Normalizedreflectance . wy y www.OSSES www. 400 500 600 700 800 400 500 600 700 800 Wavelength / nm Wavelength / nm FIG . 21 Patent Application Publication Jun . 20 , 2019 Sheet 22 of 22 US 2019 /0187331 A1 MMM 1cm 600 -Inair -Inisopropanol-Inmethanol 500 Wavelength/nm M ' . " h , N .. 400 ma * 1cm . .. IMAM www. am www . Normalized reflectance FIG.22 700 WWMA Inair -Inisopropanol -Inmethanol 600 Wavelength/nm 1cm * 500 Any . www. 400 New Normalized reflectance US 2019 /0187331 A1 Jun .