Table of Contents
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FOREWORD
PREFACE
State of the Art: Raman Vibrational Spectroscopy and Surface Enhanced Raman Spectroscopy
Abstract
1.1. INTRODUCTION RAMAN VIBRATIONAL SPECTROSCOPY
1.1.1. History
1.1.2. Basic Theory
1.1.3. Raman Active Vibrations
1.1.4. Rule of Mutual Exclusion
1.1.5. Raman Spectrometer Instrumentation
1.1.6. Raman Spectrum
1.1.7. Applications of Raman Spectroscopy
1.1.7.1. Chemical Analysis
1.1.7.2. Solid State Physics
1.1.7.3. Nanotechnology
1.1.7.4. Bio-pharmaceutical Industry
1.1.7.5. Study of Historical Painting and Documents
1.1.7.6. Explosives
1.1.7.7. Sensing Based on Raman Spectroscopy
1.2. SURFACE-ENHANCED RAMAN SCATTERING (SERS)
1.2.1. Short History
1.2.2. SERS Mechanism
1.2.3. SERS Technique
1.2.4. SERS Substrates
1.2.5. Applications of SERS
1.2.5.1. Biomarkers
1.2.5.2. Toxic Chemical and Chemical Warfare Agents
1.2.5.3. Narcotic and Doping Drugs
1.2.5.4. Food Monitoring
1.2.5.5. Verification and Authentication of Luxury Goods and Currency
1.3. SURFACE ENHANCED RESONANCE RAMAN SPECTROSCOPY (SERRS)
1.3.1. Advantages of SERRS Over SERS
CONCLUSION
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Enhancement Mechanisms and Theory of SERS
Abstract
2.1. INTRODUCTION
2.1.1. Introduction to SERS
2.2. ENHANCEMENT MECHANISMS
2.2.1. Electromagnetic Mechanism (EM)
2.2.1.1. Localized Surface Plasmon Resonance (LSPR)
2.2.2. Chemical Mechanism (CHEM)
2.2.3. Electronic Mechanism
2.3. ENHANCEMENT FACTORS
2.4. E4 ENHANCEMENT
2.5. FACTORS AFFECTING ENHANCEMENT FACTOR
2.5.1. SERS Substrate
2.5.2. Wavelength Dependence
2.5.3. Distance Dependence
2.5.4. Dependence on the Size and Shape of the Nanoparticles
2.6. TWO-PHOTON EXCITED SERS
2.7. SINGLE MOLECULE DETECTION USING SERS
2.8. HOT SPOTS
2.8.1. Generations of Hot Spots
CONCLUSION
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Plasmonic and Non-plasmonic Resonance Materials in SERS
Abstract
3.1. INTRODUCTION
3.2. RAMAN REPORTER MOLECULES (RRM)
3.3. MATERIALS USED IN SERS
3.3.1. Plasmonic SERS Nanomaterials
3.3.2. Non-plasmonic SERS Materials
3.4. Solid SERS Substrates
CONCLUDING REMARKS
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Application of Raman Spectroscopy in Amyloid Research
Abstract
4.1. INTRODUCTION
4.1.1. Basics of Raman Spectroscopy
4.1.2. Raman Spectra of Proteins and Peptides
4.1.3. Raman Techniques in Bio-Analysis
4.2. AMYLOID PROTEIN AGGREGATES AND THEIR RAMAN SIGNATURE
4.2.1. Amyloid Protein Aggregates
4.2.2. Raman Signature of Amyloid Aggregates of Human Proteins
4.2.3. Raman Features of Protein Aggregates Produced by Lysozyme
4.2.4. An Estimation of Protein Secondary Structure by Amide I Band Analysis
4.2.5. Amyloid Fibril Formation Mechanism by Raman Analysis
CONCLUSION AND PERSPECTIVES
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Surface-Enhanced Raman Scattering Based Rapid Pathogen Detection
Abstract
5.1. INTRODUCTION
5.2. APPLICATIONS OF SERS
5.3. SERS BASED DETECTION OF VARIOUS BIOMOLECULES
5.3.1. Nucleotides and Nucleic Acids
5.3.2. Amino Acids and Peptides/Proteins
5.4. APPLICATIONS OF SERS IN PATHOGEN DETECTION
5.5. RAMAN SPECTROSCOPY BASED DETECTION FOR COVID-19 TESTING
5.6. LIMITATION OF SERS TECHNIQUE IN PATHOGEN DETECTION AND FUTURE TREND
CONCLUSIONS
CONSENT FOR PUBLICATION
CONFLICT OF NTEREST
ACKNOWLEDGEMENTS
REFERENCES
From Cells to Clinic - Direct Biomolecule Quantification of Clinically Relevant Biomolecules
Abstract
6.1. INTRODUCTION
6.2. DIAGNOSTIC SERS: KEY FEATURES AND ADVANTAGES
6.3. NEUROLOGICAL DISEASES
6.3.1. General Features
6.3.2. Detection of Neurotransmitters by SERS
6.3.3. New Technique: Surface Enhanced Spatially Offset Raman Spectroscopy (SESORS)
6.4. DIABETES-GLUCOSE MONITORING
6.4.1. The Rising Phenomenon Called Diabetes
6.4.2. Continuous Glucose Monitoring
6.4.3. Development of SERS Sensors for CGM
6.5. DISCREET CELLULAR MOLECULES AND CELLULAR MICROENVIRONMENT
6.6. MEDICAL IMAGING THROUGH SERS
CONCLUDING REMARKS
