Preface

Chapter 6 **SERS Research Applied to Polymer Based Nanocomposites 91** Sara Fateixa, Helena I.S. Nogueira and Tito Trindade

Chapter 7 **SERS-Based Sensitive Detection of Organophosphorus**

Qian Zhao, Guangqiang Liu and Weiping Cai

Chapter 8 **Raman Spectroscopy of Graphitic Nanomaterials 155**

Chapter 10 **Surface-Enhanced Raman Spectroscopy Characterization of Pristine and Functionalized Carbon Nanotubes and**

**Section 4 Raman Spectroscopy of Ferrite Nanomaterials 221**

Chapter 11 **Raman Spectroscopy in Zinc Ferrites Nanoparticles 223**

Chapter 12 **Structural Transformations in Ferroelectrics Discovered by**

**Section 5 Raman Spectroscopy Applied to Biomedical Sciences 273**

Chapter 13 **Raman Spectroscopy Applied to Health Sciences 275** Alexandra Nunes and Sandra Magalhães

Chapter 14 **Raman Spectroscopy for In Vivo Medical Diagnosis 293**

Miguel Ghebré Ramírez-Elías and Francisco Javier González

**Raman Spectroscopy 253**

Chapter 9 **Graphene Nanocomposites Studied by Raman**

Elena Iuliana Bîru and Horia Iovu

**Section 3 SERS and Raman Spectroscopy: Carbon Nanomaterials 153**

Daniel Casimir, Iman Ahmed, Raul Garcia-Sanchez, Prabhakar Misra

Sabina Botti, Alessandro Rufoloni, Tomas Rindzevicius and Michael

Pietro Galinetto, Benedetta Albini, Marcella Bini and Maria Cristina

Kai Jiang, Liping Xu, Jinzhong Zhang, Zhigao Hu and Junhao Chu

**Nerve Agents 127**

**VI** Contents

and Fabiola Diaz

**Spectroscopy 179**

**Graphene 203**

Stenbæk Schmidt

Mozzati

This book brings some examples of the state-of-the-art applications of Raman spectroscopy in characterization of materials and biomaterials, mainly through intensification processes, such as resonance Raman (RR) and Surface-enhanced Raman spectroscopy (SERS). The main goal of this book is to open up to an extended audience the wide possibilities of appli‐ cations of Raman spectroscopy for academic, industrial, biomedical, and environmental pur‐ poses. All authors and editors try to use fluent language in order to make the reading possible for a non-specialized public. In fact, this collective work will be beneficial to stu‐ dents, teachers, and researchers of many areas who are interested to expand their knowl‐ edge about Raman spectroscopy applied to nanotechnology, biotechnology, environmental science, inorganic chemistry, in situ and in vivo detection, and health sciences.

This book is organized starting from an introductory chapter that discusses basic aspects of conventional Raman Spectroscopy and also the special cases where the Raman scattering signal can be strongly amplified. Many examples are exploited. The book is organized in five main sections: (i) Introduction, (ii) Surface-Enhanced Raman Spectroscopy: Nanosub‐ strates and Applications, (iii) SERS and Raman Spectroscopy: Carbon Nanomaterials, (iv) Raman Spectroscopy of Ferrite Nanomaterials, and (v) Raman Spectroscopy Applied to Bio‐ medical Sciences.

The second section (ii) has three chapters that focus on preparation of highly sensible nano‐ materials to be used as efficient and reliable platforms for SERS measurements: (a) In the first chapter, the authors (M. Chirumamilla et al.) studied the synthesis and characterization of three-dimensional (3D) nanostructures with multiple branches (MB) as SERS substrates with breakthrough performances in hotspot-mediated ultra-sensitive detection; (b) in the follow‐ ing chapter (Marcin Pisarek et al.), the results of recent investigations into TiO2 nanotubular oxide layers on Ti metal loaded with Ag nanoparticles are investigated. The efficiency of these materials is discussed as surface plasmon resonators for precise surface analytical investiga‐ tions of numerous types of organic molecules at concentrations as low as, e.g., 10-9 M, and (c) finally, the synthesis of precisely controllable anisotropic noble metal nanoparticles (NPs) is reviewed (M. Xu and J. Zhang). This review has demonstrated the correlation of the key mor‐ phological parameters to achieve the strong E-field and ultra-sensitive SERS detection.

In fact, the SERS effect and also surface chemistry in general can be studied at molecular level when the conventional Raman system is joined to a scanning tunneling microscope (STM); in this case, the technique is appropriately named Tip-enhanced Raman spectroscopy (TERS-STM). The origin of the chemical enhancement has been the subject of much debate over the years. In this chapter (I. Rzeznicka and H. Horino), the effects of adsorption state of a molecule and its orientation over Raman signal are studied from the standpoint of surface

chemistry at the nanoscale. In addition, two chapters deal with special applications of SERS technique: (a) the recent research on the development of SERS substrates based on polymer nanocomposites and their applications in different fields is reviewed (S. Fateixa et al.). In addition, the joint use of Raman imaging and SERS in nanocomposite development is dis‐ cussed, and (b) the detection of organophosphorus molecules (W. Cai et al.) is the main fo‐ cus of the last chapter; the authors showed a route that could be suitable for detection of some organophosphorus nerve agents and other molecules weakly interacted with the coin metal substrates by choosing the appropriate modifiers.

