1111111111111111111inmuuu~ (12) United States Patent (io) Patent No.: US 9,546,958 B2 Shih (45) Date of Patent: Jan. 17, 2017 (54) METHOD OF STAMPING (58) Field of Classification Search SURFACE-ENHANCE RAMAN CPC .... GO1N 21/65; GO1N 21/656; GO1N 21/658; SPECTROSCOPY FOR LABEL-FREE, GO1J 3/02; GO1J 3/44 MULTIPLEXED, MOLECULAR SENSING See application file for complete search history. AND IMAGING (56) References Cited (71) Applicant: UNIVERSITY OF HOUSTON U.S. PATENT DOCUMENTS SYSTEM, Houston, TX (US) 2004/0009298 Al * 1/2004 Moran ................... H05K 3/182 (72) Inventor: Wei-Chuan Shih, Houston, TX (US) 427/304 2012/0081703 Al 4/2012 Moskovits et al. (73) Assignee: UNIVERSITY OF HOUSTON 2012/0309080 Al 12/2012 Cunningham et al. 2014/0002816 Al 1/2014 Liu et al. SYSTEM, Houston, TX (US) 2014/0104606 Al 4/2014 Shih (*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 U.S.C. 154(b) by 72 days. Wo 2006/134376 A2 12/2006 (21) Appl. No.: 14/699,025 OTHER PUBLICATIONS (22) Filed: Apr. 29, 2015 Lee, Chang H., et al.; Paper Based SERS Swab for Rapid Trace Detection on Real-World Surfaces; Applied Materials & Interfaces, (65) Prior Publication Data vol. 2, No. 12, 3429-3435, 2010. US 2015/0308960 Al Oct. 29, 2015 (Continued) Primary Examiner Abdullahi Nur (74) Attorney, Agent, or Firm Jackson Walker LLP Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 61/985,984, filed on Apr. The present disclosure relates the use of a stamping surface 29, 2014. enhanced Raman scattering (S-SERS) technique with nano- (51) Int. Cl. porous gold disk( NPGD)p lasmonic substrates to produce a GOIJ 3/44 (2006.01) label-free, multiplexed molecular sensing and imaging tech- GOIN 21/65 (2006.01) nique. A NPGD SERS substrate is stamped onto a surface B82Y 30100 (2011.01) containing one or more target molecules, followed by SERS GOIJ 3102 (2006.01) measurement of the target molecules located between the surface and SERS substrate. The target molecules may be (52) U.S. Cl. deposited on the surface, which may be a carrier substrate CPC ............. GOIN 21/658 (2013.01); B82Y 30100 such as polydimethylsiloxane (PDMS). (2013.01); GOIJ 3102 (2013.01); GOIJ 3144 (2013.01) 21 Claims, 11 Drawing Sheets Rx,,m stilt 9 'i US 9,546,958 B2 Page 2 (56) References Cited OTHER PUBLICATIONS Li, Jian Feng, et al.; Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy; Nature, vol. 464, 392-395, 2010. Qi, Ji, et al.; Surface-Enhanced Raman Spectroscopy With Mono- lithic Nanoporous Gold Disk Substrates; Nanoscale, vol. 5, 4105- 4109, 2013. Wang, Hui, et al; Quantitative Analysis of Creatinine in Urine by Metalized Nanostructured Parylene, vol. 15, No. 2, 027004-1-5, 2010. Korean Intellectual Property Office; International Search Report and Written Opinion; PCT Application No. PCT/US2015/028135; Jul. 29, 2015. * cited by examiner 1 e r u g i F b o 0 1 d l e a 1 p m M) am or 0 / a 4, t N e n S 0 r io U at 2 tr n e c 1 C n o C [ ` cg l - 0 all 0n 0 a 1 m a tR ) N N ( : —10P_1P..,,..100 n nil—10 100 p 600 „ 3 ; C)C a M ~ M 9 0 0 4) 11 - ] m 14 1) 0c p 0 ( n ( 2t o 1f ti i .. [Concentra ormal 1000 Shman , -1 N a 0R !) 0 ~ 8 M 3 M P M nM P 0 0n 0 1010 1 P10IO 10 00 _ 6 ~ €, ~ , I I 0 0 0 0 7 6 1 1 0 0 0 0 151100 1300 900 shift (cm"1)Raman 1200 14800 1000 shift (cm")Raman 0 0 70 60 0 0 5 3 e r u g i F U.S. Patent Jan. 17, 2017 Sheet 4 of 11 US 9,546,958 B2 liq ci C U.S. Patent Jan. 17, 2017 Sheet 5 of 11 US 9,546,958 B2 Detection of Glucose x 10, IN In 800 1000 1200 1400 1600 U.S. Patent Jan. 17, 2017 Sheet 6 of 11 US 9,546,958 B2 Figure 6 4 4 1 s ',-1mm-1 t 8 me om1 4$ c07 c ti 727 t 6m' .1m-, * 1n'! 6 men ccm " • 602 573 . cm-' 900 c. + •1654 a1417 cm°l f 4 2 Measure r 0 ( ( ( '1 4 3 -2 F91 b 0 , 7 e r u g i ti F A W S a m a l U U o U.S. Patent Jan. 17, 2017 Sheet 8 of 11 US 9,546,958 B2 N 1106 600 800 1000 1200 1400 1600 Raman Shift( cm-1)