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Smartphone Based Biosensors on Lateral Flow Assay Coupled to SERS: Point-of-Care Applications
Abstract
7.1. INTRODUCTION
7.1.1. What is POC Procedure
7.1.2. Recent POC Technologies
7.1.3. Biosensors
7.1.4. Smartphone-Based Biosensors
7.1.5. Challenges of Accepting POC in Emergency Department
7.1.6. Influence of POC on Clinical Results in the Emergency Department
7.1.7. Essential Features of POC Procedures
7.1.8. Surface Enhanced Raman Spectroscopy (SERS) and its Possible Advantages
7.1.9. Type of Substrates
7.1.10. What is it Used For
7.1.11. Usual SERS Investigational System
7.1.12. The Role of Surface Plasmons and Nanostructures
7.2. SERS BASED DNA AND PROTEIN DETERMINATIONS
7.3. DETERMINATION OF OTHER BIOLOGICALLY RELATED NANOPARTICLES
CONCLUSIONS
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Surface Enhanced Raman Spectroscopy- Bottlenecks and Improvement Strategies
Abstract
8.1. INTRODUCTION
8.1.1. Research
8.1.2. Commercialization
8.2. IMPROVEMENT STRATEGIES
8.2.1. Tip enhanced Raman Spectroscopy
8.2.2. Shell Isolated Nanoparticle-enhanced Raman Spectroscopy
8.2.3. Interference Enhanced Raman Spectroscopy (IERS)
8.2.4. Approach Based on Combinations and Spatio-temporal Resolution by Nanostructures
8.2.5. Improved Nanofabrication
8.2.5.1. Label Method
8.2.5.2. Label-free Method
8.2.6. Molecular Generality or Selectivity/Specificity Based Improvement Strategies
8.2.6.1. Reaction-SERS Method
8.2.6.2. Antibody-SERS Method
8.2.6.3. Aptamer-SERS Method
8.2.6.4. MIPs-SERS
8.2.6.5. Microfluidics-SERS
8.2.7. Collaborative Experimental and Theoretical Approaches
8.3. DEVELOPMENT IN INSTRUMENTATION
8.4. HANDHELD PORTABLE DEVICES
CONCLUSION
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Surface Enhanced Raman Spectroscopy: Biosensing and
Diagnostic Technique for Healthcare Applications
Edited by
Swati Jain
Amity Institute of Nanotechnology, Amity University,
Noida, UP,
India
&
Sruti Chattopadhyay
Center for Biomedical Engineering, Indian Institute of Technology Delhi
New Delhi,
India
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FOREWORD
“The fundamental importance of the subject of molecular diffraction came first to be recognized through the theoretical work of the late Lord Rayleigh on the blue light of the sky, which he showed to be the result of the scattering of sunlight by the gases of the atmosphere.” CV Raman.
“…the highly interesting result that the colour of sunlight scattered in a highly purified sample of glycerine was a brilliant green instead of the usual blue.”
Sir CV Raman
The quest to find the unknown drives scientists working in all possible conditions to unravel the mystery created through the fusion of natural phenomena. Sir Chandrasekhara Venkata Raman’s path breaking discovery and its theoretical prediction conceptualized into a spectroscopic technique impertinently used in the chemical world. Raman spectroscopy is like panning for gold. A wealth of information is there if you can just sift through the rock, dirt, and sand obscuring it. In the 1970’s, another astounding revelation was made about light scattering. Experiments conducted by Fleischmann from University of Southampton led to a chance discovery of SERS phenomenon where the unexpected rise in Raman signals was reported when the sample of interest was added onto silver metallic particles. This phenomenon was later explained and detailed by Prof. Richard Van Duyne whois credited with the discovery of SERS technique – explanation of magnificent rise of Raman signals, postulation of enhancement factor - electromagnetic theory for SERS and its eventual applications in analytical and bioanalytical chemistry. Over the years, the perspective in SERS has dramatically changed owing to highly advanced synthetic methods developed for the preparation of novel nanomaterials, which become the bed for the creation of ‘hot-spot’ suitable for signal enhancement. Thus, SERS has gained equitable momentum in the biological world as chemical analysis, where the possibility of single molecule detection has been proposed.