Nogueira, Horia Iovu, Iman Ahmed, Izabela Rzeznicka, Jan Krajczewski, Jiatao Zhang, Jinz‐ hong Zhang, Junhao Chu, Kai Jiang, Kjeld Pedersen, Liping Xu, Manohar Chirumamilla, Marcella Bini, Marcin Holdyński, Marcin Pisarek, Maria Cristina Mozzati, Maria Janik-Cza‐ chor, Meng Xu, Michael Stenbæk Schmidt, Miguel Ghebré Ramírez-Elías, Mirosław Krawc‐ zyk, Peter Kjær Kristensen, Pietro Galinetto, Prabhakar Misra, Qian Zhao, Raul Garcia-Sanchez, Remo Proietti Zaccaria, Roman Krahne, Sabina Botti, Sandra Magalhães, Sergey I. Bozhevolnyi, S. Fateixa, Tomas Rindzevicius, Tomasz Płociński, T. Trindade, Weiping Cai, and Zhigao Hu. Special thanks go to Ms. Marina Dusevic for supporting and assisting with

> **Gustavo Morari do Nascimento** Federal University of ABC Santo André, Brazil

Preface IX

the book edition.

The third section (iii) brings chapters that used conventional Raman spectroscopy and SERS in the study of different carbon allotropes. The versatility of Raman spectroscopy is illustrat‐ ed in the characterization of single (SWNT) and multi-walled (MWNT) carbon nanotubes, few layers of graphene, and its functionalized forms, with an emphasis on gas-sensing appli‐ cations (P. Misra et al.). The characteristic features in Raman spectra of carbon allotropes are exposed, and the D and G band intensities are deeply investigated. In particular, one chapter is devoted to graphene and different types of graphene oxide and its nanocomposites (E.I. Bîru and H. Iovu). The last chapter (S. Botti and A. Rufoloni) in this section brings new results in the SERS studies of carbon nanotubes and graphene at pristine and also modified condi‐ tions. These materials can amplify the SERS signal mainly by chemical mechanism.

The fourth section (iv) brings two chapters that use Raman spectroscopy as a powerful tool for characterization of some important materials, such as ferrite nanoparticles and ferroelec‐ tric oxides. The first chapter gives a broad overview (P. Galinetto et al.) of the Raman spec‐ troscopy results in the characterization of ZnFe2O4 nanoparticles. The sensitivity of the Raman signal to probe cation disorder favored the appearance of several detailed works on a rich variety of nanosized zinc ferrites. An overview on the experimental results is reported and discussed at variance with synthesis methods, grain dimensions, and dopants. The sec‐ ond chapter systematically studies the structure of ferroelectric oxides and rare-earth ele‐ ment-doped ferroelectric materials (Junhao Chu et al.). Structural transformations that alter the crystal symmetry often have a significant effect on the Raman signal. The Curie tempera‐ ture (TC), distortion degree, and phase structure of the ferroelectric materials have been monitored by temperature-dependent Raman spectroscopy.

The last section (v) is composed of two chapters dedicated to special applications of Raman spectroscopy in biomedical area. The use of Raman spectroscopy as a tool for biochemical investigation is the main focus of the first chapter in this section (A. Nunes and S. Magal‐ hães). Raman spectroscopy, mainly SERS, was already applied to successfully diagnose sev‐ eral types of cancer and infections, and preliminary results are also promising in the context of Alzheimer's disease. The success of Raman spectroscopy in biomedical applications is based on the fact that the molecular composition of healthy tissue is different from diseased tissue; also several disease biomarkers can be identified in Raman spectra, which can be used to diagnose or monitor the progress of certain medical conditions (M. G. R-Elías and F. J. González). This chapter outlines an overview of the use of Raman spectroscopy for in vivo medical diagnostics and demonstrates the potential of this technique to address biomedical issues related to human health.Finally, I would like to give special thanks to all authors that contributed for this book (in alphabetical order): Alessandro Rufoloni, Alexander S. Roberts, Alexandra Nunes, Andrea Cerea, Andrea Toma, Andrzej Kudelski, Anisha Chirumamilla, Benedetta Albini, Daniel Casimir, Duncan S. Sutherland, Elena Iuliana Bîru, Esben Skovsen, Francesco De Angelis, Francisco Javier González, Guangqiang Liu, Hideyuki Horino, H.I.S.

