Surface-Enhanced Raman Spectroscopy: Bioanalytical, Biomolecular and Medical Applications

230 Pages·2016·6.295 MB·English

by  Marek Procházka

Biological and Medical Physics, Biomedical Engineering
Marek Procházka
Surface-
Enhanced
Raman
Spectroscopy
Bioanalytical, Biomolecular and Medical
Applications
Surface-Enhanced Raman Spectroscopy
BIOLOGICAL AND MEDICAL PHYSICS,
BIOMEDICAL ENGINEERING
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Editor-in-Chief:
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EditorialBoard:
MasuoAizawa,DepartmentofBioengineering, JudithHerzfeld,DepartmentofChemistry,
TokyoInstituteofTechnology,Yokohama,Japan BrandeisUniversity,Waltham,Massachusetts,USA
OlafS.Andersen,DepartmentofPhysiology, MarkS.Humayun,DohenyEyeInstitute,
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CornellUniversity,NewYork,USA PierreJoliot,InstitutedeBiologie
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ImperialCollegeofScience,Technology AcademyofSciences,Szeged,Hungary
andMedicine,London,England RobertS.Knox,DepartmentofPhysics
HowardC.Berg,DepartmentofMolecular andAstronomy,UniversityofRochester,Rochester,
andCellularBiology,HarvardUniversity, NewYork,USA
Cambridge,Massachusetts,USA AaronLewis,DepartmentofAppliedPhysics,
VictorBloomfield,DepartmentofBiochemistry, HebrewUniversity,Jerusalem,Israel
UniversityofMinnesota,St.Paul,Minnesota,USA StuartM.Lindsay,DepartmentofPhysics
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MarkolfNiemz,MedicalFacultyMannheim,
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UniversityofHeidelberg,Mannheim,Germany
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VanderbiltUniversity,Nashville,Tennessee,USA
NationalInstitutesofHealth,Bethesda,
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More information about this series at http://www.springer.com/series/3740
á
Marek Proch zka
Surface-Enhanced Raman
Spectroscopy
Bioanalytical, Biomolecular and Medical
Applications
123
MarekProcházka
Institute of Physics
CharlesUniversity inPrague
Prague 2
Czech Republic
ISSN 1618-7210 ISSN 2197-5647 (electronic)
Biological andMedical Physics,Biomedical Engineering
ISBN978-3-319-23990-3 ISBN978-3-319-23992-7 (eBook)
DOI 10.1007/978-3-319-23992-7
LibraryofCongressControlNumber:2015950036
SpringerChamHeidelbergNewYorkDordrechtLondon
©SpringerInternationalPublishingSwitzerland2016
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This book is dedicated to Prof. Blanka
Vlčková from the Department of Physical
and Macromolecular Chemistry, Faculty
of Science, Charles University in Prague,
on the occasion of her jubilee.
Preface
About 40 years after its discovery, surface-enhanced Raman scattering (SERS)
spectroscopyhasbecomeafullygrownspectroscopictechniqueandthenumberof
applications in the chemical, material, and particularly in life sciences has been
rapidlyexpanding.SeveralmonographscoveringSERStheoryandapplicationsare
available, but a compact monograph written by one author and focused on
bio-relatedSERSapplicationsismissing.Themotivationtocompilethisbookwas
to provide the best possible overview of the bioanalytical, biomolecular and
medical applications of SERS. Please regard this book primarily as a review of
selected bio-related SERS applications reported during the past two decades. Of
course, it was impossible to include all applications from the extensive SERS
literature in one book. I must apologize to all colleagues whose work is not
describedorcitedhere.Ihopethisbookwillbeusefulforstudentsandnewcomers
with only little background in SERS spectroscopy as well as for experts who just
need a quick overview of SERS applications with keyword “bio”.
AsanM.Sc.studentatFacultyofMathematicsandPhysics,CharlesUniversity
in Prague, I chose SERS spectroscopy as my research topic with very little
knowledge about it and even less knowledge about how complicated it could be.
During the twenty plus years that I have been working on SERS spectroscopy I
have discovered how mysterious it is and at the same time what a fascinating
researchfielditis.WhenIwasresearchingmaterialforthisbook,themostexciting
thing for me was the appreciation I got from seeing the great amount of progress
that has been made in SERS spectroscopy over the past two decades.
I would like to thank two special persons/teachers: Prof. Blanka Vlčková from
the Department of Physical and Macromolecular Chemistry, Faculty of Science,
CharlesUniversityinPrague,apioneerofSERSinCzechRepublicandProf.Josef
Štěpánek from the Institute of Physics, Faculty of Mathematics and Physics,
Charles University in Prague. I was infected with their enthusiasm for scientific
work and without them I would never have come to the position where I now find
myself.
vii
viii Preface
IthankalsomycolleaguesandstudentsfromDivisionofBiomolecularPhysics,
Institute of Physics, Faculty of Mathematics and Physics, Charles University in
Prague for encouraging me during my work on this book. In particular, I should
mention those who helped me in the completion of this book. I thank Dr. Eva
Kočišováforreadingthemanuscriptandhelpingwiththegraphics.IthankmyPh.D.