This e-book is intended as a nodal point for budding researchers, senior academicians and scientists who will gain a different perspective in the field of SERS based biosensing. It gave me immense pleasure when Dr. Swati and Dr. Sruti approached me for writing the foreword of this book as this book intends to bridge the fissure between physical and biological aspects of SERS and thus is easily readable for people from different scientific backgrounds. This book feature ‘updated and recent’, details on colloids and nanostructures, their fabrication, surface engineering and immobilization methods, all in context to SERS based biosensing.
The framework of the book is in the order of hierarchy with different sections devoted for each subject in the SERS technique. Each section comprising of 1-2 chapters, is designed to move from basic concepts of technique towards its real biological applications. The preface sets the stage, which duals as introductory chapter moves to chapter 1 about Raman vibrational spectroscopy technique authored by Dr. Mittal, who has long experience with the technique and its chemical analysis. This chapter also introduces SERS to readers. The second chapter is devoted to the theoretical understanding of SERS and enhancement factors. The creation of hot-spots and two-photon excited SERS are also explained in this chapter. Section B begins with 3rd chapter highlighting the role of novel nanoarchitecture materials, plasmonic and non-plasmonic nanomaterials and progression in nanofabrication procedures for the development of nanomaterials written in detail by Dr. Ranu Nayak. Proceeding chapters included in section C include biomedical and biosensing applications of SERS. In the first chapter of the section, consecrated efforts are directed to illustrate the significance of SERS for amyloid research by Dr. Nakul Maity. Amyloids have become ubiquitous in understanding disease pathogenesis and hence are quite useful for understanding disease and therapeutic interventions. The proceeding chapters orient the readers toward SERS biosensing of pathogens and other clinically relevant biomolecules for real applicability of the technique in healthcare settings as detailed in Chapters 5 and 6. This section concludes with the design of smartphone biosensors with SERS technique for point of care testing devices. Last section D of the e-book elucidates problems encountered by researchers in academia and companies working towards realising SERS technique for making commercially feasible tools. It also details improvising strategies such as tip enhanced, interference enhanced (TIRS); shell isolated nanoparticle-enhanced (SINRS) and spatially offset Raman spectroscopy (SORS) by authors hailing from both academic institutes and companies.
I hope this book stimulates thought and presents engaging rationale of SERS and its multiple diverse applications primarily in the biological system. The e-Book has the potential to channelize a deeper understanding of basic science as well as its applications in analysis and sensing, in nano sciences, surface chemistry, as a biological probe as well as in daughter disciplines such as plasmonics and near-field optics.
Dr. Surender M. Kharbanda
Department of Adult Oncology,
Dana Farber Cancer Institute
Harvard Medical School
Boston, MA 02115, USA
Scientific Founder, President &
Chief Scientific Officer
Genus Oncology LLC
Boston, MA 02118, USA
PREFACE
Swati JainSruti Chattopadhyay
Amity Institute of Nanotechnology
Amity University, Noida, UP, India
Center for Biomedical Engineering
IIT Delhi, Hauz Khas, New Delhi, India
Million-fold enhancement of characteristic Raman signal of molecules presented as a monolayer on the surface of rough nanostructured metals refuelled the interest in Raman spectroscopy which initially was reserved for pure sample analysis. The amplification in signal now referred to as surface enhanced Raman spectroscopy (SERS) has been explored for numerous applications in physical, analytical, chemical, material, surface/topographical and biomedical sciences. The aim of this book is to comprehensively understand the concept of biological applications using SERS technique for sensing and imaging various analytes in in-vitro as well as in-vivo conditions.
Individual bonds in molecules give rise to unique vibrations by inelastic scattering resulting in molecularly specific spectra, namely Raman spectra. These inherently weak signals were later on developed by researchers into highly intense peaks using metallic nanostructures and this SERS phenomenon gained popularity, particularly in healthcare and medical applications. SERS offers high sensitivity, fingerprint analysis, optimization towards near infra-red signal, minimization of photo-bleaching and photo-degradation.
Nowadays, dramatic emphasis is devoted towards rapid and sensitive detection methodologies as well as gaining insight into molecular dynamics in in-vivo conditions through imaging. SERS based nanomaterials and devices, including novel plasmonic and non-plasmonic nanostructures and the development of stable Raman Reporter Molecules (RRMs) have propelled amended signalling attributes in SERS biosensing and diagnostic procedures. The instrument design has also changed focus towards SERS hand-held devices, smart phone integration and point-care-devices applicable in remote and intermittent sensing of target analytes.
