摘要
合成了核壳结构的表面增强拉曼散射(Surface-Enhanced Raman Scattering, SERS)探针,用于大型客体及曲面客体表面的潜指纹成像。以对硝基苯硫酚(4-Nitrothiophenol,pNTP)为拉曼小分子,修饰在纳米金表面,然后在其表面覆盖一层SiO_2壳层,制备Au@pNTP@SiO_2核壳纳米结构,经溶菌酶适配体功能化修饰制得SERS探针。对探针结构进行透射电镜(TEM)、能量色散光谱(EDS)和SERS增强效应的测试,然后将探针与不同客体表面的老化潜指纹进行孵育,使SERS探针与指纹嵴线中的溶菌酶结合,用透明胶带转移指纹,采用共聚焦拉曼显微镜进行SERS信号的检测、成像。结果表明,核壳SERS探针粒径分布均一,多集中于~60 nm,具有优良的稳定性和分散性; SERS增强效应显著,其信号强度高、重现性好,并且在723、855、1081、1343和1572 cm~(-1)处具有显著的特征峰。将SERS探针用于胶带潜指纹成像时,不仅可呈现指纹的一级结构(图案),而且指纹的二级结构(细节)如嵴中断、叉等结构也清晰可见。本研究发展的适配体功能化的SERS探针结合胶带转移潜指纹的指纹识别策略,为法医学领域提供了一种有效的潜指纹识别方法,并在食品安全等公共安全检测领域具有潜在应用价值。
Adhesive tape combined with the core-shell SERS nanoprobe was used to recognize the latent fingerprints on the surface of the object, which provided an effective solution for the imaging of latent fingerprint on large immobile object and surface object. First, Au@ pNTP@SiO_2 SERS probes modified by aptamers specific to lysozyme was prepared and characterized by TEM/EDS. The SERS enhancement activity was also tested. Then the probe was incubated with the aged-latent fingerprints on the surface of different object. Afterwards, the dried latent fingerprint with modified SERS probes was transferred on the adhesive tape and imaged under the confocal Raman microscope. The results showed that the size distribution of the core-shell SERS probe was uniform, mostly concentrated in 60 nm, leading to excellent stability and dispersity. The SERS probe also had enhanced SERS effect, strong SERS intensity and reproducibility with the characteristic peak at 723, 855, 1081, 1343 and 1572 cm~(-1), which was consistent with the previous reports. When applied this SERS probe into the tape-transferred latent fingerprint's imaging, not only the first-level structure(pattern) of fingerprint but also the second structure of fingerprint such as the ridge interruption and ridge fork could be clearly seen. The successful development of the SERS imaging of transferred latent fingerprint on adhesive tapes combined with the aptamer-functionalized SERS probe provides an effective method for recognizing latent fingerprints in forensic science, which also has the potential application in the other areas such as food safety and public safety testing.
引文
1 Hazarika P,Jickells S M,Wolff K,Russell D A.Angew.Chem.Int.Edit.,2008,47(52):10167-10170
2 Almog J,Hirshfeld A,Klug J T.Foren.Sci.,1982,27(4):912-917
3 Hazarika P,Russell D A.Angew.Chem.Int.Edit.,2012,51(15):3524-3531
4 Becue A.Anal.Methods,2016,8(45):7983-8003
5 Ewing A V,Kazarian S G.Analyst,2017,142(2):257-272
6 ZHAO Ya-Bin,LUO Ya-Ping.Foren.Sci.Tech.,2015,40(4):312-317赵雅彬,罗亚平.刑事技术,2015,40(4):312-317
7 Wang Y Q,Wang J,Ma Q Q,Li Z H,Yuan Q.Nano Res.,2018,11(10):5499-5518
8 Xu L R,Zhang C Z,He Y Y,Su B.Sci.China Chem.,2015,58(7):1090-1096
9 Wood M,Maynard P,Spindler X,Lennard C,Roux C.Angew.Chem.Int.Edit.,2012,51(49):12272-12274
10 Kim Y J,Jung H S,Lim J,Ryu S J,Lee J K.Langmuir,2016,32(32):8077-8083
11 Chen H,Ma R L,Chen Y,Fan L J.ACS Appl.Mater.Interfaces,2017,9(5):4908-4915