students Mgr. Vlastimil Peksa for valuable comments on the manuscript and Mgr.
Martin Šubr for reference database. I thank Dr. Vladimír Kopecký, Jr. for typog-
raphy.Finally,IwouldliketothankMr.MarshallJohnsonforEnglisheditingofthis
book. Please note that I used British English. Financial support from the Czech
Science Foundation(Project number P205/13/20110S) isalso greatlyappreciated.
Prague, June 2015 Marek Procházka
Contents
1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Basics of Raman Scattering (RS) Spectroscopy . . . . . . . . . . . . . . . 7
2.1 Short History of Raman Effect. . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Basic Theory of RS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3 Molecular Vibrations and Their Raman Activity. . . . . . . . . . . . . 12
2.4 Raman Experiment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.5 Raman Spectroscopy for Biomolecular Studies. . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3 Basics of Surface-Enhanced Raman Scattering (SERS). . . . . . . . . . 21
3.1 SERS Mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.1.1 EM Mechanism of SERS . . . . . . . . . . . . . . . . . . . . . . . 22
3.1.2 Chemical (Molecular) Mechanism of SERS. . . . . . . . . . . 24
3.2 SERS EFs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.3 SM-SERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.4 SERS-Active Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.4.1 Metallic NP Hydrosols. . . . . . . . . . . . . . . . . . . . . . . . . 30
3.4.2 NPs and Nanostructures on Planar Supports
Prepared by Bottom-Up Techniques. . . . . . . . . . . . . . . . 34
3.4.3 Nanostructures Fabricated Using Nanolithographic
(Top-Down) Techniques. . . . . . . . . . . . . . . . . . . . . . . . 37
3.4.4 Highly Ordered Metallic Nanostructures Fabricated
by Template Techniques. . . . . . . . . . . . . . . . . . . . . . . . 39
3.4.5 Commercially Available Substrates . . . . . . . . . . . . . . . . 47
3.5 Practical Aspects of SERS. . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.6 Related Enhanced Techniques . . . . . . . . . . . . . . . . . . . . . . . . . 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
ix
x Contents
4 Bioanalytical SERS Applications. . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.1 Quantitative SERS Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.1.1 SERS-Active Substrates for Quantitative SERS . . . . . . . . 61
4.1.2 Internal Intensity Standards for Quantitative SERS. . . . . . 65
4.1.3 Sensitivity and Specificity of SERS Sensor. . . . . . . . . . . 68
4.2 SERS Sensing of Pharmaceuticals and Drugs. . . . . . . . . . . . . . . 70
4.2.1 SERS Sensing of Pharmaceuticals . . . . . . . . . . . . . . . . . 70
4.2.2 SERS Sensing of Drugs . . . . . . . . . . . . . . . . . . . . . . . . 72
4.3 SERS Sensing of Pollutants, Food Contaminants
and Food Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
4.3.1 SERS Sensing of Pollutants and Pesticides . . . . . . . . . . . 77
4.3.2 SERS Sensing of Melamine . . . . . . . . . . . . . . . . . . . . . 82
4.3.3 SERS Sensing of Food Colourants. . . . . . . . . . . . . . . . . 84
4.4 SERS Identification of Biowarfare Agent Anthrax . . . . . . . . . . . 86
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5 Biomolecular SERS Applications. . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.1 SERS Biomolecular Detection Schemes . . . . . . . . . . . . . . . . . . 93
5.2 Nucleic Acids (NAs) and Their Components . . . . . . . . . . . . . . . 95
5.2.1 Intrinsic Detection of NAs . . . . . . . . . . . . . . . . . . . . . . 96
5.2.2 Intrinsic NA Detection Using Hybridization . . . . . . . . . . 98
5.2.3 Intrinsic NA Detection Using TERS. . . . . . . . . . . . . . . . 100
5.2.4 Extrinsic Detection of NAs. . . . . . . . . . . . . . . . . . . . . . 100
5.2.5 Extrinsic NA Detection Using Hybridization. . . . . . . . . . 102
5.3 Proteins and Their Components . . . . . . . . . . . . . . . . . . . . . . . . 104
5.3.1 Intrinsic Detection of Proteins. . . . . . . . . . . . . . . . . . . . 104
5.3.2 Extrinsic Detection of Proteins. . . . . . . . . . . . . . . . . . . . 108
5.3.3 Immunoassays. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.4 Lipids and Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
6 SERS Investigations of Cells, Viruses and Microorganisms. . . . . . . 127
6.1 Intracellular SERS Investigations . . . . . . . . . . . . . . . . . . . . . . . 127
6.1.1 Intracellular SERS Detection Strategies. . . . . . . . . . . . . . 127
6.1.2 Delivery of the Metallic NPs Inside the Cells . . . . . . . . . 129
6.1.3 Chemical Probing in Cells by Intrinsic SERS Spectra. . . . 131
6.1.4 Chemical Probing in Cells Using SERS Tags
with RRMs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
6.1.5 Endosomal pH Monitored by SERS. . . . . . . . . . . . . . . . 137
6.1.6 Intracellular SERS Using Tip-like Substrates. . . . . . . . . . 139
6.1.7 Experimental Aspects of Intracellular SERS Studies. . . . . 140
6.2 Detection and Identification of Viruses and Microorganisms . . . . 141
6.2.1 Detection and Identification of Viruses. . . . . . . . . . . . . . 141