Clearly, the time for a book is appropriate that summarizes basic notions and trends about thinking of SERS as a device for bioanalytical and biosensing tool defining what we know and understanding the deficiency in the technique in a way to harness this understanding into opportunities for the betterment of SERS and its biological applications. This is our ambition for assembling this e-book. International researchers in their respective sub-fields of SERS have contributed to this book. Their diverse background and training ranging from physics to inorganic chemistry to biomedical engineering, in my opinion, directly reflects the justification towards the multidisciplinary nature of SERS and its biological applications. The e-book is intended as a reference book for researchers and academicians working in SERS. It will also provide comprehensive concepts to newcomers starting to work in this field irrespective of their background in a simple manner.
Updated and recent analysis of materials and processes are detailed, all in context with SERS spectroscopy and its applicability in biomedical and healthcare fields. The book is planned in a hierarchical scale with discussions on theoretical beginnings of Raman and SERS spectroscopy moving towards chemical structures in SERS. Hence, the selection of topics covered in the preceding 8 chapters is highly subjective. The e-book is categorically differentiated into specific sections, each containing chapters catering to various aspects of SERS technique and biosensing applications. The sections move from basic physics of Raman spectroscopy and SERS towards plasmonic colloids and rough metal nanostructures, highlighting their synthesis as well as advancement in nano-assemblies. This includes active nanomaterials and nanodevices, including plasmonic and non-plasmonic nanostructures as well as Raman Reporter Molecules (RRMs). The largest section is, however, reserved for biosensing and diagnostic applications of SERS in biology and medicine. We have also put efforts towards understanding the concept of SERS for ultimately gaining perspective in developing an improvised biosensing system in a clinical setting. The book covers all, from basic knowledge to new exciting research and development in the field of SERS and its application for biosensing, diagnostics and imaging techniques.
Lastly, this book also summarizes lacunae of SERS technique, highlighting the need for optimization of signal acquisition parameters to prepare commercially viable and field deployable instruments. Remedial measures adopted for developing biosensing methodologies are also discussed with improved versions of SERS coming to the fore.
We cordially thank all our authors for their hard work and commitment to this book that they have invested in, writing highly relevant as well as excellent chapters. This international project would not have been possible without their efforts and dedication. We thank Ms. Humaira Hashmi at Bentham Publications, who suggested initiating this project to edit this SERS based e-Book. Finally, Dr. Swati Jain and Dr. Sruti are extremely thankful and grateful to their families for the continual support and motivation. We have tremendous faith that this e-book has the potential to stimulate thought processes leading to in-depth understanding of SERS so as to fully exploit this technique in innumerable biological applications.
Swati Jain
Amity Institute of Nanotechnology
Amity University
Noida, UP
India
Department of Science & Technology
Technology Bhawan
New Mehrauli Road
New Delhi, IndiaSruti Chattopadhyay
Center for Biomedical Engineering
Indian Institute of Technology Delhi
New Delhi, India
State of the Art: Raman Vibrational Spectroscopy and Surface Enhanced Raman Spectroscopy
Jagjiwan Mittal1,*,Robin Kumar1
1 Amity Institute of Nanotechnology, Amity University, Sector125, Noida, Uttar Pradesh 201313, India
Abstract
Raman spectroscopy depends on inelastic scattering of photons, known as Raman scattering. It uses monochromatic light using a laser and determines vibrational modes of molecules. This technique is commonly used for the identification of molecules by providing its structural fingerprint. Due to very low inelastic scattering, however, signals obtained by Raman spectroscopy are inherently weak and the problem is more with visible light. These weak Raman signals can be used by amplifying them by the method known as surface enhanced Raman spectroscopy (SERS). SERS is a powerful vibrational spectroscopy technique that allows for highly sensitive structural detection of low concentration analytes. The current chapter summarizes the basics of Raman spectroscopy and SERS, instrumentation, mechanisms differences and applications.
Keywords: Raman Scattering, SERS, Surface Enhanced Resonance Raman Spectroscopy SERRS, Vibrational Spectroscopy.
*Corresponding author Jagjiwan Mittal: Amity Institute of Nanotechnology, Amity University, Sector125, Noida, Uttar Pradesh 201313, India; Tel: +919899010491; E-mail:
[email protected]CONSENT FOR PUBLICATION
Not applicable.
CONFLICT OF INTEREST
The authors declare no conflict of interest, financial or otherwise.
ACKNOWLEDGEMENTS
Declared none.
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