12 Zhang S J,Liu R H,Cui Q L,Yang Y,Cao Q,Xu W Q,Li L D.ACS Appl.Mater.Interfaces,2017,9(50):44134-44145
13 Chen Y H,Kuo S Y,Tasi W K,Ke C S,Liao C H,Chen C P,Wang Y T,Chen H W,Chan Y H.Anal.Chem.,2016,88(23):11616-11623
14 Wang J K,He K,Zhu Y L,An Z B,Chen P,Grimes C A,Nie Z,Cai Q Y.Chem.Commun.,2018,54(6):591-594
15 Hai J,Li T R,Su J X,Liu W S,Ju Y M,Wang B D,Hou Y L.Angew.Chem.Int.Edit.,2018,57(23):6786-6790
16 Tan J,Xu L R,Li R,Su B,Wu J M.Angew.Chem.Int.Edit.,2014,53(37):9822-9826
17 Xu L R,Li Y,He Y Y,Su B.Analyst,2013,138(8):2357-2362
18 Xu L R,Zhou Z Y,Zhang C Z,He Y Y,Su B.Chem.Commun.,2014,50(65):9097-9100
19 Xu L R,Yan L,Wu S Z,Liu X H,Su B.Angew.Chem.Int.Edit.,2012,51(32):8068-8072
20 Jaber N,Adam L,Hadar G,Sanaa S,Daniel M,Joseph A.Angew.Chem.Int.Edit.,2012,51(49):12224-12227
21 He Y Y,Xu L R,Zhu Y,Wei Q H,Zhang M Q,Su B.Angew.Chem.Int.Edit.,2014,53(46):12609-12612
22 Stauffer E,Becue A,Singh K V,Ravindranathan Thampi K,Champod C,Margot P.Foren.Sci.Inter.,2007,168(1):E5-E9
23 Schnetz B,Margot P.Foren.Sci.Inter.,2001,118(1):21-28
24 Amin M O,Madkour M,Al-Hetlani E.Anal.Bioanal.Chem.,2018,410(20):4815-4827
25 Chaurand P.Analyst,2018,143(15):3586-3594
26 Svidrnoch M,Maier V,Havlíˇcek V,Lemr K.Anal.Chim.Acta,2018,1030:25-32
27 Manicke N E,Dill A L,Cooks R G,Ifa D R.Science,2008,321(5890):805
28 Wu J,Fang J H,Yang X H,Wang C N.Nanotechnology,2018,29(46):465701
29 Xie Y F,Chen T,Guo Y H,Cheng Y L,He Q,Yao Q R.Food Chem.,2019,270:173-180
30 Singha S S,Mondal S,Bhattacharya T S,Das L,Sen K,Satpati B,Das K,Singha A.Biosens.Bioelectron.,2018,119:10-17
31 WANG Xiao-Meng,ZHANG Zhen,LIU Jing,ZHANG Shu-Sheng.Chinese J.Anal.Chem.,2017,45(12):2026-2031 王晓蒙,张振,刘静,张书圣.分析化学,2017,45(12):2026-2031
32 Venkatakrishnan K,Tan B.Nat.Commun.,2018,9(1):3065-3065
33 Zhao J J,Zhang K,Li Y X,Ji J,Liu B H.ACS Appl.Mater.Interfaces,2016,8(23):14389-14395
34 Zhao L,Wang W,Hu W H.Anal.Chem.,2016,88(21):10357-10361
35 Zhao L,Huang X Q,Hu W H.ACS Appl.Mater.Interfaces,2017,9(42):37350-37356
36 Wang Z J,Luo Y,Xie X Y,Hu X J,Song H Y,Zhao Y,Shi J Y,Wang L H,Glinsky G,Chen N,Lal R,Fan C H.Angew.Chem.Int.Edit.,2018,57(4):972-976
37 Kwak G,Lee W E,Kim W H,Lee H.Chem.Commun.,2009,16:2112-2114
38 Yang S Y,Wang C F,Chen S.Angew.Chem.Int.Edit.,2011,50(16):3706-3709
39 Li M,Guo X D,Li H,Zuo X L,Hao R Z,Song H B,Aldalbahi A,Ge Z L,Li L,Li Q,Song S P,Li S H.ACS Appl.Mater.Interfaces,2018,10(1):341-349
40 Benjamin F,Chen Y K,Kyla B,Andrew F,Fu D.Anal.Chem.,2017,89(8):4468-4473
41 Tran D T,Janssen K P,Pollet J,Lammertyn E,Anne J,Schepdael A V,Lammertyn J.Molecules,2010,15(3):1127-1140
42 Ellington A D.Bioorgan.Med.Chem.,2001,9(10):2525-2531
43 Frens G.Nature,1973,241:20-22
44 Zhang H,Zhang X G,Wei J,Wang C,Chen S,Sun N L,Wang Y H,Chen B H,Yang Z L,Wu D Y,Li J F,Tian ZQ.J.Am.Chem.Soc.,2017,139(30):10339-10346
45 Li K,Qin W W,Li F,Zhao X C,Jing B W,Wang K,Deng S H,Fan C H,Li D.Angew.Chem.Int.Edit.,2013,52(44):11542-11545
46 Zhang Y Y,Zhou W,Xue Y,Yang J,Liu D B.Anal.Chem.,2016,88(24):12502-12507