Nogueira, Horia Iovu, Iman Ahmed, Izabela Rzeznicka, Jan Krajczewski, Jiatao Zhang, Jinz‐ hong Zhang, Junhao Chu, Kai Jiang, Kjeld Pedersen, Liping Xu, Manohar Chirumamilla, Marcella Bini, Marcin Holdyński, Marcin Pisarek, Maria Cristina Mozzati, Maria Janik-Cza‐ chor, Meng Xu, Michael Stenbæk Schmidt, Miguel Ghebré Ramírez-Elías, Mirosław Krawc‐ zyk, Peter Kjær Kristensen, Pietro Galinetto, Prabhakar Misra, Qian Zhao, Raul Garcia-Sanchez, Remo Proietti Zaccaria, Roman Krahne, Sabina Botti, Sandra Magalhães, Sergey I. Bozhevolnyi, S. Fateixa, Tomas Rindzevicius, Tomasz Płociński, T. Trindade, Weiping Cai, and Zhigao Hu. Special thanks go to Ms. Marina Dusevic for supporting and assisting with the book edition.

chemistry at the nanoscale. In addition, two chapters deal with special applications of SERS technique: (a) the recent research on the development of SERS substrates based on polymer nanocomposites and their applications in different fields is reviewed (S. Fateixa et al.). In addition, the joint use of Raman imaging and SERS in nanocomposite development is dis‐ cussed, and (b) the detection of organophosphorus molecules (W. Cai et al.) is the main fo‐ cus of the last chapter; the authors showed a route that could be suitable for detection of some organophosphorus nerve agents and other molecules weakly interacted with the coin

The third section (iii) brings chapters that used conventional Raman spectroscopy and SERS in the study of different carbon allotropes. The versatility of Raman spectroscopy is illustrat‐ ed in the characterization of single (SWNT) and multi-walled (MWNT) carbon nanotubes, few layers of graphene, and its functionalized forms, with an emphasis on gas-sensing appli‐ cations (P. Misra et al.). The characteristic features in Raman spectra of carbon allotropes are exposed, and the D and G band intensities are deeply investigated. In particular, one chapter is devoted to graphene and different types of graphene oxide and its nanocomposites (E.I. Bîru and H. Iovu). The last chapter (S. Botti and A. Rufoloni) in this section brings new results in the SERS studies of carbon nanotubes and graphene at pristine and also modified condi‐

The fourth section (iv) brings two chapters that use Raman spectroscopy as a powerful tool for characterization of some important materials, such as ferrite nanoparticles and ferroelec‐ tric oxides. The first chapter gives a broad overview (P. Galinetto et al.) of the Raman spec‐ troscopy results in the characterization of ZnFe2O4 nanoparticles. The sensitivity of the Raman signal to probe cation disorder favored the appearance of several detailed works on a rich variety of nanosized zinc ferrites. An overview on the experimental results is reported and discussed at variance with synthesis methods, grain dimensions, and dopants. The sec‐ ond chapter systematically studies the structure of ferroelectric oxides and rare-earth ele‐ ment-doped ferroelectric materials (Junhao Chu et al.). Structural transformations that alter the crystal symmetry often have a significant effect on the Raman signal. The Curie tempera‐ ture (TC), distortion degree, and phase structure of the ferroelectric materials have been

The last section (v) is composed of two chapters dedicated to special applications of Raman spectroscopy in biomedical area. The use of Raman spectroscopy as a tool for biochemical investigation is the main focus of the first chapter in this section (A. Nunes and S. Magal‐ hães). Raman spectroscopy, mainly SERS, was already applied to successfully diagnose sev‐ eral types of cancer and infections, and preliminary results are also promising in the context of Alzheimer's disease. The success of Raman spectroscopy in biomedical applications is based on the fact that the molecular composition of healthy tissue is different from diseased tissue; also several disease biomarkers can be identified in Raman spectra, which can be used to diagnose or monitor the progress of certain medical conditions (M. G. R-Elías and F. J. González). This chapter outlines an overview of the use of Raman spectroscopy for in vivo medical diagnostics and demonstrates the potential of this technique to address biomedical issues related to human health.Finally, I would like to give special thanks to all authors that contributed for this book (in alphabetical order): Alessandro Rufoloni, Alexander S. Roberts, Alexandra Nunes, Andrea Cerea, Andrea Toma, Andrzej Kudelski, Anisha Chirumamilla, Benedetta Albini, Daniel Casimir, Duncan S. Sutherland, Elena Iuliana Bîru, Esben Skovsen, Francesco De Angelis, Francisco Javier González, Guangqiang Liu, Hideyuki Horino, H.I.S.

tions. These materials can amplify the SERS signal mainly by chemical mechanism.

metal substrates by choosing the appropriate modifiers.

VIII Preface

monitored by temperature-dependent Raman spectroscopy.

#### **Gustavo Morari do Nascimento**

Federal University of ABC Santo André, Brazil

**Section 1**

**Introduction**

**Section 1**
